WorldWideScience

Sample records for high mass-resolution ion

  1. High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

    CERN Document Server

    Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

    2001-01-01

    Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

  2. Ultra High-Mass Resolution Paper Spray by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Kevin D. Quinn

    2012-01-01

    Full Text Available Paper Spray Ionization is an atmospheric pressure ionization technique that utilizes an offline electro-osmotic flow to generate ions off a paper medium. This technique can be performed on a Bruker SolariX Fourier transform ion cyclotron resonance mass spectrometer by modifying the existing nanospray source. High-resolution paper spray spectra were obtained for both organic and biological samples to demonstrate the benefit of linking the technique with a high-resolution mass analyzer. Error values in the range 0.23 to 2.14 ppm were obtained for calf lung surfactant extract with broadband mass resolving power (m/Δm50% above 60,000 utilizing an external calibration standard.

  3. Electrostatic ion trap and Fourier transform measurements for high-resolution mass spectrometry

    International Nuclear Information System (INIS)

    Bhushan, K. G.; Gadkari, S. C.; Yakhmi, J. V.; Sahni, V. C.

    2007-01-01

    We report on the development of an electrostatic ion trap for high-resolution mass spectrometry. The trap works on purely electrostatic fields and hence trapping and storing of ions is not mass restrictive, unlike other techniques based on Penning, Paul, or radio frequency quadrupole ion traps. It allows simultaneous trapping and studying of multiple mass species over a large mass range. Mass spectra were recorded in ''dispersive'' and ''self-bunching'' modes of ions. Storage lifetimes of about 100 ms and mass resolving power of about 20 000 could be achieved from the fifth harmonic Fourier transform spectrum of Xe ions recorded in the self-bunching mode

  4. Ion optics of a high resolution multipassage mass spectrometer with electrostatic ion mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Sakurai, T [Osaka Univ. (Japan). Dept. of Physics; Baril, M [Departement de Physique, Faculte des Sciences et de Genie, Universite Laval, Ste-Foy, Quebec G1K 7P4 (Canada)

    1995-09-01

    Ion trajectories in an electrostatic ion mirror are calculated. The interferences of the extended fringing fields of the mirror with finite aperture are studied. The results of the calculations are represented by three transfer matrices, which describe ion trajectories under the effects of a fringing field at the entrances, of an idealized mirror region, and of a fringing field at the exit. The focusing effects and ion-optical properties of mass spectrometers with electrostatic ion mirrors can be evaluated by using these transfer matrices. A high performance multipassage mass spectrometer is designed. The system has one magnet and four electrostatic sector analyzers and two ion mirrors. The double focusing condition and stigmatic focusing condition are achieved in any passage of the system. The mass resolution increases linearly with the number of passages in a magnet. (orig.).

  5. A high-resolution mass spectrometer to measure atmospheric ion composition

    Directory of Open Access Journals (Sweden)

    H. Junninen

    2010-08-01

    Full Text Available In this paper we present recent achievements on developing and testing a tool to detect the composition of ambient ions in the mass/charge range up to 2000 Th. The instrument is an Atmospheric Pressure Interface Time-of-Flight Mass Spectrometer (APi-TOF, Tofwerk AG. Its mass accuracy is better than 0.002%, and the mass resolving power is 3000 Th/Th. In the data analysis, a new efficient Matlab based set of programs (tofTools were developed, tested and used. The APi-TOF was tested both in laboratory conditions and applied to outdoor air sampling in Helsinki at the SMEAR III station. Transmission efficiency calibrations showed a throughput of 0.1–0.5% in the range 100–1300 Th for positive ions, and linearity over 3 orders of magnitude in concentration was determined. In the laboratory tests the APi-TOF detected sulphuric acid-ammonia clusters in high concentration from a nebulised sample illustrating the potential of the instrument in revealing the role of sulphuric acid clusters in atmospheric new particle formation. The APi-TOF features a high enough accuracy, resolution and sensitivity for the determination of the composition of atmospheric small ions although the total concentration of those ions is typically only 400–2000 cm−3. The atmospheric ions were identified based on their exact masses, utilizing Kendrick analysis and correlograms as well as narrowing down the potential candidates based on their proton affinities as well isotopic patterns. In Helsinki during day-time the main negative ambient small ions were inorganic acids and their clusters. The positive ions were more complex, the main compounds were (polyalkyl pyridines and – amines. The APi-TOF provides a near universal interface for atmospheric pressure sampling, and this key feature will be utilized in future laboratory and field studies.

  6. Time‐of‐flight secondary ion mass spectrometry imaging of biological samples with delayed extraction for high mass and high spatial resolutions

    Science.gov (United States)

    Vanbellingen, Quentin P.; Elie, Nicolas; Eller, Michael J.; Della‐Negra, Serge; Touboul, David

    2015-01-01

    Rationale In Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS), pulsed and focused primary ion beams enable mass spectrometry imaging, a method which is particularly useful to map various small molecules such as lipids at the surface of biological samples. When using TOF‐SIMS instruments, the focusing modes of the primary ion beam delivered by liquid metal ion guns can provide either a mass resolution of several thousand or a sub‐µm lateral resolution, but the combination of both is generally not possible. Methods With a TOF‐SIMS setup, a delayed extraction applied to secondary ions has been studied extensively on rat cerebellum sections in order to compensate for the effect of long primary ion bunches. Results The use of a delayed extraction has been proven to be an efficient solution leading to unique features, i.e. a mass resolution up to 10000 at m/z 385.4 combined with a lateral resolution of about 400 nm. Simulations of ion trajectories confirm the experimental determination of optimal delayed extraction and allow understanding of the behavior of ions as a function of their mass‐to‐charge ratio. Conclusions Although the use of a delayed extraction has been well known for many years and is very popular in MALDI, it is much less used in TOF‐SIMS. Its full characterization now enables secondary ion images to be recorded in a single run with a submicron spatial resolution and with a mass resolution of several thousand. This improvement is very useful when analyzing lipids on tissue sections, or rare, precious, or very small size samples. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26395603

  7. High-Resolution Mass Spectrometers

    Science.gov (United States)

    Marshall, Alan G.; Hendrickson, Christopher L.

    2008-07-01

    Over the past decade, mass spectrometry has been revolutionized by access to instruments of increasingly high mass-resolving power. For small molecules up to ˜400 Da (e.g., drugs, metabolites, and various natural organic mixtures ranging from foods to petroleum), it is possible to determine elemental compositions (CcHhNnOoSsPp…) of thousands of chemical components simultaneously from accurate mass measurements (the same can be done up to 1000 Da if additional information is included). At higher mass, it becomes possible to identify proteins (including posttranslational modifications) from proteolytic peptides, as well as lipids, glycoconjugates, and other biological components. At even higher mass (˜100,000 Da or higher), it is possible to characterize posttranslational modifications of intact proteins and to map the binding surfaces of large biomolecule complexes. Here we review the principles and techniques of the highest-resolution analytical mass spectrometers (time-of-flight and Fourier transform ion cyclotron resonance and orbitrap mass analyzers) and describe some representative high-resolution applications.

  8. New approach to 3-D, high sensitivity, high mass resolution space plasma composition measurements

    International Nuclear Information System (INIS)

    McComas, D.J.; Nordholt, J.E.

    1990-01-01

    This paper describes a new type of 3-D space plasma composition analyzer. The design combines high sensitivity, high mass resolution measurements with somewhat lower mass resolution but even higher sensitivity measurements in a single compact and robust design. While the lower resolution plasma measurements are achieved using conventional straight-through time-of-flight mass spectrometry, the high mass resolution measurements are made by timing ions reflected in a linear electric field (LEF), where the restoring force that an ion experiences is proportional to the depth it travels into the LEF region. Consequently, the ion's equation of motion in that dimension is that of a simple harmonic oscillator and its travel time is simply proportional to the square root of the ion's mass/charge (m/q). While in an ideal LEF, the m/q resolution can be arbitrarily high, in a real device the resolution is limited by the field linearity which can be achieved. In this paper we describe how a nearly linear field can be produced and discuss how the design can be optimized for various different plasma regimes and spacecraft configurations

  9. Automated data processing of high-resolution mass spectra

    DEFF Research Database (Denmark)

    Hansen, Michael Adsetts Edberg; Smedsgaard, Jørn

    of the massive amounts of data. We present an automated data processing method to quantitatively compare large numbers of spectra from the analysis of complex mixtures, exploiting the full quality of high-resolution mass spectra. By projecting all detected ions - within defined intervals on both the time...... infusion of crude extracts into the source taking advantage of the high sensitivity, high mass resolution and accuracy and the limited fragmentation. Unfortunately, there has not been a comparable development in the data processing techniques to fully exploit gain in high resolution and accuracy...... infusion analyses of crude extract to find the relationship between species from several species terverticillate Penicillium, and also that the ions responsible for the segregation can be identified. Furthermore the process can automate the process of detecting unique species and unique metabolites....

  10. A fragmentation study of kaempferol using electrospray quadrupole time-of-flight mass spectrometry at high mass resolution

    Science.gov (United States)

    March, Raymond E.; Miao, Xiu-Sheng

    2004-02-01

    A mass spectrometric method based on the combined use of electrospray ionization, collision-induced dissociation and tandem mass spectrometry at high mass resolution has been applied to an investigation of the structural characterization of protonated and deprotonated kaempferol (3,5,7,4'-tetrahydroxyflavone). Low-energy product ion mass spectra of [M+H]+ ions showed simple fragmentations of the C ring that permitted characterization of the substituents in the A and B rings. In addition, four rearrangement reactions accompanied by losses of C2H2O, CHO[radical sign], CO, and H2O were observed. Low-energy product ion mass spectra of [M-H]- ions showed only four rearrangement reactions accompanied by losses of OH[radical sign], CO, CH2O, and C2H2O. The use of elevated cone voltages permitted observation of product ion mass spectra of selected primary and secondary fragment ions so that each fragment ion reported was observed as a direct product of its immediate precursor ion. Product ion mass spectra examined at high mass resolution allowed unambiguous determination of the elemental composition of fragment ions and resolution of two pairs of isobars. Fragmentation mechanisms and ion structures have been proposed.

  11. SIEMENS ADVANCED QUANTRA FTICR MASS SPECTROMETER FOR ULTRA HIGH RESOLUTION AT LOW MASS

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, W; Laura Tovo, L

    2008-07-08

    The Siemens Advanced Quantra Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometer was evaluated as an alternative instrument to large double focusing mass spectrometers for gas analysis. High resolution mass spectrometers capable of resolving the common mass isomers of the hydrogen isotopes are used to provide data for accurate loading of reservoirs and to monitor separation of tritium, deuterium, and helium. Conventional double focusing magnetic sector instruments have a resolution that is limited to about 5000. The Siemens FTICR instrument achieves resolution beyond 400,000 and could possibly resolve the tritium ion from the helium-3 ion, which differ by the weight of an electron, 0.00549 amu. Working with Y-12 and LANL, SRNL requested Siemens to modify their commercial Quantra system for low mass analysis. To achieve the required performance, Siemens had to increase the available waveform operating frequency from 5 MHz to 40 MHz and completely redesign the control electronics and software. However, they were able to use the previous ion trap, magnet, passive pump, and piezo-electric pulsed inlet valve design. NNSA invested $1M in this project and acquired four systems, two for Y-12 and one each for SRNL and LANL. Siemens claimed a $10M investment in the Quantra systems. The new Siemens Advanced Quantra demonstrated phenomenal resolution in the low mass range. Resolution greater than 400,000 was achieved for mass 2. The new spectrometer had a useful working mass range to 500 Daltons. However, experiments found that a continuous single scan from low mass to high was not possible. Two useful working ranges were established covering masses 1 to 6 and masses 12 to 500 for our studies. A compromise performance condition enabled masses 1 to 45 to be surveyed. The instrument was found to have a dynamic range of about three orders of magnitude and quantitative analysis is expected to be limited to around 5 percent without using complex fitting algorithms

  12. Food contaminant analysis at ultra-high mass resolution: application of hybrid linear ion trap - orbitrap mass spectrometry for the determination of the polyether toxins, azaspiracids, in shellfish.

    LENUS (Irish Health Repository)

    2010-10-30

    The biotoxins, azaspiracids (AZAs), from marine phytoplankton accumulate in shellfish and affect human health by causing severe gastrointestinal disturbance, diarrhea, nausea and vomiting. Specific and sensitive methods have been developed and validated for the determination of the most commonly occurring azaspiracid analogs. An LTQ Orbitrap mass spectrometer is a hybrid instrument that combines linear ion trap (LIT) mass spectrometry (MS) with high-resolution Fourier transform (FT) MS and this was exploited to perform simultaneous ultra-high-resolution full-scan MS analysis and collision-induced dissociation (CID) tandem mass spectrometry (MS\\/MS). Using the highest mass resolution setting (100,000 FWHM) in full-scan mode, the methodology was validated for the determination of six AZAs in mussel (Mytilus galloprovincialis) tissue extracts. Ultra-high mass resolution, together with a narrow mass tolerance window of ±2 mDa, dramatically improved detection sensitivity. In addition to employing chromatographic resolution to distinguish between the isomeric azaspiracid analogs, AZA1\\/AZA6 and AZA4\\/AZA5, higher energy collisionally induced dissociation (HCD) fragmentation on selected precursor ions were performed in parallel with full-scan FTMS. Using HCD MS\\/MS, most precursor and product ion masses were determined within 1 ppm of the theoretical m\\/z values throughout the mass spectral range and this enhanced the reliability of analyte identity.For the analysis of mussels (M. galloprovincialis), the method limit of quantitation (LOQ) was 0.010 µg\\/g using full-scan FTMS and this was comparable with the LOQ (0.007 µg\\/g) using CID MS\\/MS. The repeatability data were; intra-day RSD% (1.8-4.4%; n = 6) and inter-day RSD% (4.7-8.6%; n = 3). Application of these methods to the analysis of mussels (M. edulis) that were naturally contaminated with azaspiracids, using high-resolution full-scan Orbitrap MS and low-resolution CID MS\\/MS, produced

  13. Practical application of in silico fragmentation based residue screening with ion mobility high-resolution mass spectrometry.

    Science.gov (United States)

    Kaufmann, Anton; Butcher, Patrick; Maden, Kathry; Walker, Stephan; Widmer, Mirjam

    2017-07-15

    A screening concept for residues in complex matrices based on liquid chromatography coupled to ion mobility high-resolution mass spectrometry LC/IMS-HRMS is presented. The comprehensive four-dimensional data (chromatographic retention time, drift time, mass-to-charge and ion abundance) obtained in data-independent acquisition (DIA) mode was used for data mining. An in silico fragmenter utilizing a molecular structure database was used for suspect screening, instead of targeted screening with reference substances. The utilized data-independent acquisition mode relies on the MS E concept; where two constantly alternating HRMS scans (low and high fragmentation energy) are acquired. Peak deconvolution and drift time alignment of ions from the low (precursor ion) and high (product ion) energy scan result in relatively clean product ion spectra. A bond dissociation in silico fragmenter (MassFragment) supplied with mol files of compounds of interest was used to explain the observed product ions of each extracted candidate component (chromatographic peak). Two complex matrices (fish and bovine liver extract) were fortified with 98 veterinary drugs. Out of 98 screened compounds 94 could be detected with the in silico based screening approach. The high correlation among drift time and m/z value of equally charged ions was utilized for an orthogonal filtration (ranking). Such an orthogonal ion mobility based filter removes multiply charged ions (e.g. peptides and proteins from the matrix) as well as noise and artefacts. Most significantly, this filtration dramatically reduces false positive findings but hardly increases false negative findings. The proposed screening approach may offer new possibilities for applications where reference compounds are hardly or not at all commercially available. Such areas may be the analysis of metabolites of drugs, pyrrolizidine alkaloids, marine toxins, derivatives of sildenafil or novel designer drugs (new psychoactive substances

  14. Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

    Science.gov (United States)

    Kiss, András; Smith, Donald F; Jungmann, Julia H; Heeren, Ron M A

    2013-12-30

    Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high-speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with polyatomic primary ion sources, are required to exploit the full potential of microscope mode mass spectrometry imaging, i.e. to efficiently push the limits of ultra-high spatial resolution, sample throughput and sensitivity. In this work, a C60 primary source was combined with a commercial mass microscope for microscope mode secondary ion mass spectrometry imaging. The detector setup is a pixelated detector from the Medipix/Timepix family with high-voltage post-acceleration capabilities. The system's mass spectral and imaging performance is tested with various benchmark samples and thin tissue sections. The high secondary ion yield (with respect to 'traditional' monatomic primary ion sources) of the C60 primary ion source and the increased sensitivity of the high voltage detector setup improve microscope mode secondary ion mass spectrometry imaging. The analysis time and the signal-to-noise ratio are improved compared with other microscope mode imaging systems, all at high spatial resolution. We have demonstrated the unique capabilities of a C60 ion microscope with a Timepix detector for high spatial resolution microscope mode secondary ion mass spectrometry imaging. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Applicability of hybrid linear ion trap-high resolution mass spectrometry and quadrupole-linear ion trap-mass spectrometry for mycotoxin analysis in baby food.

    Science.gov (United States)

    Rubert, Josep; James, Kevin J; Mañes, Jordi; Soler, Carla

    2012-02-03

    Recent developments in mass spectrometers have created a paradoxical situation; different mass spectrometers are available, each of them with their specific strengths and drawbacks. Hybrid instruments try to unify several advantages in one instrument. In this study two of wide-used hybrid instruments were compared: hybrid quadrupole-linear ion trap-mass spectrometry (QTRAP®) and the hybrid linear ion trap-high resolution mass spectrometry (LTQ-Orbitrap®). Both instruments were applied to detect the presence of 18 selected mycotoxins in baby food. Analytical parameters were validated according to 2002/657/CE. Limits of quantification (LOQs) obtained by QTRAP® instrument ranged from 0.45 to 45 μg kg⁻¹ while lower limits of quantification (LLOQs) values were obtained by LTQ-Orbitrap®: 7-70 μg kg⁻¹. The correlation coefficients (r) in both cases were upper than 0.989. These values highlighted that both instruments were complementary for the analysis of mycotoxin in baby food; while QTRAP® reached best sensitivity and selectivity, LTQ-Orbitrap® allowed the identification of non-target and unknowns compounds. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. High-resolution high-sensitivity elemental imaging by secondary ion mass spectrometry: from traditional 2D and 3D imaging to correlative microscopy

    International Nuclear Information System (INIS)

    Wirtz, T; Philipp, P; Audinot, J-N; Dowsett, D; Eswara, S

    2015-01-01

    Secondary ion mass spectrometry (SIMS) constitutes an extremely sensitive technique for imaging surfaces in 2D and 3D. Apart from its excellent sensitivity and high lateral resolution (50 nm on state-of-the-art SIMS instruments), advantages of SIMS include high dynamic range and the ability to differentiate between isotopes. This paper first reviews the underlying principles of SIMS as well as the performance and applications of 2D and 3D SIMS elemental imaging. The prospects for further improving the capabilities of SIMS imaging are discussed. The lateral resolution in SIMS imaging when using the microprobe mode is limited by (i) the ion probe size, which is dependent on the brightness of the primary ion source, the quality of the optics of the primary ion column and the electric fields in the near sample region used to extract secondary ions; (ii) the sensitivity of the analysis as a reasonable secondary ion signal, which must be detected from very tiny voxel sizes and thus from a very limited number of sputtered atoms; and (iii) the physical dimensions of the collision cascade determining the origin of the sputtered ions with respect to the impact site of the incident primary ion probe. One interesting prospect is the use of SIMS-based correlative microscopy. In this approach SIMS is combined with various high-resolution microscopy techniques, so that elemental/chemical information at the highest sensitivity can be obtained with SIMS, while excellent spatial resolution is provided by overlaying the SIMS images with high-resolution images obtained by these microscopy techniques. Examples of this approach are given by presenting in situ combinations of SIMS with transmission electron microscopy (TEM), helium ion microscopy (HIM) and scanning probe microscopy (SPM). (paper)

  17. Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams.

    Science.gov (United States)

    Shon, Hyun Kyong; Yoon, Sohee; Moon, Jeong Hee; Lee, Tae Geol

    2016-06-09

    The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration.

  18. Depth resolution of secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Pustovit, A.N.

    2004-01-01

    The effect of the solid body discreteness in the direction of the normal to the sample surface on the depth resolution of the secondary ion mass spectrometry method is analyzed. It is shown that for this case the dependence of the width at the semi-height of the delta profiles of the studied elements depth distribution on the energy and angle of incidence of the initial ions should have the form of the stepwise function. This is experimentally proved by the silicon-germanium delta-layers in the silicon samples [ru

  19. Correlation of precursor and product ions in single-stage high resolution mass spectrometry. A tool for detecting diagnostic ions and improving the precursor elemental composition elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Borràs, S. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Kaufmann, A., E-mail: anton.kaufmann@klzh.ch [Official Food Control Authority, Fehrenstrasse 15, 8032 Zürich (Switzerland); Companyó, R. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)

    2013-04-15

    Highlights: ► We are describing a technique to spot ions which are derived from each other. ► Single stage high resolution data is used. ► This “in silicon” technique is compared to conventional precursor scan. ► Some applications for this technique are presented. -- Abstract: Monitoring of common diagnostic fragments is essential for recognizing molecules which are members of a particular compound class. Up to now, unit resolving tandem quadrupole mass spectrometers, operating in the precursor ion scan mode, have been typically used to perform such analysis. By means of high-resolution mass spectrometry (HRMS) a much more sensitive and selective detection can be achieved. However, using a single-stage HRMS instrument, there is no unequivocal link to the corresponding precursor ion, since such instrumentation does not permit a previous precursor selection. Thus, to address this limitation, an in silico approach to locate precursor ions, based on diagnostic fragments, was developed. Implemented as an Excel macro, the algorithm rapidly assembles and surveys exact mass data to provide a list of feasible precursor candidates according to the correlation of the chromatographic peak shape profile and other additional filtering criteria (e.g. neutral losses and isotopes). The macro was tested with two families of veterinary drugs, sulfonamides and penicillins, which are known to yield diagnostic product ions when fragmented. Data sets obtained from different food matrices (fish and liver), both at high and low concentration of the target compounds, were investigated in order to evaluate the capabilities and limitations of the reported approach. Finally, other possible applications of this technique, such as the elucidation of elemental compositions based on product ions and corresponding neutral losses, were also presented and discussed.

  20. Correlation of precursor and product ions in single-stage high resolution mass spectrometry. A tool for detecting diagnostic ions and improving the precursor elemental composition elucidation

    International Nuclear Information System (INIS)

    Borràs, S.; Kaufmann, A.; Companyó, R.

    2013-01-01

    Highlights: ► We are describing a technique to spot ions which are derived from each other. ► Single stage high resolution data is used. ► This “in silicon” technique is compared to conventional precursor scan. ► Some applications for this technique are presented. -- Abstract: Monitoring of common diagnostic fragments is essential for recognizing molecules which are members of a particular compound class. Up to now, unit resolving tandem quadrupole mass spectrometers, operating in the precursor ion scan mode, have been typically used to perform such analysis. By means of high-resolution mass spectrometry (HRMS) a much more sensitive and selective detection can be achieved. However, using a single-stage HRMS instrument, there is no unequivocal link to the corresponding precursor ion, since such instrumentation does not permit a previous precursor selection. Thus, to address this limitation, an in silico approach to locate precursor ions, based on diagnostic fragments, was developed. Implemented as an Excel macro, the algorithm rapidly assembles and surveys exact mass data to provide a list of feasible precursor candidates according to the correlation of the chromatographic peak shape profile and other additional filtering criteria (e.g. neutral losses and isotopes). The macro was tested with two families of veterinary drugs, sulfonamides and penicillins, which are known to yield diagnostic product ions when fragmented. Data sets obtained from different food matrices (fish and liver), both at high and low concentration of the target compounds, were investigated in order to evaluate the capabilities and limitations of the reported approach. Finally, other possible applications of this technique, such as the elucidation of elemental compositions based on product ions and corresponding neutral losses, were also presented and discussed

  1. [Screening and confirmation of 24 hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    Science.gov (United States)

    Li, Zhaoyong; Wang, Fengmei; Niu, Zengyuan; Luo, Xin; Zhang, Gang; Chen, Junhui

    2014-05-01

    A method of ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was established to screen and confirm 24 hormones in cosmetics. Various cosmetic samples were extracted with methanol. The extract was loaded onto a Waters ACQUITY UPLC BEH C18 column (50 mm x 2.1 mm, 1.7 microm) using a gradient elution of acetonitrile/water containing 0.1% (v/v) formic acid for the separation. The accurate mass of quasi-molecular ion was acquired by full scanning of electrostatic field orbitrap. The rapid screening was carried out by the accurate mass of quasi-molecular ion. The confirmation analysis for targeted compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode. Under the optimal conditions, the 24 hormones were routinely detected with mass accuracy error below 3 x 10(-6) (3 ppm), and good linearities were obtained in their respective linear ranges with correlation coefficients higher than 0.99. The LODs (S/N = 3) of the 24 compounds were hormones in 50 cosmetic samples. The results demonstrate that the method is a useful tool for the rapid screening and identification of the hormones in cosmetics.

  2. A new processing scheme for ultra-high resolution direct infusion mass spectrometry data

    Science.gov (United States)

    Zielinski, Arthur T.; Kourtchev, Ivan; Bortolini, Claudio; Fuller, Stephen J.; Giorio, Chiara; Popoola, Olalekan A. M.; Bogialli, Sara; Tapparo, Andrea; Jones, Roderic L.; Kalberer, Markus

    2018-04-01

    High resolution, high accuracy mass spectrometry is widely used to characterise environmental or biological samples with highly complex composition enabling the identification of chemical composition of often unknown compounds. Despite instrumental advancements, the accurate molecular assignment of compounds acquired in high resolution mass spectra remains time consuming and requires automated algorithms, especially for samples covering a wide mass range and large numbers of compounds. A new processing scheme is introduced implementing filtering methods based on element assignment, instrumental error, and blank subtraction. Optional post-processing incorporates common ion selection across replicate measurements and shoulder ion removal. The scheme allows both positive and negative direct infusion electrospray ionisation (ESI) and atmospheric pressure photoionisation (APPI) acquisition with the same programs. An example application to atmospheric organic aerosol samples using an Orbitrap mass spectrometer is reported for both ionisation techniques resulting in final spectra with 0.8% and 8.4% of the peaks retained from the raw spectra for APPI positive and ESI negative acquisition, respectively.

  3. Final Technical Report for DE-FG02-06ER15835: Chemical Imaging with 100nm Spatial Resolution: Combining High Resolution Flurosecence Microscopy and Ion Mobility Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Buratto, Steven K. [UC Santa Barbara

    2013-09-03

    We have combined, in a single instrument, high spatial resolution optical microscopy with the chemical specificity and conformational selectivity of ion mobility mass spectrometry. We discuss the design and construction of this apparatus as well as our efforts in applying this technique to thin films of molecular semiconductor materials.

  4. Fourier Transfrom Ion Cyclotron Resonance Mass Spectrometry at High Magnetic Field

    Science.gov (United States)

    Marshall, Alan G.

    1998-03-01

    At high magnetic field (9.4 tesla at NHMFL), Fourier transform ion cyclotron resonance mass spectrometry performance improves dramatically: mass resolving power, axialization efficiency, and scan speed (each proportional to B), maximum ion mass, dynamic range, ion trapping period, kinetic energy, and electron self-cooling rate for sympathetic cooling (each proportional to B^2), and ion coalescence tendency (proportional 1/B^2). These advantages may apply singly (e.g., unit mass resolution for proteins of >100,000 Da), or compound (e.g., 10-fold improvement in S/N ratio for 9.4 T vs. 6 T at the same resolving power). Examples range from direct determination of molecular formulas of diesel fuel components by accurate mass measurement (=B10.1 ppm) to protein structure and dynamics probed by H/D exchange. This work was supported by N.S.F. (CHE-93-22824; CHE-94-13008), N.I.H. (GM-31683), Florida State University, and the National High Magnetic Field Laboratory in Tallahassee, FL.

  5. Bioconversion of red ginseng saponins in the gastro-intestinal tract in vitro model studied by high-performance liquid chromatography-high resolution Fourier transform ion cyclotron resonance mass spectrometry

    NARCIS (Netherlands)

    Kong, H.; Wang, M.; Venema, K.; Maathuis, A.; Heijden, R. van der; Greef, J. van der; Xu, G.; Hankemeier, T.

    2009-01-01

    A high-performance liquid chromatography-high resolution Fourier transform ion cyclotron resonance mass spectrometry (HPLC-FTICR-MS) method was developed to investigate the metabolism of ginsenosides in in vitro models of the gastro-intestinal tract. The metabolites were identified by

  6. Bayesian Peptide Peak Detection for High Resolution TOF Mass Spectrometry.

    Science.gov (United States)

    Zhang, Jianqiu; Zhou, Xiaobo; Wang, Honghui; Suffredini, Anthony; Zhang, Lin; Huang, Yufei; Wong, Stephen

    2010-11-01

    In this paper, we address the issue of peptide ion peak detection for high resolution time-of-flight (TOF) mass spectrometry (MS) data. A novel Bayesian peptide ion peak detection method is proposed for TOF data with resolution of 10 000-15 000 full width at half-maximum (FWHW). MS spectra exhibit distinct characteristics at this resolution, which are captured in a novel parametric model. Based on the proposed parametric model, a Bayesian peak detection algorithm based on Markov chain Monte Carlo (MCMC) sampling is developed. The proposed algorithm is tested on both simulated and real datasets. The results show a significant improvement in detection performance over a commonly employed method. The results also agree with expert's visual inspection. Moreover, better detection consistency is achieved across MS datasets from patients with identical pathological condition.

  7. Accurate and precise 40Ar/39Ar dating by high-resolution, multi-collection, mass spectrometry

    DEFF Research Database (Denmark)

    Storey, Michael; Rivera, Tiffany; Flude, Stephanie

    New generation, high resolution, multi-collector noble gas mass spectrometers equipped with ion-counting electron multipliers provide opportunities for improved accuracy and precision in 40Ar/39Ar dating. Here we report analytical protocols and age cross-calibration studies using a NU-Instruments......New generation, high resolution, multi-collector noble gas mass spectrometers equipped with ion-counting electron multipliers provide opportunities for improved accuracy and precision in 40Ar/39Ar dating. Here we report analytical protocols and age cross-calibration studies using a NU......-Instruments multi-collector Noblesse noble gas mass spectrometer configured with a faraday detector and three ion-counting electron multipliers. The instrument has the capability to measure several noble gas isotopes simultaneously and to change measurement configurations instantaneously by the use of QUAD lenses...... (zoom optics). The Noblesse offer several advantages over previous generation noble gas mass spectrometers and is particularly suited for single crystal 40Ar/39Ar dating because of: (i) improved source sensitivity (ii) ion-counting electron multipliers, which have much lower signal to noise ratios than...

  8. Time of flight secondary ion mass spectrometry: A powerful high throughput screening tool

    International Nuclear Information System (INIS)

    Smentkowski, Vincent S.; Ostrowski, Sara G.

    2007-01-01

    Combinatorial materials libraries are becoming more complicated; successful screening of these libraries requires the development of new high throughput screening methodologies. Time of flight secondary ion mass spectrometry (ToF-SIMS) is a surface analytical technique that is able to detect and image all elements (including hydrogen which is problematic for many other analysis instruments) and molecular fragments, with high mass resolution, during a single measurement. Commercial ToF-SIMS instruments can image 500 μm areas by rastering the primary ion beam over the region of interest. In this work, we will show that large area analysis can be performed, in one single measurement, by rastering the sample under the ion beam. We show that an entire 70 mm diameter wafer can be imaged in less than 90 min using ToF-SIMS stage (macro)rastering techniques. ToF-SIMS data sets contain a wealth of information since an entire high mass resolution mass spectrum is saved at each pixel in an ion image. Multivariate statistical analysis (MVSA) tools are being used in the ToF-SIMS community to assist with data interpretation; we will demonstrate that MVSA tools provide details that were not obtained using manual (univariate) analysis

  9. An ultra-sensitive instrument for collision activated dissociation mass spectrometry with high mass resolution

    International Nuclear Information System (INIS)

    Louter, G.J.

    1982-01-01

    During the last decade Collision Activated Dissociation Mass Spectrometry (CAD-MS) has developed into an important and sometimes unique technique for the structure elucidation of ions. An extensive description of the double stage MS is given, which has been especially devloped for CAD-MS. A high mass resolution and a very high sensitivity are obtained by application of special techniques like post-acceleration of fragment ions, quadrupole (Q-pole) lenses and an electro-optical, simultaneous ion detection system. The operation of the rather complex ion-optics is demonstrated by application of a computer simulation of the tandem MS. Special attention is given to the action of the four Q-pole lenses and the second sector magnet upon curvature and position of the mass focal plane. Two mass calibration methods are described for the fragment spectra. The so-called polynomial-method applies a fifth-order polynomial approximation of the functional relation between position on the detector and corresponding relative momentum of fragment ions. The second method uses the matrix model of the instrument. The detector consists of two channelplates (CEMA), a fibre optics slab, coated with a phosphor layer, a camera objective and a 1024-channels photodiode-array. A bio-chemical and an organic-chemical application of the instrument are given. As bio-chemical application the peak m/z 59 in the pyrolysis mass spectrum of complete mycobacteria is identified. As an example of organic-chemical application the fragmentation process of 2,3-butadienoic acid has been investigated. (Auth.)

  10. [Application of liquid chromatography-high resolution mass spectrometry in toxicological screening].

    Science.gov (United States)

    Li, Xiao-Wen; Shen, Bao-Hua; Zhuo, Xian-Yi

    2011-10-01

    Due to the diversity of toxicologically relevant substances, the uncertainty of target compounds and the specificity of samples, toxicological screening techniques have always been valued by the forensic toxicologists. Depending on its powerful separation ability, superhigh resolution and accurate mass measurement, combined with the two levels spectrum database matching and abundance ratio of isotope ion, the liquid chromatography-high resolution mass spectrometry (LC-HRMS) analyzers have increasingly advantage in screening and identification of chemical compound. This review focuses on the applications of LC-HRMS in screening and identification of drug-of-abuse, prescription drugs, pesticide and stimulant. The prospect of LC-HRMS in forensic toxicology analysis is also included.

  11. High spatial resolution and high brightness ion beam probe for in-situ elemental and isotopic analysis

    Science.gov (United States)

    Long, Tao; Clement, Stephen W. J.; Bao, Zemin; Wang, Peizhi; Tian, Di; Liu, Dunyi

    2018-03-01

    A high spatial resolution and high brightness ion beam from a cold cathode duoplasmatron source and primary ion optics are presented and applied to in-situ analysis of micro-scale geological material with complex structural and chemical features. The magnetic field in the source as well as the influence of relative permeability of magnetic materials on source performance was simulated using COMSOL to confirm the magnetic field strength of the source. Based on SIMION simulation, a high brightness and high spatial resolution negative ion optical system has been developed to achieve Critical (Gaussian) illumination mode. The ion source and primary column are installed on a new Time-of-Flight secondary ion mass spectrometer for analysis of geological samples. The diameter of the ion beam was measured by the knife-edge method and a scanning electron microscope (SEM). Results show that an O2- beam of ca. 5 μm diameter with a beam intensity of ∼5 nA and an O- beam of ca. 5 μm diameter with a beam intensity of ∼50 nA were obtained, respectively. This design will open new possibilities for in-situ elemental and isotopic analysis in geological studies.

  12. Development and analytical characterization of a Grimm-type glow discharge ion source operated with high gas flow rates and coupled to a mass spectrometer with high mass resolution

    International Nuclear Information System (INIS)

    Beyer, Claus; Feldmann, Ingo; Gilmour, Dave; Hoffmann, Volker; Jakubowski, Norbert

    2002-01-01

    A Grimm-type glow discharge ion source has been developed and was coupled to a commercial inductively coupled plasma mass spectrometer (ICP-MS) with high mass resolution (Axiom, ThermoElemental, Winsford, UK) by exchanging the front plate of the ICP-MS interface system only. In addition to high discharge powers of up to 70 W, which are typical for a Grimm-type design, this source could be operated with relative high gas flow rates of up to 240 ml min -1 . In combination with a high discharge voltage the signal intensities are reaching a constant level within the first 20 s after the discharge has started. An analytical characterization of this source is given utilizing a calibration using the steel standard reference material NIST 1261A-1265A. The sensitivity for the investigated elements measured with a resolution of 4000 is in the range of 500-6000 cps μg -1 g -1 , and a relative standard deviation (R.S.D.) of the measured isotope relative to Fe of less than 8% for the major and minor components of the sample has been achieved. Limits of detection at ng g -1 levels could be obtained

  13. A four dimensional separation method based on continuous heart-cutting gas chromatography with ion mobility and high resolution mass spectrometry.

    Science.gov (United States)

    Lipok, Christian; Hippler, Jörg; Schmitz, Oliver J

    2018-02-09

    A two-dimensional GC (2D-GC) method was developed and coupled to an ion mobility-high resolution mass spectrometer, which enables the separation of complex samples in four dimensions (2D-GC, ion mobilility spectrometry and mass spectrometry). This approach works as a continuous multiheart-cutting GC-system (GC+GC), using a long modulation time of 20s, which allows the complete transfer of most of the first dimension peaks to the second dimension column without fractionation, in comparison to comprehensive two-dimensional gas chromatography (GCxGC). Hence, each compound delivers only one peak in the second dimension, which simplifies the data handling even when ion mobility spectrometry as a third and mass spectrometry as a fourth dimension are introduced. The analysis of a plant extract from Calendula officinales shows the separation power of this four dimensional separation method. The introduction of ion mobility spectrometry provides an additional separation dimension and allows to determine collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 800 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. A homemade high-resolution orthogonal-injection time-of-flight mass spectrometer with a heated capillary inlet

    International Nuclear Information System (INIS)

    Guo Changjuan; Huang Zhengxu; Gao Wei; Nian Huiqing; Chen Huayong; Dong Junguo; Shen Guoying; Fu Jiamo; Zhou Zhen

    2008-01-01

    We describe a homemade high-resolution orthogonal-injection time-of-flight (O-TOF) mass spectrometer combing a heated capillary inlet. The O-TOF uses a heated capillary tube combined with a radio-frequency only quadrupole (rf-only quadrupole) as an interface to help the ion transmission from the atmospheric pressure to the low-pressure regions. The principle, configuration of the O-TOF, and the performance of the instrument are introduced in this paper. With electrospray ion source, the performances of the mass resolution, the sensitivity, the mass range, and the mass accuracy are described. We also include our results obtained by coupling atmospheric pressure matrix-assisted laser deporption ionization with this instrument

  15. High Resolution Separations and Improved Ion Production and Transmission in Metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Metz, Thomas O.; Page, Jason S.; Baker, Erin Shammel; Tang, Keqi; Ding, Jie; Shen, Yufeng; Smith, Richard D.

    2008-03-31

    The goal of metabolomics experiments is the detection and quantitation of as many sample components as reasonably possible in order to identify “features” that can be used to characterize the samples under study. When utilizing electrospray ionization to produce ions for analysis by mass spectrometry (MS), it is imperative that metabolome sample constituents be efficiently separated prior to ion production, in order to minimize the phenomenon of ionization suppression. Similarly, optimization of the MS inlet can lead to increased measurement sensitivity. This review will focus on the role of high resolution liquid chromatography (LC) separations in conjunction with improved ion production and transmission for LC-MS-based metabolomics.

  16. Expanding the linear dynamic range for quantitative liquid chromatography-high resolution mass spectrometry utilizing natural isotopologue signals

    International Nuclear Information System (INIS)

    Liu, Hanghui; Lam, Lily; Yan, Lin; Chi, Bert; Dasgupta, Purnendu K.

    2014-01-01

    Highlights: • Less abundant isotopologue ions were utilized to decrease detector saturation. • A 25–50 fold increase in the upper limit of dynamic range was demonstrated. • Linear dynamic range was expanded without compromising mass resolution. - Abstract: The linear dynamic range (LDR) for quantitative liquid chromatography–mass spectrometry can be extended until ionization saturation is reached by using a number of target isotopologue ions in addition to the normally used target ion that provides the highest sensitivity. Less abundant isotopologue ions extend the LDR: the lower ion abundance decreases the probability of ion detector saturation. Effectively the sensitivity decreases and the upper limit of the LDR increases. We show in this paper that the technique is particularly powerful with a high resolution time of flight mass spectrometer because the data for all ions are automatically acquired, and we demonstrated this for four small organic molecules; the upper limits of LDRs increased by 25–50 times

  17. Structural characterization of suppressor lipids by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Rovillos, Mary Joy; Pauling, Josch Konstantin; Hannibal-Bach, Hans Kristian

    2016-01-01

    RATIONALE: Suppressor lipids were originally identified in 1993 and reported to encompass six lipid classes that enable Saccharomyces cerevisiae to live without sphingolipids. Structural characterization, using non-mass spectrometric approaches, revealed that these suppressor lipids are very long...... chain fatty acid (VLCFA)-containing glycerophospholipids with polar head groups that are typically incorporated into sphingolipids. Here we report, for the first time, the structural characterization of the yeast suppressor lipids using high-resolution mass spectrometry. METHODS: Suppressor lipids were...... isolated by preparative chromatography and subjected to structural characterization using hybrid quadrupole time-of-flight and ion trap-orbitrap mass spectrometry. RESULTS: Our investigation recapitulates the overall structural features of the suppressor lipids and provides an in-depth characterization...

  18. Linking high resolution mass spectrometry data with exposure ...

    Science.gov (United States)

    There is a growing need in the field of exposure science for monitoring methods that rapidly screen environmental media for suspect contaminants. Measurement and analysis platforms, based on high resolution mass spectrometry (HRMS), now exist to meet this need. Here we describe results of a study that links HRMS data with exposure predictions from the U.S. EPA's ExpoCast™ program and in vitro bioassay data from the U.S. interagency Tox21 consortium. Vacuum dust samples were collected from 56 households across the U.S. as part of the American Healthy Homes Survey (AHHS). Sample extracts were analyzed using liquid chromatography time-of-flight mass spectrometry (LC–TOF/MS) with electrospray ionization. On average, approximately 2000 molecular features were identified per sample (based on accurate mass) in negative ion mode, and 3000 in positive ion mode. Exact mass, isotope distribution, and isotope spacing were used to match molecular features with a unique listing of chemical formulas extracted from EPA's Distributed Structure-Searchable Toxicity (DSSTox) database. A total of 978 DSSTox formulas were consistent with the dust LC–TOF/molecular feature data (match score ≥ 90); these formulas mapped to 3228 possible chemicals in the database. Correct assignment of a unique chemical to a given formula required additional validation steps. Each suspect chemical was prioritized for follow-up confirmation using abundance and detection frequency results, along wi

  19. Analysis of a variety of inorganic and organic additives in food products by ion-pairing liquid chromatography coupled to high-resolution mass spectrometry.

    Science.gov (United States)

    Kaufmann, Anton; Widmer, Mirjam; Maden, Kathryn; Butcher, Patrick; Walker, Stephan

    2018-03-05

    A reversed-phase ion-pairing chromatographic method was developed for the detection and quantification of inorganic and organic anionic food additives. A single-stage high-resolution mass spectrometer (orbitrap ion trap, Orbitrap) was used to detect the accurate masses of the unfragmented analyte ions. The developed ion-pairing chromatography method was based on a dibutylamine/hexafluoro-2-propanol buffer. Dibutylamine can be charged to serve as a chromatographic ion-pairing agent. This ensures sufficient retention of inorganic and organic anions. Yet, unlike quaternary amines, it can be de-charged in the electrospray to prevent the formation of neutral analyte ion-pairing agent adducts. This process is significantly facilitated by the added hexafluoro-2-propanol. This approach permits the sensitive detection and quantification of additives like nitrate and mono-, di-, and triphosphate as well as citric acid, a number of artificial sweeteners like cyclamate and aspartame, flavor enhancers like glutamate, and preservatives like sorbic acid. This is a major advantage, since the currently used analytical methods as utilized in food safety laboratories are only capable in monitoring a few compounds or a particular category of food additives. Graphical abstract Deptotonation of ion pair agent in the electrospray interface.

  20. An Automated High Performance Capillary Liquid Chromatography Fourier Transform Ion Cyclotron Resonance Mass Spectrometer for High-Throughput Proteomics

    International Nuclear Information System (INIS)

    Belov, Mikhail E.; Anderson, Gordon A.; Wingerd, Mark A.; Udseth, Harold R.; Tang, Keqi; Prior, David C.; Swanson, Kenneth R.; Buschbach, Michael A.; Strittmatter, Eric F.; Moore, Ronald J.; Smith, Richard D.

    2004-01-01

    We report on a fully automated 9.4 tesla Fourier transform ion resonance cyclotron (FTICR) mass spectrometer coupled to reverse-phase chromatography for high-throughput proteomic studies. Modifications made to the front-end of a commercial FTICR instrument--a dual-ESI-emitter ion source; dual-channel electrodynamic ion funnel; and collisional-cooling, selection and accumulation quadrupoles--significantly improved the sensitivity, dynamic range and mass measurement accuracy of the mass spectrometer. A high-pressure capillary liquid chromatography (LC) system was incorporated with an autosampler that enabled 24 h/day operation. A novel method for accumulating ions in the ICR cell was also developed. Unattended operation of the instrument revealed the exceptional reproducibility (1-5% deviation in elution times for peptides from a bacterial proteome), repeatability (10-20% deviation in detected abundances for peptides from the same aliquot analyzed a few weeks apart) and robustness (high-throughput operation for 5 months without downtime) of the LC/FTICR system. When combined with modulated-ion-energy gated trapping, the internal calibration of FTICR mass spectra decreased dispersion of mass measurement errors for peptide identifications in conjunction with high resolution capillary LC separations to < 5 ppm over a dynamic range for each spectrum of 10 3

  1. Mini ion trap mass spectrometer

    Science.gov (United States)

    Dietrich, D.D.; Keville, R.F.

    1995-09-19

    An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

  2. Mass defect filtering-oriented classification and precursor ions list-triggered high-resolution mass spectrometry analysis for the discovery of indole alkaloids from Uncaria sinensis.

    Science.gov (United States)

    Pan, Huiqin; Yang, Wenzhi; Yao, Changliang; Shen, Yao; Zhang, Yibei; Shi, Xiaojian; Yao, Shuai; Wu, Wanying; Guo, Dean

    2017-09-22

    Discovery of new natural compounds is becoming increasingly challenging because of the interference from those known and abundant components. The aim of this study is to report a dereplication strategy, by integrating mass defect filtering (MDF)-oriented novelty classification and precursor ions list (PIL)-triggered high-resolution mass spectrometry analysis, and to validate it by discovering new indole alkaloids from the medicinal herb Uncaria sinensis. Rapid chromatographic separation was achieved on a Kinetex ® EVO C18 column (<16min). An in-house MDF algorithm, developed based on the informed phytochemistry information and molecular design, could more exactly screen the target alkaloids and divide them into three novelty levels: Known (KN), Unknown-but-Predicted (UP), and Unexpected (UN). A hybrid data acquisition method, namely PIL-triggered collision-induced dissociation-MS 2 and high-energy C-trap dissociation-MS 3 with dynamic exclusion on a linear ion trap/Orbitrap mass spectrometer, facilitated the acquisition of diverse product ions sufficient for the structural elucidation of both indole alkaloids and the N-oxides. Ultimately, 158 potentially new alkaloids, including 10 UP and 108 UN, were rapidly characterized from the stem, leaf, and flower of U. sinensis. Two new alkaloid compounds thereof were successfully isolated and identified by 1D and 2D NMR analyses. The varied ring E and novel alkaloid-acylquinic acid conjugates were first reported from the whole Uncaria genus. Conclusively, it is a practical chemical dereplication strategy that can enhance the efficiency and has the potential to be a routine approach for the discovery of new natural compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Boundaries of mass resolution in native mass spectrometry.

    Science.gov (United States)

    Lössl, Philip; Snijder, Joost; Heck, Albert J R

    2014-06-01

    Over the last two decades, native mass spectrometry (MS) has emerged as a valuable tool to study intact proteins and noncovalent protein complexes. Studied experimental systems range from small-molecule (drug)-protein interactions, to nanomachineries such as the proteasome and ribosome, to even virus assembly. In native MS, ions attain high m/z values, requiring special mass analyzers for their detection. Depending on the particular mass analyzer used, instrumental mass resolution does often decrease at higher m/z but can still be above a couple of thousand at m/z 5000. However, the mass resolving power obtained on charge states of protein complexes in this m/z region is experimentally found to remain well below the inherent instrument resolution of the mass analyzers employed. Here, we inquire into reasons for this discrepancy and ask how native MS would benefit from higher instrumental mass resolution. To answer this question, we discuss advantages and shortcomings of mass analyzers used to study intact biomolecules and biomolecular complexes in their native state, and we review which other factors determine mass resolving power in native MS analyses. Recent examples from the literature are given to illustrate the current status and limitations.

  4. Versatile lipid profiling by liquid chromatography–high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer

    International Nuclear Information System (INIS)

    Gallart-Ayala, H.; Courant, F.; Severe, S.; Antignac, J.-P.; Morio, F.; Abadie, J.; Le Bizec, B.

    2013-01-01

    Graphical abstract: -- Highlights: •Lipidomics, high resolution mass spectrometry, polarity switching, serum, canine mammary cancer. -- Abstract: Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC–HRMS or LC–MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC–HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and “all ion fragmentation” (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale

  5. Versatile lipid profiling by liquid chromatography–high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer

    Energy Technology Data Exchange (ETDEWEB)

    Gallart-Ayala, H., E-mail: laberca@oniris-nantes.fr [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France); Courant, F.; Severe, S.; Antignac, J.-P. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France); Morio, F.; Abadie, J. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), Cancers Animaux, Modèles pour la Recherche en Oncologie Comparée (AMaROC), Site de la Chantrerie–CS50707, 44307 Nantes cedex 3 (France); Le Bizec, B. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France)

    2013-09-24

    Graphical abstract: -- Highlights: •Lipidomics, high resolution mass spectrometry, polarity switching, serum, canine mammary cancer. -- Abstract: Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC–HRMS or LC–MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC–HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and “all ion fragmentation” (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale.

  6. Recent applications of gas chromatography with high-resolution mass spectrometry.

    Science.gov (United States)

    Špánik, Ivan; Machyňáková, Andrea

    2018-01-01

    Gas chromatography coupled to high-resolution mass spectrometry is a powerful analytical method that combines excellent separation power of gas chromatography with improved identification based on an accurate mass measurement. These features designate gas chromatography with high-resolution mass spectrometry as the first choice for identification and structure elucidation of unknown volatile and semi-volatile organic compounds. Gas chromatography with high-resolution mass spectrometry quantitative analyses was previously focused on the determination of dioxins and related compounds using magnetic sector type analyzers, a standing requirement of many international standards. The introduction of a quadrupole high-resolution time-of-flight mass analyzer broadened interest in this method and novel applications were developed, especially for multi-target screening purposes. This review is focused on the development and the most interesting applications of gas chromatography coupled to high-resolution mass spectrometry towards analysis of environmental matrices, biological fluids, and food safety since 2010. The main attention is paid to various approaches and applications of gas chromatography coupled to high-resolution mass spectrometry for non-target screening to identify contaminants and to characterize the chemical composition of environmental, food, and biological samples. The most interesting quantitative applications, where a significant contribution of gas chromatography with high-resolution mass spectrometry over the currently used methods is expected, will be discussed as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions

    International Nuclear Information System (INIS)

    Gilchrist, Elizabeth S.; Nesterenko, Pavel N.; Smith, Norman W.; Barron, Leon P.

    2015-01-01

    Highlights: • IC selectivity at high contents of organic solvent in eluent and elevated temperature is studied. • Solvent-enhanced IC coupled to high resolution MS is beneficial for sensitive detection of ions. • The first application of IC-HRMS to the detection of low explosives in fingermarks is shown. - Abstract: There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5–50 mM hydroxide with 0–80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20–45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30–40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks

  8. Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions

    Energy Technology Data Exchange (ETDEWEB)

    Gilchrist, Elizabeth S. [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom); Nesterenko, Pavel N. [Australian Centre for Research on Separation Science, School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart 7001 (Australia); Smith, Norman W. [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom); Barron, Leon P., E-mail: leon.barron@kcl.ac.uk [Analytical & Environmental Science Division, Department of Forensic & Analytical Science, King’s College London, 150 Stamford Street, London, SE1 9NH (United Kingdom)

    2015-03-20

    Highlights: • IC selectivity at high contents of organic solvent in eluent and elevated temperature is studied. • Solvent-enhanced IC coupled to high resolution MS is beneficial for sensitive detection of ions. • The first application of IC-HRMS to the detection of low explosives in fingermarks is shown. - Abstract: There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5–50 mM hydroxide with 0–80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20–45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30–40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks.

  9. High resolution studies of the origins of polyatomic ions in inductively coupled plasma-mass spectrometry, Part I. Identification methods and effects of neutral gas density assumptions, extraction voltage, and cone material

    International Nuclear Information System (INIS)

    Ferguson, Jill Wisnewski; Houk, R.S.

    2006-01-01

    Common polyatomic ions (ArO + , NO + , H 2 O + , H 3 O + , Ar 2 + , ArN + , OH + , ArH + , O 2 + ) in inductively coupled plasma-mass spectrometry (ICP-MS) are identified using high mass resolution and studied using kinetic gas temperatures (T gas ) determined from a dissociation reaction approach. Methods for making accurate mass measurements, confirming ion identifications, and correcting for mass bias are discussed. The effects of sampler and skimmer cone composition and extraction voltage on polyatomic ion formation are also explored. Neutral species densities at several locations in the extraction interface are estimated and the corresponding effects of the T gas value are calculated. The results provide information about the origins of background ions and indicate possible locations for their formation or removal

  10. THOR Ion Mass Spectrometer instrument - IMS

    Science.gov (United States)

    Retinò, Alessandro; Kucharek, Harald; Saito, Yoshifumi; Fraenz, Markus; Verdeil, Christophe; Leblanc, Frederic; Techer, Jean-Denis; Jeandet, Alexis; Macri, John; Gaidos, John; Granoff, Mark; Yokota, Shoichiro; Fontaine, Dominique; Berthomier, Matthieu; Delcourt, Dominique; Kistler, Lynn; Galvin, Antoniette; Kasahara, Satoshi; Kronberg, Elena

    2016-04-01

    Turbulence Heating ObserveR (THOR) is the first mission ever flown in space dedicated to plasma turbulence. Specifically, THOR will study how turbulent fluctuations at kinetic scales heat and accelerate particles in different turbulent environments within the near-Earth space. To achieve this goal, THOR payload is being designed to measure electromagnetic fields and particle distribution functions with unprecedented resolution and accuracy. Here we present the Ion Mass Spectrometer (IMS) instrument that will measure the full three-dimensional distribution functions of near-Earth main ion species (H+, He+, He++ and O+) at high time resolution (~ 150 ms for H+ , ~ 300 ms for He++) with energy resolution down to ~ 10% in the range 10 eV/q to 30 keV/q and angular resolution ~ 10°. Such high time resolution is achieved by mounting multiple sensors around the spacecraft body, in similar fashion to the MMS/FPI instrument. Each sensor combines a top-hat electrostatic analyzer with deflectors at the entrance together with a time-of-flight section to perform mass selection. IMS electronics includes a fast sweeping high voltage board that is required to make measurements at high cadence. Ion detection includes Micro Channel Plates (MCP) combined with Application-Specific Integrated Circuits (ASICs) for charge amplification, discrimination and time-to-digital conversion (TDC). IMS is being designed to address many of THOR science requirements, in particular ion heating and acceleration by turbulent fluctuations in foreshock, shock and magnetosheath regions. The IMS instrument is being designed and will be built by an international consortium of scientific institutes with main hardware contributions from France, USA, Japan and Germany.

  11. Position sensitive detection coupled to high-resolution time-of-flight mass spectrometry: Imaging for molecular beam deflection experiments

    International Nuclear Information System (INIS)

    Abd El Rahim, M.; Antoine, R.; Arnaud, L.; Barbaire, M.; Broyer, M.; Clavier, Ch.; Compagnon, I.; Dugourd, Ph.; Maurelli, J.; Rayane, D.

    2004-01-01

    We have developed and tested a high-resolution time-of-flight mass spectrometer coupled to a position sensitive detector for molecular beam deflection experiments. The major achievement of this new spectrometer is to provide a three-dimensional imaging (X and Y positions and time-of-flight) of the ion packet on the detector, with a high acquisition rate and a high resolution on both the mass and the position. The calibration of the experimental setup and its application to molecular beam deflection experiments are discussed

  12. Quantification of steroid hormones in human serum by liquid chromatography-high resolution tandem mass spectrometry.

    Science.gov (United States)

    Matysik, Silke; Liebisch, Gerhard

    2017-12-01

    A limited specificity is inherent to immunoassays for steroid hormone analysis. To improve selectivity mass spectrometric analysis of steroid hormones by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been introduced in the clinical laboratory over the past years usually with low mass resolution triple-quadrupole instruments or more recently by high resolution mass spectrometry (HR-MS). Here we introduce liquid chromatography-high resolution tandem mass spectrometry (LC-MS/HR-MS) to further increase selectivity of steroid hormone quantification. Application of HR-MS demonstrates an enhanced selectivity compared to low mass resolution. Separation of isobaric interferences reduces background noise and avoids overestimation. Samples were prepared by automated liquid-liquid extraction with MTBE. The LC-MS/HR-MS method using a quadrupole-Orbitrap analyzer includes eight steroid hormones i.e. androstenedione, corticosterone, cortisol, cortisone, 11-deoxycortisol, 17-hydroxyprogesterone, progesterone, and testosterone. It has a run-time of 5.3min and was validated according to the U.S. Food and Drug Administration (FDA) and the European Medicines Agency (EMA) guidelines. For most of the analytes coefficient of variation were 10% or lower and LOQs were determined significantly below 1ng/ml. Full product ion spectra including accurate masses substantiate compound identification by matching their masses and ratios with authentic standards. In summary, quantification of steroid hormones by LC-MS/HR-MS is applicable for clinical diagnostics and holds also promise for highly selective quantification of other small molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. A compact time-of-flight mass spectrometer for ion source characterization

    International Nuclear Information System (INIS)

    Chen, L.; Wan, X.; Jin, D. Z.; Tan, X. H.; Huang, Z. X.; Tan, G. B.

    2015-01-01

    A compact time-of-flight mass spectrometer with overall dimension of about 413 × 250 × 414 mm based on orthogonal injection and angle reflection has been developed for ion source characterization. Configuration and principle of the time-of-flight mass spectrometer are introduced in this paper. The mass resolution is optimized to be about 1690 (FWHM), and the ion energy detection range is tested to be between about 3 and 163 eV with the help of electron impact ion source. High mass resolution and compact configuration make this spectrometer useful to provide a valuable diagnostic for ion spectra fundamental research and study the mass to charge composition of plasma with wide range of parameters

  14. Development of high-spatial and high-mass resolution mass spectrometric imaging (MSI) and its application to the study of small metabolites and endogenous molecules of plants

    Energy Technology Data Exchange (ETDEWEB)

    Jun, Ji Hyun [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for molecular species. MS imaging with high mass resolution was also achieved by utilizing the LTQ-Orbitrap mass spectrometer for the direct identification of the surface metabolites on the Arabidopsis stem and root and differentiation of isobaric ions having the same nominal mass with no need of tandem mass spectrometry (MS/MS). MS imaging at high-spatial and high-mass resolution was also applied to cer1 mutant of the model system Arabidopsis thaliana to demonstrate its usefulness in biological studies and reveal associated metabolite changes in terms of spatial distribution and/or abundances compared to those of wild-type. The spatial

  15. Strategies for dereplication of natural compounds using high-resolution tandem mass spectrometry.

    Science.gov (United States)

    Kind, Tobias; Fiehn, Oliver

    2017-09-01

    Complete structural elucidation of natural products is commonly performed by nuclear magnetic resonance spectroscopy (NMR), but annotating compounds to most likely structures using high-resolution tandem mass spectrometry is a faster and feasible first step. The CASMI contest 2016 (Critical Assessment of Small Molecule Identification) provided spectra of eighteen compounds for the best manual structure identification in the natural products category. High resolution precursor and tandem mass spectra (MS/MS) were available to characterize the compounds. We used the Seven Golden Rules, Sirius2 and MS-FINDER software for determination of molecular formulas, and then we queried the formulas in different natural product databases including DNP, UNPD, ChemSpider and REAXYS to obtain molecular structures. We used different in-silico fragmentation tools including CFM-ID, CSI:FingerID and MS-FINDER to rank these compounds. Additional neutral losses and product ion peaks were manually investigated. This manual and time consuming approach allowed for the correct dereplication of thirteen of the eighteen natural products.

  16. Use of ultra-high pressure liquid chromatography coupled to high resolution mass spectrometry for fast screening in high throughput doping control.

    Science.gov (United States)

    Musenga, Alessandro; Cowan, David A

    2013-05-03

    We describe a sensitive, comprehensive and fast screening method based on liquid chromatography-high resolution mass spectrometry for the detection of a large number of analytes in sports samples. UHPLC coupled to high resolution mass spectrometry with polarity switching capability is applied for the rapid screening of a large number of analytes in human urine samples. Full scan data are acquired alternating both positive and negative ionisation. Collision-induced dissociation with positive ionisation is also performed to produce fragment ions to improve selectivity for some analytes. Data are reviewed as extracted ion chromatograms based on narrow mass/charge windows (±5ppm). A simple sample preparation method was developed, using direct enzymatic hydrolysis of glucuronide conjugates, followed by solid phase extraction with mixed mode ion-exchange cartridges. Within a 10min run time (including re-equilibration) the method presented allows for the analysis of a large number of analytes from most of the classes in the World Anti-Doping Agency (WADA) Prohibited List, including anabolic agents, β2-agonists, hormone antagonists and modulators, diuretics, stimulants, narcotics, glucocorticoids and β-blockers, and does so while meeting the WADA sensitivity requirements. The high throughput of the method and the fast sample pre-treatment reduces analysis cost and increases productivity. The method presented has been used for the analysis of over 5000 samples in about one month and proved to be reliable. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Prediction of collision cross section and retention time for broad scope screening in gradient reversed-phase liquid chromatography-ion mobility-high resolution accurate mass spectrometry

    DEFF Research Database (Denmark)

    Mollerup, Christian Brinch; Mardal, Marie; Dalsgaard, Petur Weihe

    2018-01-01

    artificial neural networks (ANNs). Prediction was based on molecular descriptors, 827 RTs, and 357 CCS values from pharmaceuticals, drugs of abuse, and their metabolites. ANN models for the prediction of RT or CCS separately were examined, and the potential to predict both from a single model......Exact mass, retention time (RT), and collision cross section (CCS) are used as identification parameters in liquid chromatography coupled to ion mobility high resolution accurate mass spectrometry (LC-IM-HRMS). Targeted screening analyses are now more flexible and can be expanded for suspect...

  18. Ion-optical design of the high-resolution mass separator for the Japanese Hadron Project

    International Nuclear Information System (INIS)

    Sunaoshi, Hitoshi; Fujioka, Manabu; Shinozuka, Tsutomu; Wollnik, Hermann; Meuser, Stefan; Nomura, Toru; Kubono, Shigeru.

    1991-12-01

    An ion-optical design of the JHP-ISOL is presented. This separator consists of a beam guidance system, a main magnetic separator stage and an electrostatic energy focusing stage. This separator is to be coupled with a heavy-ion linac for post-acceleration of mass separated ions up to 6.5 MeV/u. The design goal of the separator is to realize a mass resolving power of R M = 20,000 (basal) at a transmission approaching 100 % with the initial phase space of ± 0.2 mm x ± 20 mrad. (author)

  19. High-resolution measurements of x rays from ion-atom collisions

    International Nuclear Information System (INIS)

    Knudson, A.R.

    1974-01-01

    High resolution measurements of K x-ray spectra produced by ion-atom collisions at MeV energies are presented. These measurements indicate that a distribution of L-shell vacancies accompanies K-shell excitation. The variation of these spectra as a function of incident ion energy and atomic number is discussed. Difficulties in the analysis of these spectra due to rearrangement of vacancies between the time of the collision and the time of x-ray emission are considered. The use of high resolution x-ray measurements to obtain information on projectile ion vacancy configurations is demonstrated by data for Ar ions in KCl. X-ray spectra from Al projectiles in a variety of targets were measured and the effect of target composition on these spectra is discussed

  20. Detection of high mass cluster ions sputtered from Bi surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Shepard, A; Hewitt, R W; Slusser, G J; Baitinger, W E; Cooks, R G; Winograd, N [Purdue Univ., Lafayette, Ind. (USA). Dept. of Chemistry; Delgass, W N [Purdue Univ., Lafayette, Ind. (USA); Varon, A; Devant, G [Societe RIBER, 92 - Rueil-Malmaison (France)

    1976-12-01

    The technique of secondary ion mass spectrometry (SIMS) has been employed to detect Bi/sup 3 +/ ions and associated oxides Bi/sub 3/Osub(x)sup(+)(x=1 to 4) from a Bi foil. Using a 3 keV Ar/sup +/ ion primary beam of 5x10/sup -7/ A/cm/sup 2/, mass resolution to nearly 700 with the requisite sensitivity has been achieved. The Bi surface was also monitored by X-ray photoelectron spectroscopy (XPS or ESCA). The presence of a weak O 1s peak at 532.7 eV and a strong SIMS Bi/sup 3 +/ peak is interpreted to mean that the oxygen is weakly incorporated into the Bi lattice without disrupting metal-metal bonds.

  1. Ozone-induced dissociation on a traveling wave high-resolution mass spectrometer for determination of double-bond position in lipids.

    Science.gov (United States)

    Vu, Ngoc; Brown, Jeffery; Giles, Kevin; Zhang, Qibin

    2017-09-15

    The position of C=C within fatty acyl chains affects the biological function of lipids. Ozone-induced dissociation mass spectrometry (OzID-MS) has great potential in determination of lipid double-bond position, but has generally been implemented on low-resolution ion trap mass spectrometers. In addition, most of the OzID-MS experiments carried out so far were focused on the sodiated adducts of lipids; fragmentation of the most commonly observed protonated ions generated in LC/MS-based lipidomics workflow has been less explored. Ozone generated in line from an ozone generator was connected to the trap and transfer gas supply line of a Synapt G2 high-resolution mass spectrometer. Protonated ions of different phosphatidylcholines (PC) were generated by electrospray ionization through direct infusion. Different parameters, including traveling wave height and velocity, trap entrance and DC potential, were adjusted to maximize the OzID efficiency. sn-positional isomers and cis/trans isomers of lipids were compared for their reactivity with ozone. Traveling wave height and velocity were tuned to prolong the encounter time between lipid ions and ozone, and resulted in improved OzID efficiency, as did increasing trapping region DC and entrance potential. Under optimized settings, at least 1000 times enhancement in OzID efficiency was achieved compared to that under default settings for monounsaturated PC standards. Monounsaturated C=C in the sn-2 PC isomer reacted faster with ozone than the sn-1 isomer. Similarly, the C=C in trans PC reacted faster than in cis PC. This is the first implementation of OzID in the trap and transfer region of a traveling wave enabled high-resolution mass spectrometer. The OzID reaction efficiency is significantly improved by slowing down ions in the trap region for their prolonged interaction with ozone. This will facilitate application of high-resolution OzID-MS in lipidomics. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Quantitation of Acrylamide in Foods by High-Resolution Mass Spectrometry

    NARCIS (Netherlands)

    Troise, A.D.; Fogliano, Vincenzo

    2016-01-01

    The use of liquid chromatography high-resolution mass spectrometry (LC-HRMS) and direct analysis real-time high-resolution mass spectrometry (DART-HRMS) defines a new scenario in the analysis of thermal-induced toxicants, such as acrylamide. Several factors contribute to the definition of the

  3. Ion optics of a time-of-flight mass spectrometer with electrostatic sector analyzers

    International Nuclear Information System (INIS)

    Sakurai, T.; Ito, H.; Matsuo, T.

    1995-01-01

    The ion optics for a high resolution time-of-flight mass spectrometer with electrostatic sector analyzers have been investigated. The multiple focusing (triple isochronous focusing and triple spacial focusing) conditions can be achieved by using a symmetrical arrangement of the sectors in a mass spectrometer. Both high mass resolution and high ion transmission can be accomplished simultaneously. The principles of MS/MS and MS/MS/MS analyses using a TOF mass spectrometer with electrostatic sector analyzers have been proposed. Product ion spectra can be obtained by measuring the total flight times and the kinetic energy of the products without any additional separation processes, any coincidence techniques or any special timing circuits. In an experiment, MS/MS and MS/MS/MS mass spectra have been obtained. The first generation product ions have been produced by a metastable decay, and the second generation products have been produced by a sequential decay. (orig.)

  4. Utility of Higher Harmonics in Electrospray Ionization Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometry.

    Science.gov (United States)

    Dziekonski, Eric T; Johnson, Joshua T; McLuckey, Scott A

    2017-04-18

    Mass resolution (M/ΔM fwhm) is observed to linearly increase with harmonic order in a Fourier transform electrostatic linear ion trap (ELIT) mass spectrometer. This behavior was predicted by Grosshans and Marshall for frequency-multiple detection in a Fourier transform ion cyclotron resonance mass spectrometer only for situations when the prominent mechanism for signal decay is ion ejection from the trap. As the analyzer pressure in our ELIT chamber is relatively high, such that collisional scattering and collision-induced dissociation are expected to underlie much of the ion loss, we sought to explore the relationship between harmonic order and mass resolution. Mass resolutions of 36 900 (fundamental), 75 850 (2nd harmonic), and 108 200 (3rd harmonic) were obtained for GdO + (avg. m/z 173.919) with a transient length of 300 ms. To demonstrate that the mass resolution was truly increasing with harmonic order, the unresolved isotopes at the fundamental distribution of cytochrome c +8 (m/z ∼ 1549) were nearly baseline, resolved at the third harmonic (mass resolution ≈ 23 000) with a transient length of only 200 ms. This experiment demonstrates that, when the ion density is sufficiently low, ions with frequency differences of less than 4 Hz remain uncoalesced. Higher harmonics can be used to increase the effective mass resolution for a fixed transient length and thereby may enable the resolution of closely spaced masses, determination of a protein ion's charge state, and study of the onset of peak coalescence when the resolution at the fundamental frequency is insufficient.

  5. Beam-transport system for high-resolution heavy-ion spectroscopy

    International Nuclear Information System (INIS)

    Roussel, P.; Kashy, E.

    1980-01-01

    A method is given to adjust a beam-transport system to the requirements of high-energy resolution heavy-ion spectroscopy. The results of a test experiment performed on a MP tandem with a 12 C beam are shown. A drastic improvement in energy resolution is obtained for a kinematical factor K=1/p dp/dtheta=0.12 [fr

  6. High resolution spectrometry for relativistic heavy ions

    Energy Technology Data Exchange (ETDEWEB)

    Gabor, G; Schimmerling, W; Greiner, D; Bieser, F; Lindstrom, P [California Univ., Berkeley (USA). Lawrence Berkeley Lab.

    1975-12-01

    Several techniques are discussed for velocity and energy spectrometry of relativistic heavy ions with good resolution. A foil telescope with chevron channel plate detectors is described. A test of this telescope was performed using 2.1 GeV/A C/sup 6 +/ ions, and a time-of-flight resolution of 160 ps was measured. Qualitative information on the effect of foil thickness was also obtained.

  7. A high resolution ion microscope for cold atoms

    International Nuclear Information System (INIS)

    Stecker, Markus; Schefzyk, Hannah; Fortágh, József; Günther, Andreas

    2017-01-01

    We report on an ion-optical system that serves as a microscope for ultracold ground state and Rydberg atoms. The system is designed to achieve a magnification of up to 1000 and a spatial resolution in the 100 nm range, thereby surpassing many standard imaging techniques for cold atoms. The microscope consists of four electrostatic lenses and a microchannel plate in conjunction with a delay line detector in order to achieve single particle sensitivity with high temporal and spatial resolution. We describe the design process of the microscope including ion-optical simulations of the imaging system and characterize aberrations and the resolution limit. Furthermore, we present the experimental realization of the microscope in a cold atom setup and investigate its performance by patterned ionization with a structure size down to 2.7 μ m. The microscope meets the requirements for studying various many-body effects, ranging from correlations in cold quantum gases up to Rydberg molecule formation. (paper)

  8. Suspected-target pesticide screening using gas chromatography-quadrupole time-of-flight mass spectrometry with high resolution deconvolution and retention index/mass spectrum library.

    Science.gov (United States)

    Zhang, Fang; Wang, Haoyang; Zhang, Li; Zhang, Jing; Fan, Ruojing; Yu, Chongtian; Wang, Wenwen; Guo, Yinlong

    2014-10-01

    A strategy for suspected-target screening of pesticide residues in complicated matrices was exploited using gas chromatography in combination with hybrid quadrupole time-of-flight mass spectrometry (GC-QTOF MS). The screening workflow followed three key steps of, initial detection, preliminary identification, and final confirmation. The initial detection of components in a matrix was done by a high resolution mass spectrum deconvolution; the preliminary identification of suspected pesticides was based on a special retention index/mass spectrum (RI/MS) library that contained both the first-stage mass spectra (MS(1) spectra) and retention indices; and the final confirmation was accomplished by accurate mass measurements of representative ions with their response ratios from the MS(1) spectra or representative product ions from the second-stage mass spectra (MS(2) spectra). To evaluate the applicability of the workflow in real samples, three matrices of apple, spinach, and scallion, each spiked with 165 test pesticides in a set of concentrations, were selected as the models. The results showed that the use of high-resolution TOF enabled effective extractions of spectra from noisy chromatograms, which was based on a narrow mass window (5 mDa) and suspected-target compounds identified by the similarity match of deconvoluted full mass spectra and filtering of linear RIs. On average, over 74% of pesticides at 50 ng/mL could be identified using deconvolution and the RI/MS library. Over 80% of pesticides at 5 ng/mL or lower concentrations could be confirmed in each matrix using at least two representative ions with their response ratios from the MS(1) spectra. In addition, the application of product ion spectra was capable of confirming suspected pesticides with specificity for some pesticides in complicated matrices. In conclusion, GC-QTOF MS combined with the RI/MS library seems to be one of the most efficient tools for the analysis of suspected-target pesticide residues

  9. Localization of iron in rice grain using synchrotron X-ray fluorescence microscopy and high resolution secondary ion mass spectrometry

    KAUST Repository

    Kyriacou, Bianca; Moore, Katie L.; Paterson, David J.; De Jonge, Martin Daly; Howard, Daryl Lloyd; Stangoulis, James Constantine R; Tester, Mark A.; Lombi, E.; Johnson, Alexander A T

    2014-01-01

    Cereal crops accumulate low levels of iron (Fe) of which only a small fraction (5-10%) is bioavailable in human diets. Extensive co-localization of Fe in outer grain tissues with phytic acid, a strong chelator of metal ions, results in the formation of insoluble complexes that cannot be digested by humans. Here we describe the use of synchrotron X-ray fluorescence microscopy (XFM) and high resolution secondary ion mass spectrometry (NanoSIMS) to map the distribution of Fe, zinc (Zn), phosphorus (P) and other elements in the aleurone and subaleurone layers of mature grain from wild-type and an Fe-enriched line of rice (Oryza sativa L.). The results obtained from both XFM and NanoSIMS indicated that most Fe was co-localized with P (indicative of phytic acid) in the aleurone layer but that a small amount of Fe, often present as "hotspots", extended further into the subaleurone and outer endosperm in a pattern that was not co-localized with P. We hypothesize that Fe in subaleurone and outer endosperm layers of rice grain could be bound to low molecular weight chelators such as nicotianamine and/or deoxymugineic acid. © 2014.

  10. Localization of iron in rice grain using synchrotron X-ray fluorescence microscopy and high resolution secondary ion mass spectrometry

    KAUST Repository

    Kyriacou, Bianca

    2014-03-01

    Cereal crops accumulate low levels of iron (Fe) of which only a small fraction (5-10%) is bioavailable in human diets. Extensive co-localization of Fe in outer grain tissues with phytic acid, a strong chelator of metal ions, results in the formation of insoluble complexes that cannot be digested by humans. Here we describe the use of synchrotron X-ray fluorescence microscopy (XFM) and high resolution secondary ion mass spectrometry (NanoSIMS) to map the distribution of Fe, zinc (Zn), phosphorus (P) and other elements in the aleurone and subaleurone layers of mature grain from wild-type and an Fe-enriched line of rice (Oryza sativa L.). The results obtained from both XFM and NanoSIMS indicated that most Fe was co-localized with P (indicative of phytic acid) in the aleurone layer but that a small amount of Fe, often present as "hotspots", extended further into the subaleurone and outer endosperm in a pattern that was not co-localized with P. We hypothesize that Fe in subaleurone and outer endosperm layers of rice grain could be bound to low molecular weight chelators such as nicotianamine and/or deoxymugineic acid. © 2014.

  11. Atom-probe field-ion-microscope mass spectrometer

    International Nuclear Information System (INIS)

    Nishikawa, Osamu

    1983-01-01

    The titled analyzer, called simply atom-probe, has been developed by combining a field ion microscope (FIM) and a mass spectrometer, and is divided into the time-of-flight type, magnetic sector type, and quadrupole type depending on the types of mass spectrometers. In this paper, the author first describes on the principle and construction of a high resolution, time-of-flight atom-probe developed and fabricated in his laboratory. The feature of the atom-probe lies in the analysis of atoms and molecules in hyper-fine structure region one by one utilizing the high resolution of FIM. It also has the advantages of directly determining the composition by a ratio of the numbers of respective ions because of a constant detection sensitivity regardless of mass numbers, of the resolution as high as single atom layer in depth direction, and of detecting the positional relationship among detected ions by the order of detection in a sample. To determine the composition in a hyperfine structure region, the limited small number of atoms and molecules in the region must be identified distinctly one by one. In the analyzed result of Ni-silicide formed by heating Si evaporated on a Ni tip at 1000 K for 5 minutes, each isotope was not only clearly separated, but also their abundance ratio was very close to the natural abundance ratio. The second half of the paper reports on the analysis of TiC promising for a cold cathode material, adsorption of CO and alcohol, and the composition and structure of silicides, as a few application examples. (Wakatsuki, Y.)

  12. A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps

    Energy Technology Data Exchange (ETDEWEB)

    Greenwood, J. B.; Kelly, O.; Calvert, C. R.; Duffy, M. J.; King, R. B.; Belshaw, L.; Graham, L.; Alexander, J. D.; Williams, I. D. [Centre for Plasma Physics, School of Mathematics and Physics, Queen' s University Belfast, Belfast BT7 1NN (United Kingdom); Bryan, W. A. [Department of Physics, Swansea University, Swansea SA2 8PP (United Kingdom); Turcu, I. C. E.; Cacho, C. M.; Springate, E. [Central Laser Facility, STFC Rutherford Appleton Laboratory, Didcot, Oxfordshire OX11 0QX (United Kingdom)

    2011-04-15

    In this paper an algorithm for extracting spectral information from signals containing a series of narrow periodic impulses is presented. Such signals can typically be acquired by pickup detectors from the image-charge of ion bunches oscillating in a linear electrostatic ion trap, where frequency analysis provides a scheme for high-resolution mass spectrometry. To provide an improved technique for such frequency analysis, we introduce the CHIMERA algorithm (Comb-sampling for High-resolution IMpulse-train frequency ExtRAaction). This algorithm utilizes a comb function to generate frequency coefficients, rather than using sinusoids via a Fourier transform, since the comb provides a superior match to the data. This new technique is developed theoretically, applied to synthetic data, and then used to perform high resolution mass spectrometry on real data from an ion trap. If the ions are generated at a localized point in time and space, and the data is simultaneously acquired with multiple pickup rings, the method is shown to be a significant improvement on Fourier analysis. The mass spectra generated typically have an order of magnitude higher resolution compared with that obtained from fundamental Fourier frequencies, and are absent of large contributions from harmonic frequency components.

  13. [Determination of short-chain chlorinated paraffins in ambient air using high-volume sampling combined with high resolutimi gas chromatography-electron capture negative ion-low resolution mass spectrometry].

    Science.gov (United States)

    Shi, Loimeng; Gao, Yuan; Hou, Xiaohong; Zhang, Haijun; Zhang, Yichi; Chen, Jiping

    2016-02-01

    An analytical method for quantifying short-chain chlorinated paraffins (SCCPs) in ambient air using high-volume sampling combined with high resolution gas chromatography-electron capture negative ion-low resolution mass spectrometry ( HRGC-ECNI-LRMS) was developed. An acidified silica gel column and a basic alumina column were used to optimize the cleanup procedures. The results showed a good linearity (R2>0. 99) between the total response factors and the degree of chlorination of SCCPs in the content range of 58. 1%-63. 3%. The limits of detection (S/N ≥3) and the limits of quantification (S/N ≥ 10) were 4. 2 and 12 µg, respectively. The method detection limit (MDL) for SCCPs was 0. 34 ng/m3 (n = 7). The recoveries of SCCPs in air samples were in the range of 81. 9% to 94. 2%. It is demonstrated that the method is suitable for the quantitative analysis of SCCPs in air samples.

  14. Electrospray Ionization with High-Resolution Mass Spectrometry as a Tool for Lignomics: Lignin Mass Spectrum Deconvolution

    Science.gov (United States)

    Andrianova, Anastasia A.; DiProspero, Thomas; Geib, Clayton; Smoliakova, Irina P.; Kozliak, Evguenii I.; Kubátová, Alena

    2018-05-01

    The capability to characterize lignin, lignocellulose, and their degradation products is essential for the development of new renewable feedstocks. Electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR TOF-MS) method was developed expanding the lignomics toolkit while targeting the simultaneous detection of low and high molecular weight (MW) lignin species. The effect of a broad range of electrolytes and various ionization conditions on ion formation and ionization effectiveness was studied using a suite of mono-, di-, and triarene lignin model compounds as well as kraft alkali lignin. Contrary to the previous studies, the positive ionization mode was found to be more effective for methoxy-substituted arenes and polyphenols, i.e., species of a broadly varied MW structurally similar to the native lignin. For the first time, we report an effective formation of multiply charged species of lignin with the subsequent mass spectrum deconvolution in the presence of 100 mmol L-1 formic acid in the positive ESI mode. The developed method enabled the detection of lignin species with an MW between 150 and 9000 Da or higher, depending on the mass analyzer. The obtained M n and M w values of 1500 and 2500 Da, respectively, were in good agreement with those determined by gel permeation chromatography. Furthermore, the deconvoluted ESI mass spectrum was similar to that obtained with matrix-assisted laser desorption/ionization (MALDI)-HR TOF-MS, yet featuring a higher signal-to-noise ratio. The formation of multiply charged species was confirmed with ion mobility ESI-HR Q-TOF-MS. [Figure not available: see fulltext.

  15. Versatile lipid profiling by liquid chromatography-high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer.

    Science.gov (United States)

    Gallart-Ayala, H; Courant, F; Severe, S; Antignac, J-P; Morio, F; Abadie, J; Le Bizec, B

    2013-09-24

    Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC-HRMS or LC-MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC-HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and "all ion fragmentation" (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Applications of Fourier Transform Ion Cyclotron Resonance (FT-ICR) and Orbitrap Based High Resolution Mass Spectrometry in Metabolomics and Lipidomics

    Science.gov (United States)

    Ghaste, Manoj; Mistrik, Robert; Shulaev, Vladimir

    2016-01-01

    Metabolomics, along with other “omics” approaches, is rapidly becoming one of the major approaches aimed at understanding the organization and dynamics of metabolic networks. Mass spectrometry is often a technique of choice for metabolomics studies due to its high sensitivity, reproducibility and wide dynamic range. High resolution mass spectrometry (HRMS) is a widely practiced technique in analytical and bioanalytical sciences. It offers exceptionally high resolution and the highest degree of structural confirmation. Many metabolomics studies have been conducted using HRMS over the past decade. In this review, we will explore the latest developments in Fourier transform mass spectrometry (FTMS) and Orbitrap based metabolomics technology, its advantages and drawbacks for using in metabolomics and lipidomics studies, and development of novel approaches for processing HRMS data. PMID:27231903

  17. Multi-detection of corticosteroids in sports doping and veterinary control using high-resolution liquid chromatography/time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Touber, M.E.; Engelen, M.C.; Georgakopoulus, C.; Rhijn, van J.A.; Nielen, M.W.F.

    2007-01-01

    A liquid chromatography/time-of-flight mass spectrometry (LC/TOFMS) method was developed using the latest high-resolution LC column technology, the ultra performance liquid chromatography (UPLC (TM)), and electrospray ionization (ESI) in the positive ion mode. Gradient UPLC separation conditions

  18. Optimized cleanup method for the determination of short chain polychlorinated n-alkanes in sediments by high resolution gas chromatography/electron capture negative ion-low resolution mass spectrometry

    International Nuclear Information System (INIS)

    Gao Yuan; Zhang Haijun; Chen Jiping; Zhang Qing; Tian Yuzeng; Qi Peipei; Yu Zhengkun

    2011-01-01

    Graphical abstract: The sediment sample could be purified by the optimized cleanup method, and satisfying cleanup efficiency was obtained. Highlights: → The elution characters of sPCAs and interfering substances were evaluated on three adsorbents. → An optimized cleanup method was developed for sPCAs with satisfying cleanup efficiency. → The cleanup method combined with HRGC/ECNI-LRMS was applied for sPCAs analysis. → The sPCAs levels range from 53.6 ng g -1 to 289.3 ng g -1 in tested sediment samples. - Abstract: The performances of three adsorbents, i.e. silica gel, neutral and basic alumina, in the separation of short chain polychlorinated n-alkanes (sPCAs) from potential interfering substances such as polychlorinated biphenyls (PCBs) and organochlorine pesticides were evaluated. To increase the cleanup efficiency, a two-step cleanup method using silica gel column and subsequent basic alumina column was developed. All the PCB and organochlorine pesticides could be removed by this cleanup method. The very satisfying cleanup efficiency of sPCAs has been achieved and the recovery in the cleanup method reached 92.7%. The method detection limit (MDL) for sPCAs in sediments was determined to be 14 ng g -1 . Relative standard deviation (R.S.D.) of 5.3% was obtained for the mass fraction of sPCAs by analyzing four replicates of a spiked sediment sample. High resolution gas chromatography/electron capture negative ion-low resolution mass spectrometry (HRGC/ECNI-LRMS) was used for sPCAs quantification by monitoring [M-HCl]· - ions. When applied to the sediment samples from the mouth of the Daliao River, the optimized cleanup method in conjunction with HRGC/ECNI-LRMS allowed for highly selective identifications for sPCAs. The sPCAs levels in sediment samples are reported to range from 53.6 ng g -1 to 289.3 ng g -1 . C 10 - and C 11 -PCAs are the dominant residue in most of investigated sediment samples.

  19. HighResNPS.com – an Internet Database for Liquid Chromatography - High Resolution Mass Spectrometry Screening for New Psychoactive Substances

    DEFF Research Database (Denmark)

    Dalsgaard, Petur Weihe; Mollerup, Christian Brinch; Mardal, Marie

    /Discussions: . The overlapping entries of the database verify that similar fragment ions can be observed from identical compounds across different LC-HRMS systems. The inclusion of fragment ions from other labs can reduce false positive identifications, when no reference standard is available in-house. HighResNPS can serve......Background/Introduction: The number of new psychoactive substances (NPS) is constantly increasing which makes it challenging to keep the screening libraries updated with the relevant analytical targets. Liquid chromatography coupled High Resolution Mass Spectrometry (LC-HRMS) screening methods...... with most screening platforms after minor formatting. Results: Currently, 11 users from 9 laboratories in 7 counties have contributed with 318 entries to the database with experimental data containing at least one fragment ion. 66% of the uploaded data were based on reference standards. Synthetic...

  20. Photoionization of H2O at high resolution

    International Nuclear Information System (INIS)

    Dehmer, P.M.; Chupka, W.A.

    1978-01-01

    The relative photoionization cross sections for the formation of H 2 O + , OH + , and H + from H 2 O were measured at high wavelength resolution using a 3-meter photoionization mass spectrometer equipped with a quadrupole mass flter and a 1-meter photoionization mass spectrometer equipped with a 12-inch radius, 60 0 sector magnetic mass spectrometer. Discrete structure in the parent ion photoionization efficiency curve is interpreted in terms of Rydberg series converging to excited states of the H 2 O + ion. 9 references

  1. Time-of-flight mass spectrographs—From ions to neutral atoms

    Science.gov (United States)

    Möbius, E.; Galvin, A. B.; Kistler, L. M.; Kucharek, H.; Popecki, M. A.

    2016-12-01

    After their introduction to space physics in the mid 1980s time-of-flight (TOF) spectrographs have become a main staple in spaceborne mass spectrometry. They have largely replaced magnetic spectrometers, except when extremely high mass resolution is required to identify complex molecules, for example, in the vicinity of comets or in planetary atmospheres. In combination with electrostatic analyzers and often solid state detectors, TOF spectrographs have become key instruments to diagnose space plasma velocity distributions, mass, and ionic charge composition. With a variety of implementation schemes that also include isochronous electric field configurations, TOF spectrographs can respond to diverse science requirements. This includes a wide range in mass resolution to allow the separation of medium heavy isotopes or to simply provide distributions of the major species, such as H, He, and O, to obtain information on source tracers or mass fluxes. With a top-hat analyzer at the front end, or in combination with deflectors for three-axis stabilized spacecraft, the distribution function of ions can be obtained with good time resolution. Most recently, the reach of TOF ion mass spectrographs has been extended to include energetic neutral atoms. After selecting the arrival direction with mechanical collimation, followed by conversion to ions, adapted TOF sensors form a new branch of the spectrograph family tree. We review the requirements, challenges, and implementation schemes for ion and neutral atom spectrographs, including potential directions for the future, while largely avoiding overlap with complementary contributions in this special issue.

  2. Fourier transform ion cyclotron resonance mass spectrometry

    Science.gov (United States)

    Marshall, Alan G.

    1998-06-01

    As for Fourier transform infrared (FT-IR) interferometry and nuclear magnetic resonance (NMR) spectroscopy, the introduction of pulsed Fourier transform techniques revolutionized ion cyclotron resonance mass spectrometry: increased speed (factor of 10,000), increased sensitivity (factor of 100), increased mass resolution (factor of 10,000-an improvement not shared by the introduction of FT techniques to IR or NMR spectroscopy), increased mass range (factor of 500), and automated operation. FT-ICR mass spectrometry is the most versatile technique for unscrambling and quantifying ion-molecule reaction kinetics and equilibria in the absence of solvent (i.e., the gas phase). In addition, FT-ICR MS has the following analytically important features: speed (~1 second per spectrum); ultrahigh mass resolution and ultrahigh mass accuracy for analysis of mixtures and polymers; attomole sensitivity; MSn with one spectrometer, including two-dimensional FT/FT-ICR/MS; positive and/or negative ions; multiple ion sources (especially MALDI and electrospray); biomolecular molecular weight and sequencing; LC/MS; and single-molecule detection up to 108 Dalton. Here, some basic features and recent developments of FT-ICR mass spectrometry are reviewed, with applications ranging from crude oil to molecular biology.

  3. Triple Quadrupole Versus High Resolution Quadrupole-Time-of-Flight Mass Spectrometry for Quantitative LC-MS/MS Analysis of 25-Hydroxyvitamin D in Human Serum

    Science.gov (United States)

    Geib, Timon; Sleno, Lekha; Hall, Rabea A.; Stokes, Caroline S.; Volmer, Dietrich A.

    2016-08-01

    We describe a systematic comparison of high and low resolution LC-MS/MS assays for quantification of 25-hydroxyvitamin D3 in human serum. Identical sample preparation, chromatography separations, electrospray ionization sources, precursor ion selection, and ion activation were used; the two assays differed only in the implemented final mass analyzer stage; viz. high resolution quadrupole-quadrupole-time-of-flight (QqTOF) versus low resolution triple quadrupole instruments. The results were assessed against measured concentration levels from a routine clinical chemiluminescence immunoassay. Isobaric interferences prevented the simple use of TOF-MS spectra for extraction of accurate masses and necessitated the application of collision-induced dissociation on the QqTOF platform. The two mass spectrometry assays provided very similar analytical figures of merit, reflecting the lack of relevant isobaric interferences in the MS/MS domain, and were successfully applied to determine the levels of 25-hydroxyvitamin D for patients with chronic liver disease.

  4. DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY – HIGH RESOLUTION MASS SPECTROMETRY

    Science.gov (United States)

    Nikcevic, Irena; Wyrzykiewicz, Tadeusz K.; Limbach, Patrick A.

    2010-01-01

    Summary An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described. Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3′-terminal phosphate monoester and 3′-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N3 (2-cyanoethyl) adducts

  5. Cluster ion formation during sputtering processes: a complementary investigation by ToF-SIMS and plasma ion mass spectrometry

    International Nuclear Information System (INIS)

    Welzel, T; Ellmer, K; Mändl, S

    2014-01-01

    Plasma ion mass spectrometry using a plasma process monitor (PPM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been complementarily employed to investigate the sputtering and ion formation processes of Al-doped zinc oxide. By comparing the mass spectra, insights on ion formation and relative cross-sections have been obtained: positive ions as measured during magnetron sputtering by PPM are originating from the plasma while those in SIMS start at the surface leading to large differences in the mass spectra. In contrast, negative ions originating at the surface will be accelerated through the plasma sheath. They arrive at the PPM after traversing the plasma nearly collisionless as seen from the rather similar spectra. Hence, it is possible to combine the high mass resolution of ToF-SIMS to obtain insight for separating cluster ions, e.g. Zn x and ZnO y , and the energy resolution of PPM to find fragmentation patterns for negative ions. While the ion formation processes during both experiments can be assumed to be similar, differences may arise due to the lower volume probed by SIMS. In the latter case, there is a chance of small target inhomogeneities being able to be enhanced and lower surface temperatures leading to less outgassing and, thus, retention of volatile compounds. (paper)

  6. Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

    Science.gov (United States)

    Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana

    2018-01-01

    Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

  7. Development and Evaluation of a Reverse-Entry Ion Source Orbitrap Mass Spectrometer

    Science.gov (United States)

    Poltash, Michael L.; McCabe, Jacob W.; Patrick, John W.; Laganowsky, Arthur; Russell, David H.

    2018-05-01

    As a step towards development of a high-resolution ion mobility mass spectrometer using the orbitrap mass analyzer platform, we describe herein a novel reverse-entry ion source (REIS) coupled to the higher-energy C-trap dissociation (HCD) cell of an orbitrap mass spectrometer with extended mass range. Development of the REIS is a first step in the development of a drift tube ion mobility-orbitrap MS. The REIS approach retains the functionality of the commercial instrument ion source which permits the uninterrupted use of the instrument during development as well as performance comparisons between the two ion sources. Ubiquitin (8.5 kDa) and lipid binding to the ammonia transport channel (AmtB, 126 kDa) protein complex were used as model soluble and membrane proteins, respectively, to evaluate the performance of the REIS instrument. Mass resolution obtained with the REIS is comparable to that obtained using the commercial ion source. The charge state distributions for ubiquitin and AmtB obtained on the REIS are in agreement with previous studies which suggests that the REIS-orbitrap EMR retains native structure in the gas phase.

  8. An (e, 2e + ion) study of low-energy electron-impact ionization and fragmentation of tetrahydrofuran with high mass and energy resolutions

    Science.gov (United States)

    Ren, Xueguang; Pflüger, Thomas; Weyland, Marvin; Baek, Woon Yoon; Rabus, Hans; Ullrich, Joachim; Dorn, Alexander

    2014-10-01

    We study the low-energy (E0 = 26 eV) electron-impact induced ionization and fragmentation of tetrahydrofuran using a reaction microscope. All three final-state charged particles, i.e., two outgoing electrons and one fragment ion, are detected in triple coincidence such that the momentum vectors and, consequently, the kinetic energies for charged reaction products are determined. The ionic fragments are clearly identified in the experiment with a mass resolution of 1 amu. The fragmentation pathways of tetrahydrofuran are investigated by measuring the ion kinetic energy spectra and the binding energy spectra where an energy resolution of 1.5 eV has been achieved using the recently developed photoemission electron source. Here, we will discuss the fragmentation reactions for the cations C4H8O+, C4H7O+, C2H3O+, C3H_6^+, C3H_5^+, C3H_3^+, CH3O+, CHO+, and C2H_3^+.

  9. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    International Nuclear Information System (INIS)

    Manard, Manuel J.; Weeks, Stephan; Kyle, Kevin

    2010-01-01

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

  10. A compact high resolution ion mobility spectrometer for fast trace gas analysis.

    Science.gov (United States)

    Kirk, Ansgar T; Allers, Maria; Cochems, Philipp; Langejuergen, Jens; Zimmermann, Stefan

    2013-09-21

    Drift tube ion mobility spectrometers (IMS) are widely used for fast trace gas detection in air, but portable compact systems are typically very limited in their resolving power. Decreasing the initial ion packet width improves the resolution, but is generally associated with a reduced signal-to-noise-ratio (SNR) due to the lower number of ions injected into the drift region. In this paper, we present a refined theory of IMS operation which employs a combined approach for the analysis of the ion drift and the subsequent amplification to predict both the resolution and the SNR of the measured ion current peak. This theoretical analysis shows that the SNR is not a function of the initial ion packet width, meaning that compact drift tube IMS with both very high resolution and extremely low limits of detection can be designed. Based on these implications, an optimized combination of a compact drift tube with a length of just 10 cm and a transimpedance amplifier has been constructed with a resolution of 183 measured for the positive reactant ion peak (RIP(+)), which is sufficient to e.g. separate the RIP(+) from the protonated acetone monomer, even though their drift times only differ by a factor of 1.007. Furthermore, the limits of detection (LODs) for acetone are 180 pptv within 1 s of averaging time and 580 pptv within only 100 ms.

  11. A simple and rapid method for high-resolution visualization of single-ion tracks

    Directory of Open Access Journals (Sweden)

    Masaaki Omichi

    2014-11-01

    Full Text Available Prompt determination of spatial points of single-ion tracks plays a key role in high-energy particle induced-cancer therapy and gene/plant mutations. In this study, a simple method for the high-resolution visualization of single-ion tracks without etching was developed through the use of polyacrylic acid (PAA-N, N’-methylene bisacrylamide (MBAAm blend films. One of the steps of the proposed method includes exposure of the irradiated films to water vapor for several minutes. Water vapor was found to promote the cross-linking reaction of PAA and MBAAm to form a bulky cross-linked structure; the ion-track scars were detectable at a nanometer scale by atomic force microscopy. This study demonstrated that each scar is easily distinguishable, and the amount of generated radicals of the ion tracks can be estimated by measuring the height of the scars, even in highly dense ion tracks. This method is suitable for the visualization of the penumbra region in a single-ion track with a high spatial resolution of 50 nm, which is sufficiently small to confirm that a single ion hits a cell nucleus with a size ranging between 5 and 20 μm.

  12. A simple and rapid method for high-resolution visualization of single-ion tracks

    Energy Technology Data Exchange (ETDEWEB)

    Omichi, Masaaki [Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871 (Japan); Center for Collaborative Research, Anan National College of Technology, Anan, Tokushima 774-0017 (Japan); Choi, Wookjin; Sakamaki, Daisuke; Seki, Shu, E-mail: seki@chem.eng.osaka-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871 (Japan); Tsukuda, Satoshi [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Miyagi 980-8577 (Japan); Sugimoto, Masaki [Japan Atomic Energy Agency, Takasaki Advanced Radiation Research Institute, Gunma, Gunma 370-1292 (Japan)

    2014-11-15

    Prompt determination of spatial points of single-ion tracks plays a key role in high-energy particle induced-cancer therapy and gene/plant mutations. In this study, a simple method for the high-resolution visualization of single-ion tracks without etching was developed through the use of polyacrylic acid (PAA)-N, N’-methylene bisacrylamide (MBAAm) blend films. One of the steps of the proposed method includes exposure of the irradiated films to water vapor for several minutes. Water vapor was found to promote the cross-linking reaction of PAA and MBAAm to form a bulky cross-linked structure; the ion-track scars were detectable at a nanometer scale by atomic force microscopy. This study demonstrated that each scar is easily distinguishable, and the amount of generated radicals of the ion tracks can be estimated by measuring the height of the scars, even in highly dense ion tracks. This method is suitable for the visualization of the penumbra region in a single-ion track with a high spatial resolution of 50 nm, which is sufficiently small to confirm that a single ion hits a cell nucleus with a size ranging between 5 and 20 μm.

  13. Characterization of flux-grown Trace-element-doped titanite using the high-mass-resolution ion microprobe (SHRIMP-RG)

    Science.gov (United States)

    Mazdab, F.K.

    2009-01-01

    Crystals of titanite can be readily grown under ambient pressure from a mixture of CaO, TiO2 and SiO2 in the presence of molten sodium tetraborate. The crystals produced are euhedral and prismatic, lustrous and transparent, and up to 5 mm in length. Titanite obtained by this method contains approximately 4300 ppm Na and 220 ppm B contributed from the flux. In addition to dopant-free material, titanite containing trace alkali and alkaline earth metals (K, Sr, Ba), transition metals (Sc, Cr, Ni, Y, Zr, Nb, Hf and Ta), rare-earth elements (REE), actinides (Th, U) and p-block elements (F, S, Cl, Ge, Sn and Pb) have been prepared using the same procedure. Back-scattered electron (BSE) imaging accompanied by ion-microprobe (SHRIMP-RG) analysis confirms significant incorporation of selected trace-elements at structural sites. Regardless of some zonation, the large size of the crystals and broad regions of chemical homogeneity make these crystals useful as experimental starting material, and as matrix-matched trace-element standards for a variety of microbeam analytical techniques where amorphous titanite glass, heterogeneous natural titanite or a non-titanite standard may be less than satisfactory. Trace-element-doped synthetic crystals can also provide a convenient proxy for a better understanding of trace-element incorporation in natural titanite. Comparisons with igneous, authigenic and high-temperature metasomatic titanite are examined. The use of high-mass-resolution SIMS also demonstrates the analytical challenges inherent to any in situ mass-spectrometry-based analysis of titanite, owing to the production of difficult-to-resolve molecular interferences. These interferences are dominated by Ca-Ca, Ca-Ti and Ti-Ti dimers that are significant in the mass range of 80-100, affecting all isotopes of Sr and Zr, as well as 89Y and 93Nb. Methods do exist for the evaluation of interferences by these dimers and of polyatomic interferences on the LREE.

  14. Negative-Ion source for mass selective photodetachment photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Kaesmaier, R.; Baemann, C.; Drechsler, G.; Boesl, U.

    1995-01-01

    We have designed and constructed a negative ion source for mass spectrometry and mass selective photodetachement photoelectron spectroscopy. The characteristics of the source are high anion densities and a large variety of accessible systems. Thus, mass spectra and photoelectron spectra of large unvolatile moelcules (biomolecules), of metal-organic compounds and of molecule water clusters, especially mentioned in this article, have been measured. Combining mass spectrometry, photoelectron spectroscopy (PES) and high resolution ZEKE (zero kinetic energy)-PES (1) should make the apparatus to an ideal diagnostic tool for structural assignment

  15. Screening of environmental contaminants in honey bee wax comb using gas chromatography-high-resolution time-of-flight mass spectrometry.

    Science.gov (United States)

    Gómez-Ramos, M M; García-Valcárcel, A I; Tadeo, J L; Fernández-Alba, A R; Hernando, M D

    2016-03-01

    This study reports an analytical approach intended to be used for investigation of non-targeted environmental contaminants and to characterize the organic pollution pattern of bee wax comb samples. The method comprises a generic extraction followed by detection with gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC-TOF-MS), operated in electron impact ionization (EI) mode. The screening approach for the investigation of non-targeted contaminants consisted of initial peak detection by deconvolution and matching the first-stage mass spectra EI-MS(1) with a nominal mass spectral library. To gain further confidence in the structural characterization of the contaminants under investigation, the molecular formula of representative ions (molecular ion when present in the EI spectrum) and, for at least other two fragment ions, was provided for those with an accurate mass scoring (mass error contaminants in 50 samples of bee wax comb. This approach has allowed the tentative identification of some GC-amenable contaminants belonging to different chemical groups, among them, phthalates and polycyclic aromatic hydrocarbons (PAHs), along with residues of veterinary treatments used in apiculture.

  16. Chlorinated paraffin analysis by gas chromatography Orbitrap high-resolution mass spectrometry: Method performance, investigation of possible interferences and analysis of fish samples.

    Science.gov (United States)

    Krätschmer, Kerstin; Cojocariu, Cristian; Schächtele, Alexander; Malisch, Rainer; Vetter, Walter

    2018-03-02

    For decades, high quantities of short-chain chlorinated paraffins (SCCP) and medium-chain chlorinated paraffins (MCCP) have been widely used, for instance as plasticizers or flame retardants, leading to global pollution due to unintentional emissions from products or waste. Due to the high complexity of chlorinated paraffins with several thousand congeners there is no consensus on an analytical procedure for SCCPs and MCCPs in food samples. Amongst the multitude of methods currently in use, high-resolution mass spectrometry is particularly valuable for in-depth studies of homologue patterns. Here we analyse SCCPs and MCCPs with gas chromatography coupled to high-resolution Orbitrap mass spectrometry (GC-Orbitrap-HRMS) operated in full-scan acquisition in electron capture negative ion (ECNI) mode at 60,000 and 120,000 resolution (FWHM, m/z 200, equals roughly 30,000 and 60,000 at 5% peak height). Linear dynamic range, selectivity and sensitivity tests confirmed an excellent linearity in a concentration range of 25-15,000 pg/μL with very low limits of detection (LODs) in the low pg/μL range. Spiking experiments with high levels of native mono- and di-ortho-polychlorinated biphenyls (PCBs) and mixtures of MCCP and SCCP standards did not have a negative impact on isotope ratios of the examined homologues. Besides the [M-Cl] - fragment ions used for quantification, the mass spectra of homologues also featured [M-HCl] - ions whose abundance increased with decreasing chlorination degree. In addition, [M-HCl-Cl] - ions were detected with a relative abundance of 5-10%. Three salmon (Salmo salar) samples farmed in Norway showed a consistent CP homologue pattern which differed both from the CP pattern in a sample from Scottish aquaculture and a wild salmon sample. These measurements produce evidence that discretely different CP patterns may exist in different areas of origin. Our results demonstrate that GC/ECNI-Orbitrap-HRMS is well-suited for the analysis of CPs by

  17. 'Applications of stable isotopes in life sciences'. Lead and strontium stable isotope measurements by using a high lateral resolution secondary ion mass spectrometer (NanoSIMS)

    International Nuclear Information System (INIS)

    Sano, Yuji

    2008-01-01

    The method of Pb and Sr isotope measurements at about 5 μm resolution was developed by using a high lateral resolution secondary ion mass spectrometer (NanoSIMS NS50). Since the both elements have radiogenic nuclides such as 206 Pb, 207 Pb, and 87 Sr, natural variations of isotopic ratios are large. It is possible to detect a meaningful variation in a terrestrial sample, even though the experimental error is relatively large. In the case of monazite U-Pb dating, a 4 nA O - primary beam was used to sputter the sample and secondary positive ions were extracted for mass analysis using a Mattauch-Herzog geometry. The multi-collector system was modified to detect 140 Ce + , 204 Pb + , 206 Pb + , 238 U 16 O + , and 238 U 16 O 2 + ions simultaneously. Based on the monazite standard from North-Central Madagascar, we have determined the 206 Pb/ 238 U ratios of samples. 207 Pb/ 206 Pb ratios were measured by a magnet scanning with a single collector mode. 44 monazite grains extracted from a sedimentary rock in Taiwan were analyzed. Observed ages were consistent with the U-Th-Pb chemical ages by EPMA. Then NanoSIMS has been used to measure 87 Sr/ 86 Sr ratios in natural calcium carbonate samples. Multi-collector system was adjusted to detect 43 Ca + , 80 Ca 2 + , 86 Sr + , and 87 Sr + ions at the same time. Magnetic field was scanning for the EM no.4 counter to detect 85 Rb + , 86 Sr + and 87 Sr + , while the EM no.4b can measure 86 Sr + , 87 Sr + , and 88 Sr + , respectively. Repeated analyses of a coral skeleton standard (JCp-1) show that 87 Sr/ 86 Sr ratio agrees well with the seawater signature, after the series of corrections such as Ca dimer, 87 Rb, and a mass bias estimated by 88 Sr/ 86 Sr ratio. The method is applied to an otolith from ayu (Pleco-glossus altivelis altivelis) collected from the Yodo river, Japan. The spatial variation of 87 Sr/ 86 Sr ratios was consistent with amphidromous migration of the fish, namely, born in the lake and grown in the coastal sea

  18. Yeast expression proteomics by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Walther, Tobias C; Olsen, Jesper Velgaard; Mann, Matthias

    2010-01-01

    -translational controls contribute majorly to regulation of protein abundance, for example in heat shock stress response. The development of new sample preparation methods, high-resolution mass spectrometry and novel bioinfomatic tools close this gap and allow the global quantitation of the yeast proteome under different...

  19. Structural Characterization of a Thrombin-Aptamer Complex by High Resolution Native Top-Down Mass Spectrometry

    Science.gov (United States)

    Zhang, Jiang; Loo, Rachel R. Ogorzalek; Loo, Joseph A.

    2017-09-01

    Native mass spectrometry (MS) with electrospray ionization (ESI) has evolved as an invaluable tool for the characterization of intact native proteins and non-covalently bound protein complexes. Here we report the structural characterization by high resolution native top-down MS of human thrombin and its complex with the Bock thrombin binding aptamer (TBA), a 15-nucleotide DNA with high specificity and affinity for thrombin. Accurate mass measurements revealed that the predominant form of native human α-thrombin contains a glycosylation mass of 2205 Da, corresponding to a sialylated symmetric biantennary oligosaccharide structure without fucosylation. Native MS showed that thrombin and TBA predominantly form a 1:1 complex under near physiological conditions (pH 6.8, 200 mM NH4OAc), but the binding stoichiometry is influenced by the solution ionic strength. In 20 mM ammonium acetate solution, up to two TBAs were bound to thrombin, whereas increasing the solution ionic strength destabilized the thrombin-TBA complex and 1 M NH4OAc nearly completely dissociated the complex. This observation is consistent with the mediation of thrombin-aptamer binding through electrostatic interactions and it is further consistent with the human thrombin structure that contains two anion binding sites on the surface. Electron capture dissociation (ECD) top-down MS of the thrombin-TBA complex performed with a high resolution 15 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer showed the primary binding site to be at exosite I located near the N-terminal sequence of the heavy chain, consistent with crystallographic data. High resolution native top-down MS is complementary to traditional structural biology methods for structurally characterizing native proteins and protein-DNA complexes. [Figure not available: see fulltext.

  20. Analysis of high mass resolution PTR-TOF mass spectra from 1,3,5-trimethylbenzene (TMB) environmental chamber experiments

    Science.gov (United States)

    Müller, M.; Graus, M.; Wisthaler, A.; Hansel, A.; Metzger, A.; Dommen, J.; Baltensperger, U.

    2012-01-01

    A series of 1,3,5-trimethylbenzene (TMB) photo-oxidation experiments was performed in the 27-m3 Paul Scherrer Institute environmental chamber under various NOx conditions. A University of Innsbruck prototype high resolution Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOF) was used for measurements of gas and particulate phase organics. The gas phase mass spectrum displayed ~200 ion signals during the TMB photo-oxidation experiments. Molecular formulas CmHnNoOp were determined and ion signals were separated and grouped according to their C, O and N numbers. This allowed to determine the time evolution of the O:C ratio and of the average carbon oxidation state solid #000; color: #000;">OSC of the reaction mixture. Both quantities were compared with master chemical mechanism (MCMv3.1) simulations. The O:C ratio in the particle phase was about twice the O:C ratio in the gas phase. Average carbon oxidation states of secondary organic aerosol (SOA) samples solid #000; color: #000;">OSCSOA were in the range of -0.34 to -0.31, in agreement with expected average carbon oxidation states of fresh SOA (solid #000; color: #000;">OSC = -0.5-0).

  1. High-performance multiple-reflection time-of-flight mass spectrometers for research with exotic nuclei and for analytical mass spectrometry

    Science.gov (United States)

    Plaß, Wolfgang R.; Dickel, Timo; Ayet San Andres, Samuel; Ebert, Jens; Greiner, Florian; Hornung, Christine; Jesch, Christian; Lang, Johannes; Lippert, Wayne; Majoros, Tamas; Short, Devin; Geissel, Hans; Haettner, Emma; Reiter, Moritz P.; Rink, Ann-Kathrin; Scheidenberger, Christoph; Yavor, Mikhail I.

    2015-11-01

    A class of multiple-reflection time-of-flight mass spectrometers (MR-TOF-MSs) has been developed for research with exotic nuclei at present and future accelerator facilities such as GSI and FAIR (Darmstadt), and TRIUMF (Vancouver). They can perform highly accurate mass measurements of exotic nuclei, serve as high-resolution, high-capacity mass separators and be employed as diagnostics devices to monitor the production, separation and manipulation of beams of exotic nuclei. In addition, a mobile high-resolution MR-TOF-MS has been developed for in situ applications in analytical mass spectrometry ranging from environmental research to medicine. Recently, the MR-TOF-MS for GSI and FAIR has been further developed. A novel RF quadrupole-based ion beam switchyard has been developed that allows merging and splitting of ion beams as well as transport of ions into different directions. It efficiently connects a test and reference ion source and an auxiliary detector to the system. Due to an increase in the kinetic energy of the ions in the time-of-flight analyzer of the MR-TOF-MS, a given mass resolving power is now achieved in less than half the time-of-flight. Conversely, depending on the time-of-flight, the mass resolving power has been increased by a factor of more than two.

  2. HCN Polymers: Toward Structure Comprehension Using High Resolution Mass Spectrometry

    Science.gov (United States)

    Bonnet, Jean-Yves; Thissen, Roland; Frisari, Ma; Vuitton, Veronique; Quirico, Eric; Le Roy, Léna; Fray, Nicolas; Cottin, Hervé; Horst, Sarah; Yelle, Roger

    A lot of solar system materials, including cometary ices and Titan aerosols, contain dark matter that can be interpreted as complex nitrogen bearing organic matter [1]. In laboratory experi-ments, HCN polymers are thus analogs of great interest. In fact they may be present in Titan atmosphere and in comet nuclei and then reprocessed as a CN distributed source [2], when ices began to sublimate and ejects from the nucleus organic matter grains [3]. The presence of HCN polymers is suggested because HCN molecule has been directly observed in 1P/Halley comet [4] and others. HCN polymers are also of prebiotic interest [5] as it can form amino acid under hydrolysis conditions. Even if they have been studied during the last decades, their chemical composition and structure are still poorly understood, and a great analytical effort has to be continued. In this way we present a high resolution mass spectrometry (HRMS) and a high resolution tandem mass spectrometry (MS/HRMS) analysis of HCN polymers. It was shown [6] that this is a suitable technique to elucidate composition and structure of the soluble part of tholins analogs of Titan's atmosphere aerosols. HCN polymers have never been studied by HRMS, thus we used a LTQ-Orbitrap XL high resolution mass spectrometer to analyse the HCN polymers. These are produced at LISA by direct polymerisation of pure liquid HCN, catalyzed by ammonia. HCN polymers have been completely dissolved in methanol and then injected in the mass spectrometer by ElectroSpray Ionization (ESI). This atmospheric pressure ionization process produces protonated or deprotonated ions, but it does not fragment molecules. Thus HRMS, allows a direct access to the stoechiometry of all the ionizable molecules present in the samples. Fragmentation analyses (MS/MS) of selected ions have also been performed. Thess analysis provide information about the different chemical fonctionnalities present in HCN poly-mers and also about their structure. Thus we are able to

  3. First high-statistics and high-resolution recoil-ion data from the WITCH retardation spectrometer

    Science.gov (United States)

    Finlay, P.; Breitenfeldt, M.; Porobić, T.; Wursten, E.; Ban, G.; Beck, M.; Couratin, C.; Fabian, X.; Fléchard, X.; Friedag, P.; Glück, F.; Herlert, A.; Knecht, A.; Kozlov, V. Y.; Liénard, E.; Soti, G.; Tandecki, M.; Traykov, E.; Van Gorp, S.; Weinheimer, Ch.; Zákoucký, D.; Severijns, N.

    2016-07-01

    The first high-statistics and high-resolution data set for the integrated recoil-ion energy spectrum following the β^+ decay of 35Ar has been collected with the WITCH retardation spectrometer located at CERN-ISOLDE. Over 25 million recoil-ion events were recorded on a large-area multichannel plate (MCP) detector with a time-stamp precision of 2ns and position resolution of 0.1mm due to the newly upgraded data acquisition based on the LPC Caen FASTER protocol. The number of recoil ions was measured for more than 15 different settings of the retardation potential, complemented by dedicated background and half-life measurements. Previously unidentified systematic effects, including an energy-dependent efficiency of the main MCP and a radiation-induced time-dependent background, have been identified and incorporated into the analysis. However, further understanding and treatment of the radiation-induced background requires additional dedicated measurements and remains the current limiting factor in extracting a beta-neutrino angular correlation coefficient for 35Ar decay using the WITCH spectrometer.

  4. On-line high-resolution mass spectroscopy. Progress report, July 1, 1975--July 1, 1976

    International Nuclear Information System (INIS)

    Macfarlane, R.D.; Torgerson, D.F.

    1976-08-01

    The search for second-class currents in nuclear beta decay continued with measurements of beta--gamma correlations for the mirror decays 20 F(β - ) 20 Ne*(1.63) and 20 Na(β + ) 20 Ne*(1.63). The 20 F beta--gamma correlation was measured in beam, and the results are being compared with values obtained using the He-jet method. A careful analysis of ion velocity distributions emitted from fission fragment tracks in solids yielded new information on the nature of the process. The temperature of the microplasma formed by a fission fragment was determined to be of the order 10 4 K, and the temperature is dependent on the fission fragment's energy. A mass reflectron is being developed for high mass resolution using time-of-flight mass spectroscopy. The application of 252 Cf-PDMS (plasma desorption mass spectroscopy) to new classes of involatile compounds continued. Techniques are being studied for the routine analysis of involatile species of mass greater than 2000. The report is basically descriptive in nature. 5 figures, 1 table

  5. Development of an Apparatus for High-Resolution Auger Photoelectron Coincidence Spectroscopy (APECS) and Electron Ion Coincidence (EICO) Spectroscopy

    Science.gov (United States)

    Kakiuchi, Takuhiro; Hashimoto, Shogo; Fujita, Narihiko; Mase, Kazuhiko; Tanaka, Masatoshi; Okusawa, Makoto

    We have developed an electron electron ion coincidence (EEICO) apparatus for high-resolution Auger photoelectron coincidence spectroscopy (APECS) and electron ion coincidence (EICO) spectroscopy. It consists of a coaxially symmetric mirror electron energy analyzer (ASMA), a miniature double-pass cylindrical mirror electron energy analyzer (DP-CMA), a miniature time-of-flight ion mass spectrometer (TOF-MS), a magnetic shield, an xyz stage, a tilt-adjustment mechanism, and a conflat flange with an outer diameter of 203 mm. A sample surface was irradiated by synchrotron radiation, and emitted electrons were energy-analyzed and detected by the ASMA and the DP-CMA, while desorbed ions were mass-analyzed and detected by the TOF-MS. The performance of the new EEICO analyzer was evaluated by measuring Si 2p photoelectron spectra of clean Si(001)-2×1 and Si(111)-7×7, and by measuring Si-L23VV-Si-2p Auger photoelectron coincidence spectra (Si-L23VV-Si-2p APECS) of clean Si(001)-2×1.

  6. SPIRAL2/DESIR high resolution mass separator

    Energy Technology Data Exchange (ETDEWEB)

    Kurtukian-Nieto, T., E-mail: kurtukia@cenbg.in2p3.fr [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Baartman, R. [TRIUMF, 4004 Wesbrook Mall, Vancouver B.C., V6T 2A3 (Canada); Blank, B.; Chiron, T. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Davids, C. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Delalee, F. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Duval, M. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); El Abbeir, S.; Fournier, A. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Lunney, D. [CSNSM-IN2P3-CNRS, Université de Paris Sud, F-91405 Orsay (France); Méot, F. [BNL, Upton, Long Island, New York (United States); Serani, L. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Stodel, M.-H.; Varenne, F. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); and others

    2013-12-15

    DESIR is the low-energy part of the SPIRAL2 ISOL facility under construction at GANIL. DESIR includes a high-resolution mass separator (HRS) with a designed resolving power m/Δm of 31,000 for a 1 π-mm-mrad beam emittance, obtained using a high-intensity beam cooling device. The proposed design consists of two 90-degree magnetic dipoles, complemented by electrostatic quadrupoles, sextupoles, and a multipole, arranged in a symmetric configuration to minimize aberrations. A detailed description of the design and results of extensive simulations are given.

  7. High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

    DEFF Research Database (Denmark)

    Andersen, Thomas; Jensen, Robert; Christensen, M. K.

    2012-01-01

    We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal...

  8. Ion mobility analyzer - quadrupole mass spectrometer system design

    International Nuclear Information System (INIS)

    Cuna, C; Leuca, M; Lupsa, N; Mirel, V; Cuna, Stela; Cosma, V; Tusa, Florina; Bocos-Bintintan, V

    2009-01-01

    Because of their extremely high sensitivity for chemicals with elevated electronegativity or high proton affinity the ion mobility analysers are ideal for the ultra-trace detection of toxic or explosive chemicals, most of these situated often at concentration levels of sub-ppb (parts-per-billion). Ion mobility spectrometers (IMS) can be used to identify illicit drugs or environmental pollutants. Since resolution of an IMS is relatively low, to achieve an accurate identification of target analyte it is recommended to couple the IMS with a quadrupole mass spectrometer (QMS) or a time of flight mass spectrometer, acquiring in this way confirmatory information. This coupling is made through a specific interface. In this paper, an experimental model of such a tandem instrument, IMS-QMS is described. Accomplishment of this general purpose will be done, overcoming a series of specific issues. This implies the solving, using innovative solutions, of a series of complex issues: ensuring the stability of the ions beam generated by ion source; transfer with a good efficiency of the ionic current from IMS analyser to QMS; and realization of a special electronic circuitry which will be able to detect both positive and negative ions.

  9. Ion mobility analyzer - quadrupole mass spectrometer system design

    Energy Technology Data Exchange (ETDEWEB)

    Cuna, C; Leuca, M; Lupsa, N; Mirel, V; Cuna, Stela; Cosma, V; Tusa, Florina [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Bocos-Bintintan, V, E-mail: cornel.cuna@itim-cj.r [Babes-Bolyai University, Faculty of Environmental Sciences, 3 Fantanele, 400294 Cluj Napoca (Romania)

    2009-08-01

    Because of their extremely high sensitivity for chemicals with elevated electronegativity or high proton affinity the ion mobility analysers are ideal for the ultra-trace detection of toxic or explosive chemicals, most of these situated often at concentration levels of sub-ppb (parts-per-billion). Ion mobility spectrometers (IMS) can be used to identify illicit drugs or environmental pollutants. Since resolution of an IMS is relatively low, to achieve an accurate identification of target analyte it is recommended to couple the IMS with a quadrupole mass spectrometer (QMS) or a time of flight mass spectrometer, acquiring in this way confirmatory information. This coupling is made through a specific interface. In this paper, an experimental model of such a tandem instrument, IMS-QMS is described. Accomplishment of this general purpose will be done, overcoming a series of specific issues. This implies the solving, using innovative solutions, of a series of complex issues: ensuring the stability of the ions beam generated by ion source; transfer with a good efficiency of the ionic current from IMS analyser to QMS; and realization of a special electronic circuitry which will be able to detect both positive and negative ions.

  10. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies

    International Nuclear Information System (INIS)

    Schowalter, Steven J.; Chen Kuang; Rellergert, Wade G.; Sullivan, Scott T.; Hudson, Eric R.

    2012-01-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates.

  11. High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal.

    Science.gov (United States)

    Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Haskey, S R; Kaplan, D H

    2016-11-01

    A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. The unique combination of experimentally measured main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.

  12. Application of High-Performance Liquid Chromatography Coupled with Linear Ion Trap Quadrupole Orbitrap Mass Spectrometry for Qualitative and Quantitative Assessment of Shejin-Liyan Granule Supplements

    OpenAIRE

    Jifeng Gu; Weijun Wu; Mengwei Huang; Fen Long; Xinhua Liu; Yizhun Zhu

    2018-01-01

    A method for high-performance liquid chromatography coupled with linear ion trap quadrupole Orbitrap high-resolution mass spectrometry (HPLC-LTQ-Orbitrap MS) was developed and validated for the qualitative and quantitative assessment of Shejin-liyan Granule. According to the fragmentation mechanism and high-resolution MS data, 54 compounds, including fourteen isoflavones, eleven ligands, eight flavonoids, six physalins, six organic acids, four triterpenoid saponins, two xanthones, two alkaloi...

  13. High resolution study of high mass pairs and high transverse momentum particles

    International Nuclear Information System (INIS)

    Smith, S.R.

    1983-01-01

    Preliminary experiments involving the high resolution spectrometer (experiment 605) at Fermilab are described. The spectrometer is designed for the study of pairs of particles at large invariant masses and single particles at large transverse momenta. A number of applications of the apparatus in the study of Drell-Yan processes, e.g. transverse momentum measurement, are discussed

  14. Linear mass reflectron

    International Nuclear Information System (INIS)

    Mamyrin, B.A.; Shmikk, D.V.

    1979-01-01

    A description and operating principle of a linear mass reflectron with V-form trajectory of ion motion -a new non-magnetic time-of-flight mass spectrometer with high resolution are presented. The ion-optical system of the device consists of an ion source with ionization by electron shock, of accelerating gaps, reflector gaps, a drift space and ion detector. Ions move in the linear mass refraction along the trajectories parallel to the axis of the analyzer chamber. The results of investigations into the experimental device are given. With an ion drift length of 0.6 m the device resolution is 1200 with respect to the peak width at half-height. Small-sized mass spectrometric transducers with high resolution and sensitivity may be designed on the base of the linear mass reflectron principle

  15. Characterization of Fumonisin A-Series by High-Resolution Liquid Chromatography-Orbitrap Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Masayoshi Tamura

    2014-08-01

    Full Text Available Fumonisin A-series (FAs in a reference material of corn sample that was naturally contaminated with fumonisins was characterized using high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitap MS. Peaks for fumonisin B1 (FB1, fumonisin B2 (FB2, and fumonisin B3 (FB3, in addition to three peaks corresponding to unknown compounds I, II, and III, were detected in the chromatogram for the corn sample. Fragment ion analysis for FB1, FB2, and FB3 showed that while the ions formed at m/z values of 200–800 were similar to those formed by the cleavage of the tricarballylic acids and the hydroxyl groups, the fragmentation patterns at m/z values of 50–200 varied depending on the hydroxyl group locations in the compounds. Fragment ion analysis of compounds I–III revealed structural similarities to FBs, only differing by an additional C2H2O in the unknown compounds. Using these results and by comparing the product ion mass spectra of compound I with fumonisin A1 (FA1 synthesized from FB1 standards, compounds I–III were hypothesized to be N-acetyl analogs of FBs: fumonisins A1 (FA1, A2 (FA2, and A3 (FA3. The method for determining concentrations was validated with FA1, FB1, FB2, and FB3 standards and applied to analyze the reference material. The FB1, FB2, and FB3 analytical levels were within acceptance limits and the amount of FA1 in the material was ~15% of FB1 amount at 4.2 mg/kg.

  16. Characterization of fumonisin A-series by high-resolution liquid chromatography-orbitrap mass spectrometry.

    Science.gov (United States)

    Tamura, Masayoshi; Mochizuki, Naoki; Nagatomi, Yasushi; Toriba, Akira; Hayakawa, Kazuichi

    2014-08-21

    Fumonisin A-series (FAs) in a reference material of corn sample that was naturally contaminated with fumonisins was characterized using high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitap MS). Peaks for fumonisin B1 (FB1), fumonisin B2 (FB2), and fumonisin B3 (FB3), in addition to three peaks corresponding to unknown compounds I, II, and III, were detected in the chromatogram for the corn sample. Fragment ion analysis for FB1, FB2, and FB3 showed that while the ions formed at m/z values of 200-800 were similar to those formed by the cleavage of the tricarballylic acids and the hydroxyl groups, the fragmentation patterns at m/z values of 50-200 varied depending on the hydroxyl group locations in the compounds. Fragment ion analysis of compounds I-III revealed structural similarities to FBs, only differing by an additional C2H2O in the unknown compounds. Using these results and by comparing the product ion mass spectra of compound I with fumonisin A1 (FA1) synthesized from FB1 standards, compounds I-III were hypothesized to be N-acetyl analogs of FBs: fumonisins A1 (FA1), A2 (FA2), and A3 (FA3). The method for determining concentrations was validated with FA1, FB1, FB2, and FB3 standards and applied to analyze the reference material. The FB1, FB2, and FB3 analytical levels were within acceptance limits and the amount of FA1 in the material was ~15% of FB1 amount at 4.2 mg/kg.

  17. Limitations to depth resolution in high-energy, heavy-ion elastic recoil detection analysis

    International Nuclear Information System (INIS)

    Elliman, R.G.; Palmer, G.R.; Ophel, T.R.; Timmers, H.

    1998-01-01

    The depth resolution of heavy-ion elastic recoil detection analysis was examined for Al and Co thin films ranging in thickness from 100 to 400 nm. Measurements were performed with 154 MeV Au ions as the incident beam, and recoils were detected using a gas ionisation detector. Energy spectra were extracted for the Al and Co recoils and the depth resolution determined as a function of film thickness from the width of the high- and low- energy edges. These results were compared with theoretical estimates calculated using the computer program DEPTH. (authors)

  18. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies.

    Science.gov (United States)

    Schowalter, Steven J; Chen, Kuang; Rellergert, Wade G; Sullivan, Scott T; Hudson, Eric R

    2012-04-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates. © 2012 American Institute of Physics

  19. Structural characterization of phospholipids by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Marto, J A; White, F M; Seldomridge, S; Marshall, A G

    1995-11-01

    Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode.

  20. Differentiating Fragmentation Pathways of Cholesterol by Two-Dimensional Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

    Science.gov (United States)

    van Agthoven, Maria A; Barrow, Mark P; Chiron, Lionel; Coutouly, Marie-Aude; Kilgour, David; Wootton, Christopher A; Wei, Juan; Soulby, Andrew; Delsuc, Marc-André; Rolando, Christian; O'Connor, Peter B

    2015-12-01

    Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry is a data-independent analytical method that records the fragmentation patterns of all the compounds in a sample. This study shows the implementation of atmospheric pressure photoionization with two-dimensional (2D) Fourier transform ion cyclotron resonance mass spectrometry. In the resulting 2D mass spectrum, the fragmentation patterns of the radical and protonated species from cholesterol are differentiated. This study shows the use of fragment ion lines, precursor ion lines, and neutral loss lines in the 2D mass spectrum to determine fragmentation mechanisms of known compounds and to gain information on unknown ion species in the spectrum. In concert with high resolution mass spectrometry, 2D Fourier transform ion cyclotron resonance mass spectrometry can be a useful tool for the structural analysis of small molecules. Graphical Abstract ᅟ.

  1. High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation

    DEFF Research Database (Denmark)

    Dimzon, Ian Ken; Trier, Xenia; Frömel, Tobias

    2016-01-01

    High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid o......-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health. Graphical Abstract ᅟ....

  2. U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

    Science.gov (United States)

    Bischoff, J.L.; Wooden, J.; Murphy, F.; Williams, Ross W.

    2005-01-01

    We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ???60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few ??m deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems. Copyright ?? 2005 Elsevier Ltd.

  3. A high brightness source for nano-probe secondary ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smith, N.S. [Oregon Physics LLC, 2704 SE 39th Loop, Suite 109, Hillsboro, OR 97123 (United States)], E-mail: n.smith@oregon-physics.com; Tesch, P.P.; Martin, N.P.; Kinion, D.E. [Oregon Physics LLC, 2704 SE 39th Loop, Suite 109, Hillsboro, OR 97123 (United States)

    2008-12-15

    The two most prevalent ion source technologies in the field of surface analysis and surface machining are the Duoplasmatron and the liquid metal ion source (LMIS). There have been many efforts in this area of research to develop an alternative source [; N.S. Smith, W.P. Skoczylas, S.M. Kellogg, D.E. Kinion, P.P. Tesch, O. Sutherland, A. Aanesland, R.W. Boswell, J. Vac. Sci. Technol. B 24 (6) (2006) 2902-2906] with the brightness of a LMIS and yet the ability to produce secondary ion yield enhancing species such as oxygen. However, to date a viable alternative has not been realized. The high brightness and small virtual source size of the LMIS are advantageous for forming high resolution probes but a significant disadvantage when beam currents in excess of 100 nA are required, due to the effects of spherical aberration from the optical column. At these higher currents a source with a high angular intensity is optimal and in fact the relatively moderate brightness of today's plasma ion sources prevail in this operating regime. Both the LMIS and Duoplasmatron suffer from a large axial energy spread resulting in further limitations when forming focused beams at the chromatic limit where the figure-of-merit is inversely proportional to the square of the energy spread. Also, both of these ion sources operate with a very limited range of ion species. This article reviews some of the latest developments and some future potential in this area of instrument development. Here we present an approach to source development that could lead to oxygen ion beam SIMS imaging with 10 nm resolution, using a 'broad area' RF gas phase ion source.

  4. Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

    Science.gov (United States)

    Zheng, Jun; Yang, Dongsen; Ma, Yan; Chen, Mindong; Cheng, Jin; Li, Shizheng; Wang, Ming

    2015-10-01

    A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3-) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3- ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4- signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3-ṡ(H2O)2 (m/z 97.014) and O-ṡH2OṡHNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm-3 gaseous H2SO4 and 0.5 μg m-3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.

  5. Characterization of Athabasca lean oil sands and mixed surficial materials: Comparison of capillary electrophoresis/low-resolution mass spectrometry and high-resolution mass spectrometry.

    Science.gov (United States)

    MacLennan, Matthew S; Peru, Kerry M; Swyngedouw, Chris; Fleming, Ian; Chen, David D Y; Headley, John V

    2018-05-15

    Oil sands mining in Alberta, Canada, requires removal and stockpiling of considerable volumes of near-surface overburden material. This overburden includes lean oil sands (LOS) which cannot be processed economically but contain sparingly soluble petroleum hydrocarbons and naphthenic acids, which can leach into environmental waters. In order to measure and track the leaching of dissolved constituents and distinguish industrially derived organics from naturally occurring organics in local waters, practical methods were developed for characterizing multiple sources of contaminated water leakage. Capillary electrophoresis/positive-ion electrospray ionization low-resolution time-of-flight mass spectrometry (CE/LRMS), high-resolution negative-ion electrospray ionization Orbitrap mass spectrometry (HRMS) and conventional gas chromatography/flame ionization detection (GC/FID) were used to characterize porewater samples collected from within Athabasca LOS and mixed surficial materials. GC/FID was used to measure total petroleum hydrocarbon and HRMS was used to measure total naphthenic acid fraction components (NAFCs). HRMS and CE/LRMS were used to characterize samples according to source. The amounts of total petroleum hydrocarbon in each sample as measured by GC/FID ranged from 0.1 to 15.1 mg/L while the amounts of NAFCs as measured by HRMS ranged from 5.3 to 82.3 mg/L. Factors analysis (FA) on HRMS data visually demonstrated clustering according to sample source and was correlated to molecular formula. LRMS coupled to capillary electrophoresis separation (CE/LRMS) provides important information on NAFC isomers by adding analyte migration time data to m/z and peak intensity. Differences in measured amounts of total petroleum hydrocarbons by GC/FID and NAFCs by HRMS indicate that the two methods provide complementary information about the nature of dissolved organic species in a soil or water leachate samples. NAFC molecule class O x S y is a possible tracer for LOS

  6. The coupling of supercritical fluid chromatography and field ionization time-of-flight high-resolution mass spectrometry for rapid and quantitative analysis of petroleum middle distillates.

    Science.gov (United States)

    Qian, Kuangnan; Diehl, John W; Dechert, Gary J; DiSanzo, Frank P

    2004-01-01

    We report the first coupling of supercritical fluid chromatography (SFC) with field ionization time-of-flight high-resolution mass spectrometry (FI-ToF HRMS), in parallel with ultraviolet (UV) detection and flame ionization detection (FID), for rapid and quantitative analysis of petroleum middle distillates. SFC separates petroleum middle distillates into saturates and 1- to 3-ring aromatics. FI generates molecular ions for hydrocarbon species eluted from the SFC. The high resolution and exact mass measurements by ToF mass spectrometry provide elemental compositions of the molecules in the petroleum product. The amounts of saturates and aromatic ring types were quantified using the parallel SFC-FID assisted by SFC-UV. With a proper carbon-number calibration, the detailed composition of the petroleum middle distillate was rapidly determined.

  7. Electrochemistry-High Resolution Mass Spectrometry to Study Oxidation Products of Trimethoprim

    Directory of Open Access Journals (Sweden)

    Marc-André Lecours

    2018-01-01

    Full Text Available The study of the fate of emerging organic contaminants (EOCs, especially the identification of transformation products, after water treatment or in the aquatic environment, is a topic of growing interest. In recent years, electrochemistry coupled to mass spectrometry has attracted a lot of attention as an alternative technique to investigate oxidation metabolites of organic compounds. The present study used different electrochemical approaches, such as cyclic voltammetry, electrolysis, electro-assisted Fenton reaction coupled offline to high resolution mass spectrometry and thin-layer flow cell coupled online to high resolution mass spectrometry, to study oxidation products of the anti-infective trimethoprim, a contaminant of emerging concern frequently reported in wastewaters and surface waters. Results showed that mono- and di-hydroxylated derivatives of trimethoprim were generated in electrochemically and possibly tri-hydroxylated derivatives as well. Those compounds have been previously reported as mammalian and bacterial metabolites as well as transformation products of advance oxidation processes applied to waters containing trimethoprim. Therefore, this study confirmed that electrochemical techniques are relevant not only to mimic specific biotransformation reactions of organic contaminants, as it has been suggested previously, but also to study the oxidation reactions of organic contaminants of interest in water treatment. The key role that redox reactions play in the environment make electrochemistry-high resolution mass spectrometry a sensitive and simple technique to improve our understanding of the fate of organic contaminants in the environment.

  8. Validation of the Mass-Extraction-Window for Quantitative Methods Using Liquid Chromatography High Resolution Mass Spectrometry.

    Science.gov (United States)

    Glauser, Gaétan; Grund, Baptiste; Gassner, Anne-Laure; Menin, Laure; Henry, Hugues; Bromirski, Maciej; Schütz, Frédéric; McMullen, Justin; Rochat, Bertrand

    2016-03-15

    A paradigm shift is underway in the field of quantitative liquid chromatography-mass spectrometry (LC-MS) analysis thanks to the arrival of recent high-resolution mass spectrometers (HRMS). The capability of HRMS to perform sensitive and reliable quantifications of a large variety of analytes in HR-full scan mode is showing that it is now realistic to perform quantitative and qualitative analysis with the same instrument. Moreover, HR-full scan acquisition offers a global view of sample extracts and allows retrospective investigations as virtually all ionized compounds are detected with a high sensitivity. In time, the versatility of HRMS together with the increasing need for relative quantification of hundreds of endogenous metabolites should promote a shift from triple-quadrupole MS to HRMS. However, a current "pitfall" in quantitative LC-HRMS analysis is the lack of HRMS-specific guidance for validated quantitative analyses. Indeed, false positive and false negative HRMS detections are rare, albeit possible, if inadequate parameters are used. Here, we investigated two key parameters for the validation of LC-HRMS quantitative analyses: the mass accuracy (MA) and the mass-extraction-window (MEW) that is used to construct the extracted-ion-chromatograms. We propose MA-parameters, graphs, and equations to calculate rational MEW width for the validation of quantitative LC-HRMS methods. MA measurements were performed on four different LC-HRMS platforms. Experimentally determined MEW values ranged between 5.6 and 16.5 ppm and depended on the HRMS platform, its working environment, the calibration procedure, and the analyte considered. The proposed procedure provides a fit-for-purpose MEW determination and prevents false detections.

  9. A Computational Drug Metabolite Detection Using the Stable Isotopic Mass-Shift Filtering with High Resolution Mass Spectrometry in Pioglitazone and Flurbiprofen

    Directory of Open Access Journals (Sweden)

    Yohei Miyamoto

    2013-09-01

    Full Text Available The identification of metabolites in drug discovery is important. At present, radioisotopes and mass spectrometry are both widely used. However, rapid and comprehensive identification is still laborious and difficult. In this study, we developed new analytical software and employed a stable isotope as a tool to identify drug metabolites using mass spectrometry. A deuterium-labeled compound and non-labeled compound were both metabolized in human liver microsomes and analyzed by liquid chromatography/time-of-flight mass spectrometry (LC-TOF-MS. We computationally aligned two different MS data sets and filtered ions having a specific mass-shift equal to masses of labeled isotopes between those data using our own software. For pioglitazone and flurbiprofen, eight and four metabolites, respectively, were identified with calculations of mass and formulas and chemical structural fragmentation analysis. With high resolution MS, the approach became more accurate. The approach detected two unexpected metabolites in pioglitazone, i.e., the hydroxypropanamide form and the aldehyde hydrolysis form, which other approaches such as metabolite-biotransformation list matching and mass defect filtering could not detect. We demonstrated that the approach using computational alignment and stable isotopic mass-shift filtering has the ability to identify drug metabolites and is useful in drug discovery.

  10. Characterization of the designer drug deschloroketamine (2-methylamino-2-phenylcyclohexanone) by gas chromatography/mass spectrometry, liquid chromatography/high-resolution mass spectrometry, multistage mass spectrometry, and nuclear magnetic resonance.

    Science.gov (United States)

    Frison, Giampietro; Zamengo, Luca; Zancanaro, Flavio; Tisato, Francesco; Traldi, Pietro

    2016-01-15

    Clinical and forensic toxicology laboratories are challenged every day by the analytical aspects of the new psychoactive substances phenomenon. In this study we describe the analytical characterization of a new ketamine derivative, deschloroketamine (2-methylamino-2-phenylcyclohexanone), contained in seized powders. The analytical techniques employed include gas chromatography/mass spectrometry (GC/MS), liquid chromatography/electrospray ionization coupled with Orbitrap high-resolution/MS (LC/ESI-HRMS), multistage MS (ESI-MS(n)), and NMR. The LC/ESI-HRMS analyses consisted of accurate mass measurements of MH(+) ions in full-scan mode; comparison of experimental and calculated MH(+) isotopic patterns; and examination of the isotopic fine structure (IFS) of the M + 1, M + 2, M + 3 isotopic peaks relative to the monoisotopic M + 0 peak. The collision-induced product ions of the MH(+) ions were studied by both HRMS and MS(n). (1)H and (13)C NMR measurements were carried out to confirm the chemical structure of the analyte. The EI mass spectra obtained by GC/MS analysis showed the presence of molecular ions at m/z 203, and main fragment ions at m/z 175, 174, 160, 147, 146, and 132. The application of LC/ESI-HRMS allowed us to obtain: the accurate mass of deschloroketamine MH(+) ions with a mass accuracy of 1.47 ppm; fully superimposable experimental and calculated MH(+) isotopic patterns, with a relative isotopic abundance value of 3.69 %; and the IFS of the M + 1, M + 2, M + 3 isotopic peaks completely in accordance with theoretical values. Examination of the product ions of MH(+), as well as the study of both (1)H and (13)C NMR spectra, enabled the full characterization of the molecular structure of deschloroketamine. The combination of the employed analytical techniques allowed the characterization of the seized psychoactive substance, in spite of the lack of a reference standard. Deschloroketamine is a ketamine analogue considered to be

  11. Radio-frequency ion deflector for mass separation

    Energy Technology Data Exchange (ETDEWEB)

    Schlösser, Magnus, E-mail: magnus.schloesser@googlemail.com; Rudnev, Vitaly; Ureña, Ángel González, E-mail: laseres@pluri.ucm.es [Unidad de Láseres y Haces Moleculares, Instituto Plurisdisciplinar, Universidad Complutense de Madrid, Madrid 28040 (Spain)

    2015-10-15

    Electrostatic cylindrical deflectors act as energy analyzer for ion beams. In this article, we present that by imposing of a radio-frequency modulation on the deflecting electric field, the ion transmission becomes mass dependent. By the choice of the appropriate frequency, amplitude, and phase, the deflector can be used as mass filter. The basic concept of the new instrument as well as simple mathematic relations are described. These calculations and further numerical simulations show that a mass sensitivity is achievable. Furthermore, we demonstrate the proof-of-principle in experimental measurements, compare the results to those of from a 1 m linear time-of-flight spectrometer, and comment on the mass resolution of the method. Finally, some potential applications are indicated.

  12. Atmospheric Oxidation of Squalene: Molecular Study Using COBRA Modeling and High-Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Fooshee, David R.; Aiona, Paige K.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey; Baldi, Pierre

    2015-10-22

    Squalene is a major component of skin and plant surface lipids, and is known to be present at high concentrations in indoor dust. Its high reactivity toward ozone makes it an important ozone sink and a natural protectant against atmospheric oxidizing agents. While the volatile products of squalene ozonolysis are known, the condensed-phase products have not been characterized. We present an analysis of condensed-phase products resulting from an extensive oxidation of squalene by ozone probed by electrospray ionization (ESI) high-resolution mass spectrometry (HR-MS). A complex distribution of nearly 1,300 peaks assignable to molecular formulas is observed in direct infusion positive ion mode ESI mass spectra. The distribution of peaks in the mass spectra suggests that there are extensive cross-coupling reactions between hydroxy-carbonyl products of squalene ozonolysis. To get additional insights into the mechanism, we apply a Computational Brewing Application (COBRA) to simulate the oxidation of squalene in the presence of ozone, and compare predicted results with those observed by the HR-MS experiments. The system predicts over one billion molecular structures between 0-1450 Da, which correspond to about 27,000 distinct elemental formulas. Over 83% of the squalene oxidation products inferred from the mass spectrometry data are matched by the simulation. Simulation indicates a prevalence of peroxy groups, with hydroxyl and ether groups being the second-most important O-containing functional groups formed during squalene oxidation. These highly oxidized products of squalene ozonolysis may accumulate on indoor dust and surfaces, and contribute to their redox capacity.

  13. Precision mass measurements using the Phase-Imaging Ion-Cyclotron-Resonance detection technique

    CERN Document Server

    Karthein, Jonas

    This thesis presents the implementation and improvement of the Phase-Imaging Ion-Cyclotron-Resonance (PI-ICR) detection technique at the ISOLTRAP experiment, located at the ISOLDE / CERN, with the purpose of on-line high-precision and high-resolution mass spectrometry. Extensive simulation studies were performed with the aim of improving the phase-imaging resolution and finding the optimal position for detector placement. Following the outcome of these simulations, the detector was moved out of a region of electric-field distortion and closer to the center of the Penning trap, showing a dramatic improvement in the quality and reproducibility of the phase-imaging measurements. A new image reconstitution and analysis software for the MCP-PS detector was written in Python and ROOT and introduced in the framework of PI-ICR mass measurements. The state of the art in the field of time-of-flight ion-cyclotron-resonance measurements is illustrated through an analysis of on-line measurements of the mirror nuclei $...

  14. Fourier Transform Mass Spectrometry.

    Science.gov (United States)

    Gross, Michael L.; Rempel, Don L.

    1984-01-01

    Discusses the nature of Fourier transform mass spectrometry and its unique combination of high mass resolution, high upper mass limit, and multichannel advantage. Examines its operation, capabilities and limitations, applications (ion storage, ion manipulation, ion chemistry), and future applications and developments. (JN)

  15. High time resolution characteristics of intermediate ion distributions upstream of the earth's bow shock

    Science.gov (United States)

    Potter, D. W.

    1985-01-01

    High time resolution particle data upstream of the bow shock during time intervals that have been identified as having intermediate ion distributions often show high amplitude oscillations in the ion fluxes of energy 2 and 6 keV. These ion oscillations, observed with the particle instruments of the University of California, Berkeley, on the ISEE 1 and 2 spacecraft, are at the same frequency (about 0.04 Hz) as the magnetic field oscillations. Typically, the 6-keV ion flux increases then the 2-keV flux increases followed by a decrease in the 2-keV flux and then the 6-keV flux decreases. This process repeats many times. Although there is no entirely satisfactory explanation, the presence of these ion flux oscillations suggests that distributions often are misidentified as intermediate ion distributions.

  16. Structural characterization of ether lipids from the archaeon Sulfolobus islandicus by high-resolution shotgun lipidomics

    DEFF Research Database (Denmark)

    Jensen, Sara Munk; Brandl, Martin; Treusch, Alexander H

    2015-01-01

    The molecular structures, biosynthetic pathways and physiological functions of membrane lipids produced by organisms in the domain Archaea are poorly characterized as compared with that of counterparts in Bacteria and Eukaryota. Here we report on the use of high-resolution shotgun lipidomics......-resolution Fourier transform mass spectrometry using an ion trap-orbitrap mass spectrometer. This analysis identified five clusters of molecular ions that matched ether lipids in the database with sub-ppm mass accuracy. To structurally characterize and validate the identities of the potential lipid species, we...... performed structural analysis using multistage activation on the ion trap-orbitrap instrument as well as tandem mass analysis using a quadrupole time-of-flight machine. Our analysis identified four ether lipid species previously reported in Archaea, and one ether lipid species that had not been described...

  17. An introduction to the technique of combined ion mobility spectrometry-mass spectrometry for the analysis of complex biological samples

    International Nuclear Information System (INIS)

    McDowall, Mark A.; Bateman, Robert H.; Bajic, Steve; Giles, Kevin; Langridge, Jim; McKenna, Therese; Pringle, Steven D.; Wildgoose, Jason L.

    2008-01-01

    Full Text: Ultra Performance Liquid Chromatography (UPLC) offers several advantages compared with conventional High Performance Liquid Chromatography (HPLC) as an 'inlet system' for mass spectrometry. UPLC provides improved chromatographic resolution, increased sensitivity and reduced analysis time. This is achieved through the use of sub 2μm particles (stationary phase) combined with high-pressure solvent delivery (up to 15,000 psi). When coupled with orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (MS), UPLC presents a means to achieve high sample throughput with reduced spectral overlap, increased sensitivity, and exact mass measurement capabilities with high mass spectral resolution (Ca 20,000 FWHM). Dispersive ion mobility spectrometry (IMS) implemented within a traveling-wave ion guide provides an orthogonal separation strategy for ions in the gas phase that can resolve isobaric ions formed by either Electrospray of MALDI ionization typically in Ca 20 mille seconds. All three techniques have the potential to be combined on-line (e.g. UPLC-IMS-MS/MS) in real time to maximize peak capacity and resolving power for the analysis of complex biological mixtures including; intact proteins, modified peptides and endogenous/exogenous metabolites

  18. Extension of least squares spectral resolution algorithm to high-resolution lipidomics data

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Ying-Xu [Department of Chemistry, University of Bergen, PO Box 7803, N-5020 Bergen (Norway); Mjøs, Svein Are, E-mail: svein.mjos@kj.uib.no [Department of Chemistry, University of Bergen, PO Box 7803, N-5020 Bergen (Norway); David, Fabrice P.A. [Bioinformatics and Biostatistics Core Facility, School of Life Sciences, Ecole Polytechnique Fédérale de Lausanne (EPFL) and Swiss Institute of Bioinformatics (SIB), Lausanne (Switzerland); Schmid, Adrien W. [Proteomics Core Facility, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland)

    2016-03-31

    Lipidomics, which focuses on the global study of molecular lipids in biological systems, has been driven tremendously by technical advances in mass spectrometry (MS) instrumentation, particularly high-resolution MS. This requires powerful computational tools that handle the high-throughput lipidomics data analysis. To address this issue, a novel computational tool has been developed for the analysis of high-resolution MS data, including the data pretreatment, visualization, automated identification, deconvolution and quantification of lipid species. The algorithm features the customized generation of a lipid compound library and mass spectral library, which covers the major lipid classes such as glycerolipids, glycerophospholipids and sphingolipids. Next, the algorithm performs least squares resolution of spectra and chromatograms based on the theoretical isotope distribution of molecular ions, which enables automated identification and quantification of molecular lipid species. Currently, this methodology supports analysis of both high and low resolution MS as well as liquid chromatography-MS (LC-MS) lipidomics data. The flexibility of the methodology allows it to be expanded to support more lipid classes and more data interpretation functions, making it a promising tool in lipidomic data analysis. - Highlights: • A flexible strategy for analyzing MS and LC-MS data of lipid molecules is proposed. • Isotope distribution spectra of theoretically possible compounds were generated. • High resolution MS and LC-MS data were resolved by least squares spectral resolution. • The method proposed compounds that are likely to occur in the analyzed samples. • The proposed compounds matched results from manual interpretation of fragment spectra.

  19. Extension of least squares spectral resolution algorithm to high-resolution lipidomics data

    International Nuclear Information System (INIS)

    Zeng, Ying-Xu; Mjøs, Svein Are; David, Fabrice P.A.; Schmid, Adrien W.

    2016-01-01

    Lipidomics, which focuses on the global study of molecular lipids in biological systems, has been driven tremendously by technical advances in mass spectrometry (MS) instrumentation, particularly high-resolution MS. This requires powerful computational tools that handle the high-throughput lipidomics data analysis. To address this issue, a novel computational tool has been developed for the analysis of high-resolution MS data, including the data pretreatment, visualization, automated identification, deconvolution and quantification of lipid species. The algorithm features the customized generation of a lipid compound library and mass spectral library, which covers the major lipid classes such as glycerolipids, glycerophospholipids and sphingolipids. Next, the algorithm performs least squares resolution of spectra and chromatograms based on the theoretical isotope distribution of molecular ions, which enables automated identification and quantification of molecular lipid species. Currently, this methodology supports analysis of both high and low resolution MS as well as liquid chromatography-MS (LC-MS) lipidomics data. The flexibility of the methodology allows it to be expanded to support more lipid classes and more data interpretation functions, making it a promising tool in lipidomic data analysis. - Highlights: • A flexible strategy for analyzing MS and LC-MS data of lipid molecules is proposed. • Isotope distribution spectra of theoretically possible compounds were generated. • High resolution MS and LC-MS data were resolved by least squares spectral resolution. • The method proposed compounds that are likely to occur in the analyzed samples. • The proposed compounds matched results from manual interpretation of fragment spectra.

  20. ANL high resolution injector

    International Nuclear Information System (INIS)

    Minehara, E.; Kutschera, W.; Hartog, P.D.; Billquist, P.

    1985-01-01

    The ANL (Argonne National Laboratory) high-resolution injector has been installed to obtain higher mass resolution and higher preacceleration, and to utilize effectively the full mass range of ATLAS (Argonne Tandem Linac Accelerator System). Preliminary results of the first beam test are reported briefly. The design and performance, in particular a high-mass-resolution magnet with aberration compensation, are discussed. 7 refs., 5 figs., 2 tabs

  1. Axial spatial distribution focusing: improving MALDI-TOF/RTOF mass spectrometric performance for high-energy collision-induced dissociation of biomolecules.

    Science.gov (United States)

    Belgacem, O; Pittenauer, E; Openshaw, M E; Hart, P J; Bowdler, A; Allmaier, G

    2016-02-15

    For the last two decades, curved field reflectron technology has been used in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometers, assisting in the generation of post-source-decay (PSD) or collision-induced dissociation (CID) without decelerating precursor ions, producing true high-energy CID spectra. The result was the generation of product ion mass spectra with product ions typical of high-energy (10 keV and beyond) collision processes. The disadvantage of this approach was the lack of resolution in CID spectra resulting from the excess laser energy deposition used to generate those MS/MS spectra. The work presented in this study overcomes this limitation and includes comprehensive examples of high-energy and high-resolution CID MALDI-MS/MS spectra of biomolecules. The devices used in this study are TOF/RTOF instruments equipped with a high-vacuum MALDI ion source. High-resolution and high-energy CID spectra result from the use of axial spatial distribution focusing (ASDF) in combination with curved field reflectron technology. A CID spectrum of the P14 R1 peptide exhibits product ion resolution in excess of 10,000 (FWHM) but at the same time yields typical high-energy product ions such as w- and [y-2]-type ion series. High-energy CID spectra of lipids, exemplified by a glycerophospholipid and triglyceride, demonstrate C-C backbone fragmentation elucidating the presence of a hydroxyl group in addition to double-bond positioning. A complex high mannose carbohydrate (Man)8 (GlcNAc)2 was also studied at 20 keV collision energy and revealed further high-energy product ions with very high resolution, allowing unambiguous detection and characterization of cross-ring cleavage-related ions. This is the first comprehensive study using a MALDI-TOF/RTOF instrument equipped with a curved field reflectron and an ASDF device prior to the reflectron. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley

  2. High-resolution electron collision spectroscopy with multicharged ions in merged beams

    Energy Technology Data Exchange (ETDEWEB)

    Lestinsky, M.

    2007-04-18

    The Heidelberg ion storage ring Tsr is currently the only ring equipped with two independent devices for the collinear merging of a cold electron beam with stored ions. This greatly improves the potential of electron-ion collision experiments, as the ion beam can be cooled with one electron beam, while the other one is used as a dedicated target for energy-resolved electron collision processes, such as recombination. The work describes the implementation of this system for rst electron collision spectroscopy experiments. A detection system has been realized including an ion detector and specroscopic beam-control software and instrumentation. Moreover, in order to improve the spectroscopic resolution systematical studies of intrinsic relaxation processes in the electron beam have been carried out. These include the dependence on the electron beam density, the magnetic guiding eld strength, and the acceleration geometry. The recombination measurements on low-lying resonances in lithiumlike Sc{sup 18+} yield a high-precision measurement of the 2s-2p{sub 3/2} transition energy in this system. Operation of the two-electron-beam setup at high collision energy ({approx}1000 eV) is established using resonances of hydrogenlike Mg{sup 11+}, while the unique possibility of modifying the beam-merging geometry con rms its importance for the electron-ion recombination rate at lowest relative energy, as demonstrated on F{sup 6+}. (orig.)

  3. High-resolution electron collision spectroscopy with multicharged ions in merged beams

    International Nuclear Information System (INIS)

    Lestinsky, M.

    2007-01-01

    The Heidelberg ion storage ring Tsr is currently the only ring equipped with two independent devices for the collinear merging of a cold electron beam with stored ions. This greatly improves the potential of electron-ion collision experiments, as the ion beam can be cooled with one electron beam, while the other one is used as a dedicated target for energy-resolved electron collision processes, such as recombination. The work describes the implementation of this system for rst electron collision spectroscopy experiments. A detection system has been realized including an ion detector and specroscopic beam-control software and instrumentation. Moreover, in order to improve the spectroscopic resolution systematical studies of intrinsic relaxation processes in the electron beam have been carried out. These include the dependence on the electron beam density, the magnetic guiding eld strength, and the acceleration geometry. The recombination measurements on low-lying resonances in lithiumlike Sc 18+ yield a high-precision measurement of the 2s-2p 3/2 transition energy in this system. Operation of the two-electron-beam setup at high collision energy (∼1000 eV) is established using resonances of hydrogenlike Mg 11+ , while the unique possibility of modifying the beam-merging geometry con rms its importance for the electron-ion recombination rate at lowest relative energy, as demonstrated on F 6+ . (orig.)

  4. Quantitative imaging of magnesium distribution at single-cell resolution in brain tumors and infiltrating tumor cells with secondary ion mass spectrometry (SIMS)

    Science.gov (United States)

    Chandra, Subhash; Parker, Dylan J.; Barth, Rolf F.; Pannullo, Susan C.

    2016-01-01

    Glioblastoma multiforme (GBM) is one of the deadliest forms of human brain tumors. The infiltrative pattern of growth of these tumors includes the spread of individual and/or clusters of tumor cells at some distance from the main tumor mass in parts of the brain protected by an intact blood-brain-barrier. Pathophysiological studies of GBM could be greatly enhanced by analytical techniques capable of in situ single-cell resolution measurements of infiltrating tumor cells. Magnesium homeostasis is an area of active investigation in high grade gliomas. In the present study, we have used the F98 rat glioma as a model of human GBM and an elemental/isotopic imaging technique of secondary ion mass spectrometry (SIMS), a CAMECA IMS-3f ion microscope, for studying Mg distributions with single-cell resolution in freeze-dried brain tissue cryosections. Quantitative observations were made on tumor cells in the main tumor mass, contiguous brain tissue, and infiltrating tumor cells in adjacent normal brain. The brain tissue contained a significantly lower total Mg concentration of 4.70 ± 0.93 mmol/Kg wet weight (mean ± SD) in comparison to 11.64 ± 1.96 mmol/Kg wet weight in tumor cells of the main tumor mass and 10.72 ± 1.76 mmol/Kg wet weight in infiltrating tumor cells (p<0.05). The nucleus of individual tumor cells contained elevated levels of bound Mg. These observations demonstrate enhanced Mg-influx and increased binding of Mg in tumor cells and provide strong support for further investigation of GBMs for altered Mg homeostasis and activation of Mg-transporting channels as possible therapeutic targets. PMID:26703785

  5. Ion-atom collisions with laser-prepared target: High resolution study of single charge exchange process

    International Nuclear Information System (INIS)

    Leredde, Arnaud

    2012-01-01

    Single charge transfer in low-energy Na"++"8"7Rb(5s,5p) collisions is investigated using magneto-optically trapped Rb atoms and high-resolution recoil-ion momentum spectroscopy. The three-dimensional reconstruction of the recoil-ion momentum provides accurate relative cross-sections for the active channels and the projectile scattering angle distributions. Thanks to the high experimental resolution, scattering structures such as diffraction-like oscillations in angular distributions are clearly observed. The measurements are compared with molecular close-coupling calculations and an excellent agreement is found. To go further in the test of the theory, the target is prepared in an oriented state. It is the first time that such collision experiments with oriented target is performed with such a high resolution. The right-left asymmetry expected for the scattering angle distribution is evidenced. The agreement between MOCC calculations and experiments is very good. Simple models developed for collisions with oriented target are also discussed. (author) [fr

  6. In-depth study of in-trap high-resolution mass separation by transversal ion ejection from a multi-reflection time-of-flight device.

    Science.gov (United States)

    Fischer, Paul; Knauer, Stefan; Marx, Gerrit; Schweikhard, Lutz

    2018-01-01

    The recently introduced method of ion separation by transversal ejection of unwanted species in electrostatic ion-beam traps and multi-reflection time-of-flight devices has been further studied in detail. As this separation is performed during the ion storage itself, there is no need for additional external devices such as ion gates or traps for either pre- or postselection of the ions of interest. The ejection of unwanted contaminant ions is performed by appropriate pulses of the potentials of deflector electrodes. These segmented ring electrodes are located off-center in the trap, i.e., between one of the two ion mirrors and the central drift tube, which also serves as a potential lift for capturing incoming ions and axially ejecting ions of interest after their selection. The various parameters affecting the selection effectivity and resolving power are illustrated with tin-cluster measurements, where isotopologue ion species provide mass differences down to a single atomic mass unit at ion masses of several hundred. Symmetric deflection voltages of only 10 V were found sufficient for the transversal ejection of ion species with as few as three deflection pulses. The duty cycle, i.e., the pulse duration with respect to the period of ion revolution, has been varied, resulting in resolving powers of up to several tens of thousands for this selection technique.

  7. Accurate Mass Measurements for Planetary Microlensing Events Using High Angular Resolution Observations

    Directory of Open Access Journals (Sweden)

    Jean-Philippe Beaulieu

    2018-04-01

    Full Text Available The microlensing technique is a unique method to hunt for cold planets over a range of mass and separation, orbiting all varieties of host stars in the disk of our galaxy. It provides precise mass-ratio and projected separations in units of the Einstein ring radius. In order to obtain the physical parameters (mass, distance, orbital separation of the system, it is necessary to combine the result of light curve modeling with lens mass-distance relations and/or perform a Bayesian analysis with a galactic model. A first mass-distance relation could be obtained from a constraint on the Einstein ring radius if the crossing time of the source over the caustic is measured. It could then be supplemented by secondary constraints such as parallax measurements, ideally by using coinciding ground and space-born observations. These are still subject to degeneracies, like the orbital motion of the lens. A third mass-distance relation can be obtained thanks to constraints on the lens luminosity using high angular resolution observations with 8 m class telescopes or the Hubble Space Telescope. The latter route, although quite inexpensive in telescope time is very effective. If we have to rely heavily on Bayesian analysis and limited constraints on mass-distance relations, the physical parameters are determined to 30–40% typically. In a handful of cases, ground-space parallax is a powerful route to get stronger constraint on masses. High angular resolution observations will be able to constrain the luminosity of the lenses in the majority of the cases, and in favorable circumstances it is possible to derive physical parameters to 10% or better. Moreover, these constraints will be obtained in most of the planets to be discovered by the Euclid and WFIRST satellites. We describe here the state-of-the-art approaches to measure lens masses and distances with an emphasis on high angular resolution observations. We will discuss the challenges, recent results and

  8. New experiments in organic, fast-atom-bomdardment, and secondary-ion mass spectrometry

    International Nuclear Information System (INIS)

    DiDonato, G.C.

    1987-01-01

    The goal of research presented in this dissertation is the creative use of new ionization and instrumental techniques in mass spectrometry. This goal manifests itself in three areas of mass spectrometry. In the first portion, modern, state-of-the-art instrumentation and new experiments were used to re-examine the mass spectra of transition-metal acetates and acetylacetonates. High resolution, chemical ionization, negative chemical ionization, and extended-mass-range mass spectrometry uncovered a wealth of new gas-phase ionic species. Energy-resolved mass spectrometry/mass spectrometry was applied to the characterization of molecular and fragment ion first-row transition-metal acetylacetonates, and comprises the second portion of the thesis. Studies in fast-atom-bombardment mass spectrometry are the subject of the third portion of the dissertation. Since fast-atom bombardment samples a liquid matrix, absolute and relative abundances of sputtered secondary ions are influenced by solution chemistry. The design and construction of an imaging secondary-ion mass spectrometer is the subject of the final portion of the thesis. This instrument provides for direct mass-spectrometric analysis of thin-layer and paper chromatograms and electrophoretograms

  9. Ion beam properties after mass filtering with a linear radiofrequency quadrupole

    International Nuclear Information System (INIS)

    Ferrer, R.; Kwiatkowski, A.A.; Bollen, G.; Lincoln, D.L.; Morrissey, D.J.; Pang, G.K.; Ringle, R.; Savory, J.; Schwarz, S.

    2014-01-01

    The properties of ion beams passing through a linear radiofrequency quadrupole mass filter were investigated with special attention to their dependence on the mass resolving power. Experimentally, an increase of the transverse emittance was observed as the mass-to-charge selectivity of the mass filter was raised. The experimental behavior was confirmed by beam transport simulations. -- Highlights: • The ion-optical properties of a Quadrupole Mass Filter (QMF) are presented. • Measured beam emittances follow a trend to larger values for smaller A/Q ratios and increasing mass resolution. • The experimental behavior was confirmed by beam transport simulations. • The use of a QMF for mass filtering comes at the cost of emittance growth of the ion beam

  10. High-resolution ion pulse ionization chamber with air filling for the {sup 222}Rn decays detection

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilyuk, Yu.M.; Gangapshev, A.M.; Gezhaev, A.M.; Etezov, R.A.; Kazalov, V.V.; Kuzminov, V.V. [Baksan Neutrino Observatory,Institute for Nuclear Research RAS, 361609 Neutrino (Russian Federation); Panasenko, S.I. [V.N.Karazin Kharkiv National University, 61022 Kharkiv (Ukraine); Ratkevich, S.S., E-mail: ssratk@gmail.com [V.N.Karazin Kharkiv National University, 61022 Kharkiv (Ukraine); Tekueva, D.A.; Yakimenko, S.P. [Baksan Neutrino Observatory,Institute for Nuclear Research RAS, 361609 Neutrino (Russian Federation)

    2015-11-21

    The construction and characteristics of the cylindrical ion pulse ionization chamber (CIPIC) with a working volume of 3.2 L are described. The chamber is intended to register α-particles from the {sup 222}Rn and its daughter's decays in the filled air sample. The detector is less sensitive to electromagnetic pick-ups and mechanical noises. The digital pulse processing method is proposed to improve the energy resolution of the ion pulse ionization chamber. An energy resolution of 1.6% has been achieved for the 5.49 MeV α-line. The dependence of the energy resolution on high voltage and working media pressure has been investigated and the results are presented. - Highlights: • The construction and characteristics of the cylindrical ion pulse ionization chamber (CIPIC) with a working volume of 3.2 L are described. • The chamber is intended to register alpha-particles from {sup 222}Rn and its daughter's decays in the filled air sample. • The detector is less sensitive to electromagnetic pick-ups and mechanical noises. • An energy resolution of 1.6% has been achieved for the 5.49 MeV alpha-line. The dependence of the energy resolution on high voltage and working media pressure have been investigated and the results are presented.

  11. Detection of atmospheric gaseous amines and amides by a high-resolution time-of-flight chemical ionization mass spectrometer with protonated ethanol reagent ions

    Directory of Open Access Journals (Sweden)

    L. Yao

    2016-11-01

    Full Text Available Amines and amides are important atmospheric organic-nitrogen compounds but high time resolution, highly sensitive, and simultaneous ambient measurements of these species are rather sparse. Here, we present the development of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS method, utilizing protonated ethanol as reagent ions to simultaneously detect atmospheric gaseous amines (C1 to C6 and amides (C1 to C6. This method possesses sensitivities of 5.6–19.4 Hz pptv−1 for amines and 3.8–38.0 Hz pptv−1 for amides under total reagent ion signals of  ∼  0.32 MHz. Meanwhile, the detection limits were 0.10–0.50 pptv for amines and 0.29–1.95 pptv for amides at 3σ of the background signal for a 1 min integration time. Controlled characterization in the laboratory indicates that relative humidity has significant influences on the detection of amines and amides, whereas the presence of organics has no obvious effects. Ambient measurements of amines and amides utilizing this method were conducted from 25 July to 25 August 2015 in urban Shanghai, China. While the concentrations of amines ranged from a few parts per trillion by volume to hundreds of parts per trillion by volume, concentrations of amides varied from tens of parts per trillion by volume to a few parts per billion by volume. Among the C1- to C6-amines, the C2-amines were the dominant species with concentrations up to 130 pptv. For amides, the C3-amides (up to 8.7 ppb were the most abundant species. The diurnal and backward trajectory analysis profiles of amides suggest that in addition to the secondary formation of amides in the atmosphere, industrial emissions could be important sources of amides in urban Shanghai. During the campaign, photo-oxidation of amines and amides might be a main loss pathway for them in daytime, and wet deposition was also an important sink.

  12. High resolution helium ion scanning microscopy of the rat kidney.

    Directory of Open Access Journals (Sweden)

    William L Rice

    Full Text Available Helium ion scanning microscopy is a novel imaging technology with the potential to provide sub-nanometer resolution images of uncoated biological tissues. So far, however, it has been used mainly in materials science applications. Here, we took advantage of helium ion microscopy to explore the epithelium of the rat kidney with unsurpassed image quality and detail. In addition, we evaluated different tissue preparation methods for their ability to preserve tissue architecture. We found that high contrast, high resolution imaging of the renal tubule surface is possible with a relatively simple processing procedure that consists of transcardial perfusion with aldehyde fixatives, vibratome tissue sectioning, tissue dehydration with graded methanol solutions and careful critical point drying. Coupled with the helium ion system, fine details such as membrane texture and membranous nanoprojections on the glomerular podocytes were visualized, and pores within the filtration slit diaphragm could be seen in much greater detail than in previous scanning EM studies. In the collecting duct, the extensive and striking apical microplicae of the intercalated cells were imaged without the shrunken or distorted appearance that is typical with conventional sample processing and scanning electron microscopy. Membrane depressions visible on principal cells suggest possible endo- or exocytotic events, and central cilia on these cells were imaged with remarkable preservation and clarity. We also demonstrate the use of colloidal gold probes for highlighting specific cell-surface proteins and find that 15 nm gold labels are practical and easily distinguishable, indicating that external labels of various sizes can be used to detect multiple targets in the same tissue. We conclude that this technology represents a technical breakthrough in imaging the topographical ultrastructure of animal tissues. Its use in future studies should allow the study of fine cellular details

  13. Characterization of aromatic organosulfur model compounds relevant to fossil fuels by using atmospheric pressure chemical ionization with CS2 and high-resolution tandem mass spectrometry.

    Science.gov (United States)

    Tang, Weijuan; Sheng, Huaming; Jin, Chunfen; Riedeman, James S; Kenttämaa, Hilkka I

    2016-04-15

    The chemistry of desulfurization involved in processing crude oil is greatly dependent on the forms of sulfur in the oil. Sulfur exists in different chemical bonding environments in fossil fuels, including those in thiophenes and benzothiophenes, thiols, sulfides, and disulfides. In this study, the fragmentation behavior of the molecular ions of 17 aromatic organosulfur compounds with various functionalities was systematically investigated by using high-resolution tandem mass spectrometry. Multiple-stage tandem mass spectrometric experiments were carried out using a linear quadrupole ion trap (LQIT) equipped with an atmospheric pressure chemical ionization (APCI) source. (+)APCI/CS2 was used to generate stable dominant molecular ions for all the compounds studied except for three sulfides that also showed abundant fragment ions. The LQIT coupled with an orbitrap mass spectrometer was used for elemental composition analysis, which facilitated the identification of the neutral molecules lost during fragmentation. The characteristic fragment ions generated in MS(2) and MS(3) experiments provide clues for the chemical bonding environment of sulfur atoms in the examined compounds. Upon collision-induced dissociation (CID), the molecular ions can lose the sulfur atom in a variety of ways, including as S (32 Da), HS(•) (33 Da), H2 S (34 Da), CS (44 Da), (•) CHS (45 Da) and CH2 S (46 Da). These neutral fragments are not only indicative of the presence of sulfur, but also of the type of sulfur present in the compound. Generally, losses of HS(•) and H2 S were found to be associated with compounds containing saturated sulfur functionalities, while losses of S, CS and (•) CHS were more common for heteroaromatic sulfur compounds. High-resolution tandem mass spectrometry with APCI/CS2 ionization is a viable approach to determining the types of organosulfur compounds. It can potentially be applied to analysis of complex mixtures, which is beneficial to improving the

  14. Gas-phase ion-molecule reactions and high-pressure mass spectrometer, 1

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo

    1977-01-01

    The reasons for the fact that the research in gas-phase ion-molecule reactions, to which wide interest is shown, have greatly contributed to the physical and chemical fields are that, first it is essential in understanding general phenomena concerning ions, second, it can furnish many unique informations in the dynamics of chemical reactions, and third, usefulness of '' chemical ionization'' methods has been established as its application to chemical analysis. In this review, the history and trend of studies and equipments in gas-phase ion-molecule reactions are surveyed. The survey includes the chemical ionization mass spectrometer for simultaneously measuring the positive and negative ions utilizing a quadrupole mass spectrometer presented by Hunt and others, flowing afterglow method derived from the flowing method which traces neutral chemical species mainly optically, ion cyclotron resonance mass spectrometer, trapped ion mass spectrometer and others. Number of reports referred to ion-molecule reactions issued during the last one year well exceeds the total number of reports concerning mass spectrometers presented before 1955. This truly shows how active the research and development are in this field. (Wakatsuki, Y.)

  15. High mass accuracy and high mass resolving power FT-ICR secondary ion mass spectrometry for biological tissue imaging

    NARCIS (Netherlands)

    Smith, D.F.; Kiss, A.; Leach, F.E.; Robinson, E.W.; Paša-Tolić, L.; Heeren, R.M.A.

    2013-01-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the sub-micrometer scale. Such experiments are typically

  16. Visualization of metallodrugs in single cells by secondary ion mass spectrometry imaging.

    Science.gov (United States)

    Wu, Kui; Jia, Feifei; Zheng, Wei; Luo, Qun; Zhao, Yao; Wang, Fuyi

    2017-07-01

    Secondary ion mass spectrometry, including nanoscale secondary ion mass spectrometry (NanoSIMS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), has emerged as a powerful tool for biological imaging, especially for single cell imaging. SIMS imaging can provide information on subcellular distribution of endogenous and exogenous chemicals, including metallodrugs, from membrane through to cytoplasm and nucleus without labeling, and with high spatial resolution and chemical specificity. In this mini-review, we summarize recent progress in the field of SIMS imaging, particularly in the characterization of the subcellular distribution of metallodrugs. We anticipate that the SIMS imaging method will be widely applied to visualize subcellular distributions of drugs and drug candidates in single cells, exerting significant influence on early drug evaluation and metabolism in medicinal and pharmaceutical chemistry. Recent progress of SIMS applications in characterizing the subcellular distributions of metallodrugs was summarized.

  17. Novel control modes to improve the performance of rectilinear ion trap mass spectrometer with dual pressure chambers

    Science.gov (United States)

    Huo, Xinming; Tang, Fei; Zhang, Xiaohua; Chen, Jin; Zhang, Yan; Guo, Cheng'an; Wang, Xiaohao

    2016-10-01

    The rectilinear ion trap (RIT) has gradually become one of the preferred mass analyzers for portable mass spectrometers because of its simple configuration. In order to enhance the performance, including sensitivity, quantitation capability, throughput, and resolution, a novel RIT mass spectrometer with dual pressure chambers was designed and characterized. The studied system constituted a quadrupole linear ion trap (QLIT) in the first chamber and a RIT in the second chamber. Two control modes are hereby proposed: Storage Quadrupole Linear Ion Trap-Rectilinear Ion Trap (SQLIT-RIT) mode, in which the QLIT was used at high pressure for ion storage and isolation, and the RIT was used for analysis; and Analysis Quadrupole Linear Ion Trap-Rectilinear Ion Trap (AQLIT-RIT) mode, in which the QLIT was used for ion storage and cooling. Subsequently, synchronous scanning and analysis were carried out by QLIT and RIT. In SQLIT-RIT mode, signal intensity was improved by a factor of 30; the limit of quantitation was reduced more than tenfold to 50 ng mL-1, and an optimal duty cycle of 96.4% was achieved. In AQLIT-RIT mode, the number of ions coexisting in the RIT was reduced, which weakened the space-charge effect and reduced the mass shift. Furthermore, the mass resolution was enhanced by a factor of 3. The results indicate that the novel control modes achieve satisfactory performance without adding any system complexity, which provides a viable pathway to guarantee good analytical performance in miniaturization of the mass spectrometer.

  18. Performance results of a mobile high-resolution MR-TOF mass spectrometer for in-situ analytical mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lippert, Wayne; Lang, Johannes [Justus-Liebig-Universitaet Giessen (Germany); Ayet San Andres, Samuel [GSI, Darmstadt (Germany); Dickel, Timo; Geissel, Hans; Plass, Wolfgang; Scheidenberger, Christoph [Justus-Liebig-Universitaet Giessen (Germany); GSI, Darmstadt (Germany); Yavor, Mikhail [RAS St. Petersburg (Russian Federation)

    2014-07-01

    A mobile multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) has been developed which provides a mass resolving power exceeding 250,000 and sub-ppm mass accuracy in a transportable format. Thus it allows resolving isobars and enables accurate determination of the composition and structure of biomolecules. Furthermore the device offers high mass resolving MS/MS capability via selective ion re-trapping and collisional-induced dissociation (CID). An atmospheric pressure interface (API) provides for routine measurements with various atmospheric ion sources. All supply electronics, DAQ and control system are mounted with the spectrometer into a single frame with a total volume of only 0.8 m{sup 3}. With the current system many applications like waste water monitoring at hot spots, mass-based classification of biomolecules and breath analysis are possible. In addition the mass spectrometer is readily scalable and can be adopted and simplified for even more specific use like in space science for instance. A characterization and first performance results are shown, and the implementation of MS/MS in combination with CID is discussed.

  19. High-resolution grazing-incidence grating spectrometer for temperature measurements of low-Z ions emitting in the 100-300 Å spectral banda)

    Science.gov (United States)

    Widmann, K.; Beiersdorfer, P.; Magee, E. W.; Boyle, D. P.; Kaita, R.; Majeski, R.

    2014-11-01

    We have constructed a high-resolution grazing-incidence spectrometer designed for measuring the ion temperature of low-Z elements, such as Li+ or Li2 +, which radiate near 199 Å and 135 Å, respectively. Based on measurements at the Livermore Electron Beam Ion Trap we have shown that the instrumental resolution is better than 48 mÅ at the 200 Å setting and better than 40 mÅ for the 135-Å range. Such a high spectral resolution corresponds to an instrumental limit for line-width based temperature measurements of about 45 eV for the 199 Å Li+ and 65 eV for the 135 Å Li2 + lines. Recently obtained survey spectra from the Lithium Tokamak Experiment at the Princeton Plasma Physics Laboratory show the presence of these lithium emission lines and the expected core ion temperature of approximately 70 eV is sufficiently high to demonstrate the feasibility of utilizing our high-resolution spectrometer as an ion-temperature diagnostic.

  20. Peptide Peak Detection for Low Resolution MALDI-TOF Mass Spectrometry.

    Science.gov (United States)

    Yao, Jingwen; Utsunomiya, Shin-Ichi; Kajihara, Shigeki; Tabata, Tsuyoshi; Aoshima, Ken; Oda, Yoshiya; Tanaka, Koichi

    2014-01-01

    A new peak detection method has been developed for rapid selection of peptide and its fragment ion peaks for protein identification using tandem mass spectrometry. The algorithm applies classification of peak intensities present in the defined mass range to determine the noise level. A threshold is then given to select ion peaks according to the determined noise level in each mass range. This algorithm was initially designed for the peak detection of low resolution peptide mass spectra, such as matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) mass spectra. But it can also be applied to other type of mass spectra. This method has demonstrated obtaining a good rate of number of real ions to noises for even poorly fragmented peptide spectra. The effect of using peak lists generated from this method produces improved protein scores in database search results. The reliability of the protein identifications is increased by finding more peptide identifications. This software tool is freely available at the Mass++ home page (http://www.first-ms3d.jp/english/achievement/software/).

  1. Ultra-High Resolution Ion Mobility Separations Utilizing Traveling Waves in a 13 m Serpentine Path Length Structures for Lossless Ion Manipulations Module

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Liulin; Ibrahim, Yehia M.; Hamid, Ahmed M.; Garimella, Sandilya V. B.; Webb, Ian K.; Zheng, Xueyun; Prost, Spencer A.; Sandoval, Jeremy A.; Norheim, Randolph V.; Anderson, Gordon A.; Tolmachev, Aleksey V.; Baker, Erin S.; Smith, Richard D.

    2016-09-20

    We report the development and initial evaluation of a 13-m path length Structures for Lossless Manipulations (SLIM) module for achieving high resolution separations using traveling waves (TW) with ion mobility (IM) spectrometry. The TW SLIM module was fabricated using two mirror-image printed circuit boards with appropriately configured RF, DC and TW electrodes and positioned with a 2.75-mm inter-surface gap. Ions were effective confined between the surfaces by RF-generated pseudopotential fields and moved losslessly through a serpentine path including 44 “U” turns using TWs. The ion mobility resolution was characterized at different pressures, gaps between the SLIM surfaces, TW and RF parameters. After initial optimization the SLIM IM-MS module provided about 5-fold higher resolution separations than present commercially available drift tube or traveling wave IM-MS platforms. Peak capacity and peak generation rates achieved were 246 and 370 s-1, respectively, at a TW speed of 148 m/s. The high resolution achieved in the TW SLIM IM-MS enabled e.g., isomeric sugars (Lacto-N-fucopentaose I and Lacto-N-fucopentaose II) to be baseline resolved, and peptides from a albumin tryptic digest much better resolved than with existing commercial IM-MS platforms. The present work also provides a foundation for the development of much higher resolution SLIM devices based upon both considerably longer path lengths and multi-pass designs.

  2. MOMA and other next-generation ion trap mass spectrometers for planetary exploration

    Science.gov (United States)

    Arevalo, R. D., Jr.; Brinckerhoff, W. B.; Getty, S.; Mahaffy, P. R.; van Amerom, F. H. W.; Danell, R.; Pinnick, V. T.; Li, X.; Grubisic, A.; Southard, A. E.; Hovmand, L.; Cottin, H.; Makarov, A.

    2016-12-01

    Since the 1970's, quadrupole mass spectrometer (QMS) systems have served as low-risk, cost-efficient means to explore the inner and outer reaches of the solar system. These legacy instruments have interrogated the compositions of the lunar exosphere (LADEE), surface materials on Mars (MSL), and the atmospheres of Venus (Pioneer Venus), Mars (MAVEN) and outer planets (Galileo and Cassini-Huygens). However, the in situ detection of organic compounds on Mars and Titan, coupled with ground-based measurements of amino acids in meteorites and a variety of organics in comets, has underlined the importance of molecular disambiguation in the characterization of high-priority planetary environments. The Mars Organic Molecule Analyzer (MOMA) flight instrument, centered on a linear ion trap, enables the in situ detection of volatile and non-volatile organics, but also the characterization of molecular structures through SWIFT ion isolation/excitation and tandem mass spectrometry (MSn). Like the SAM instrument on MSL, the MOMA investigation also includes a gas chromatograph (GC), thereby enabling the chemical separation of potential isobaric interferences based on retention times. The Linear Ion Trap Mass Spectrometer (LITMS; PI: William Brinckerhoff), developed to TRL 6 via the ROSES MatISSE Program, augments the core MOMA design and adds: expanded mass range (from 20 - 2000 Da); high-temperature evolved gas analysis (up to 1300°C); and, dual polarity detector assemblies (supporting the measurement of negative ions). The LITMS instrument will be tested in the field in 2017 through the Atacama Rover Astrobiology Drilling Studies (ARADS; PI: Brian Glass) ROSES PSTAR award. Following on these advancements, the Advanced Resolution Organic Molecule Analyzer (AROMA; PI: Ricardo Arevalo Jr.), supported through the ROSES PICASSO Program, combines a highly capable MOMA/LITMS-like linear ion trap and the ultrahigh resolution CosmOrbitrap mass analyzer developed by a consortium of five

  3. Highly charged ion based time-of-flight emission microscope

    International Nuclear Information System (INIS)

    Hamza, Alex V.; Barnes, Alan V.; Magee, Ed; Newman, Mike; Schenkel, Thomas; McDonald, Joseph W.; Schneider, Dieter H.

    2000-01-01

    An emission microscope using highly charged ions as the excitation source has been designed, constructed, and operated. A novel ''acorn'' objective lens has been used to simultaneously image electron and secondary ion emission. A resistive anode-position sensitive detector is used to determine the x-y position and time of arrival of the secondary events at the microscope image plane. Contrast in the image can be based on the intensity of the electron emission and/or the presence of particular secondary ions. Spatial resolution of better than 1 μm and mass resolution m/Δm of better than 400 were demonstrated. Background rejection from uncorrelated events of greater than an order of magnitude is also achieved. (c) 2000 American Institute of Physics

  4. Characterization of primary organic aerosol emissions from meat cooking, trash burning, and motor vehicles with high-resolution aerosol mass spectrometry and comparison with ambient and chamber observations.

    Science.gov (United States)

    Mohr, Claudia; Huffman, Alex; Cubison, Michael J; Aiken, Allison C; Docherty, Kenneth S; Kimmel, Joel R; Ulbrich, Ingrid M; Hannigan, Michael; Jimenez, Jose L

    2009-04-01

    Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikelyto be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.

  5. Co-Registered In Situ Secondary Electron and Mass Spectral Imaging on the Helium Ion Microscope Demonstrated Using Lithium Titanate and Magnesium Oxide Nanoparticles.

    Science.gov (United States)

    Dowsett, D; Wirtz, T

    2017-09-05

    The development of a high resolution elemental imaging platform combining coregistered secondary ion mass spectrometry and high resolution secondary electron imaging is reported. The basic instrument setup and operation are discussed and in situ image correlation is demonstrated on a lithium titanate and magnesium oxide nanoparticle mixture. The instrument uses both helium and neon ion beams generated by a gas field ion source to irradiate the sample. Both secondary electrons and secondary ions may be detected. Secondary ion mass spectrometry (SIMS) is performed using an in-house developed double focusing magnetic sector spectrometer with parallel detection. Spatial resolutions of 10 nm have been obtained in SIMS mode. Both the secondary electron and SIMS image data are very surface sensitive and have approximately the same information depth. While the spatial resolutions are approximately a factor of 10 different, switching between the different images modes may be done in situ and extremely rapidly, allowing for simple imaging of the same region of interest and excellent coregistration of data sets. The ability to correlate mass spectral images on the 10 nm scale with secondary electron images on the nanometer scale in situ has the potential to provide a step change in our understanding of nanoscale phenomena in fields from materials science to life science.

  6. Using matrix peaks to map topography: Increased mass resolution and enhanced sensitivity in chemical imaging

    NARCIS (Netherlands)

    McDonnell, Liam A.; Mize, Todd H.; Luxembourg, Stefan L.; Koster, Sander; Eijkel, Gert B.; Verpoorte, Elisabeth; De Rooij, Nico F.; Heeren, Ron M. A.

    2003-01-01

    It is well known in secondary ion mass spectrometry (SIMS) that sample topography leads to decreased mass resolution. Specifically, the ion's time of flight is dependent on where it was generated. Here, using matrix-enhanced SIMS, it is demonstrated that, in addition to increasing the yield of

  7. High resolution studies by Secondary Ion Mass Spectrometry of the spatial distribution of tritium in neutron irradiated beryllium pebbles

    International Nuclear Information System (INIS)

    Rabaglino, E.; Tamborini, G.; Hiernaut, J.-P.; Betti, M.

    2006-01-01

    A key issue of beryllium as a neutron multiplier in the blanket of future fusion reactors is tritium retention. Models are under development in order to predict tritium release kinetics in the typical operating conditions of the material in the blanket: the absence of experimental data in this range imposes an extrapolation of the models, therefore a detailed characterization and understanding of microscopic diffusion phenomena related to macroscopic tritium release is necessary. It has been recently shown, that the availability of evidence on such phenomena at a scale of 1 micron down to tens of nanometers enables a relevant progress in the effectiveness of model validation: therefore the need for applying and developing advanced analytical techniques based on mass spectrometry at this scale. A study of tritium spatial distribution in neutron irradiated beryllium pebbles (2 mm diameter, 480 appm 4 He, 7 appm 3 H) by means of Secondary Ion Mass Spectrometry (SIMS) is presented. Samples in different conditions (non-irradiated, at end of irradiation and at different temperatures during thermal ramp annealing) are examined by an oxygen ion primary beam with a spatial resolution of 1 micron along a diameter. The sample preparation is optimized in order to enable a quantitative comparison among the different conditions. Under an oxygen ion beam tritium is detected in the irradiated samples in a molecular form (3H 2 ), with a continuous distribution inside the grains, which suggests the presence of small clusters in agreement with TEM analyses, and in the form of peaks at grain boundaries, corresponding to large grain boundary bubbles. The evolving of molecular tritium distribution measured by SIMS during a typical thermal ramp release experiment shows precisely tritium diffusion from the centre of the grain to grain boundaries as the temperature increases: at the same time the remaining intragranular tritium inventory, given by the integral of the distribution

  8. Following the Ions through a Mass Spectrometer with Atmospheric Pressure Interface: Simulation of Complete Ion Trajectories from Ion Source to Mass Analyzer.

    Science.gov (United States)

    Zhou, Xiaoyu; Ouyang, Zheng

    2016-07-19

    Ion trajectory simulation is an important and useful tool in instrumentation development for mass spectrometry. Accurate simulation of the ion motion through the mass spectrometer with atmospheric pressure ionization source has been extremely challenging, due to the complexity in gas hydrodynamic flow field across a wide pressure range as well as the computational burden. In this study, we developed a method of generating the gas flow field for an entire mass spectrometer with an atmospheric pressure interface. In combination with the electric force, for the first time simulation of ion trajectories from an atmospheric pressure ion source to a mass analyzer in vacuum has been enabled. A stage-by-stage ion repopulation method has also been implemented for the simulation, which helped to avoid an intolerable computational burden for simulations at high pressure regions while it allowed statistically meaningful results obtained for the mass analyzer. It has been demonstrated to be suitable to identify a joint point for combining the high and low pressure fields solved individually. Experimental characterization has also been done to validate the new method for simulation. Good agreement was obtained between simulated and experimental results for ion transfer though an atmospheric pressure interface with a curtain gas.

  9. High Resolution Mass Spectrometry of Polyfluorinated Polyether-Based Formulation

    Science.gov (United States)

    Dimzon, Ian Ken; Trier, Xenia; Frömel, Tobias; Helmus, Rick; Knepper, Thomas P.; de Voogt, Pim

    2016-02-01

    High resolution mass spectrometry (HRMS) was successfully applied to elucidate the structure of a polyfluorinated polyether (PFPE)-based formulation. The mass spectrum generated from direct injection into the MS was examined by identifying the different repeating units manually and with the aid of an instrument data processor. Highly accurate mass spectral data enabled the calculation of higher-order mass defects. The different plots of MW and the nth-order mass defects (up to n = 3) could aid in assessing the structure of the different repeating units and estimating their absolute and relative number per molecule. The three major repeating units were -C2H4O-, -C2F4O-, and -CF2O-. Tandem MS was used to identify the end groups that appeared to be phosphates, as well as the possible distribution of the repeating units. Reversed-phase HPLC separated of the polymer molecules on the basis of number of nonpolar repeating units. The elucidated structure resembles the structure in the published manufacturer technical data. This analytical approach to the characterization of a PFPE-based formulation can serve as a guide in analyzing not just other PFPE-based formulations but also other fluorinated and non-fluorinated polymers. The information from MS is essential in studying the physico-chemical properties of PFPEs and can help in assessing the risks they pose to the environment and to human health.

  10. Automated, feature-based image alignment for high-resolution imaging mass spectrometry of large biological samples

    NARCIS (Netherlands)

    Broersen, A.; Liere, van R.; Altelaar, A.F.M.; Heeren, R.M.A.; McDonnell, L.A.

    2008-01-01

    High-resolution imaging mass spectrometry of large biological samples is the goal of several research groups. In mosaic imaging, the most common method, the large sample is divided into a mosaic of small areas that are then analyzed with high resolution. Here we present an automated alignment

  11. Factor analysis of combined organic and inorganic aerosol mass spectra from high resolution aerosol mass spectrometer measurements

    Directory of Open Access Journals (Sweden)

    Y. L. Sun

    2012-09-01

    Full Text Available Positive matrix factorization (PMF was applied to the merged high resolution mass spectra of organic and inorganic aerosols from aerosol mass spectrometer (AMS measurements to investigate the sources and evolution processes of submicron aerosols in New York City in summer 2009. This new approach is able to study the distribution of organic and inorganic species in different types of aerosols, the acidity of organic aerosol (OA factors, and the fragment ion patterns related to photochemical processing. In this study, PMF analysis of the unified AMS spectral matrix resolved 8 factors. The hydrocarbon-like OA (HOA and cooking OA (COA factors contain negligible amounts of inorganic species. The two factors that are primarily ammonium sulfate (SO4-OA and ammonium nitrate (NO3-OA, respectively, are overall neutralized. Among all OA factors the organic fraction of SO4-OA shows the highest degree of oxidation (O/C = 0.69. Two semi-volatile oxygenated OA (OOA factors, i.e., a less oxidized (LO-OOA and a more oxidized (MO-OOA, were also identified. MO-OOA represents local photochemical products with a diurnal profile exhibiting a pronounced noon peak, consistent with those of formaldehyde (HCHO and Ox(= O3 + NO2. The NO+/NO2+ ion ratio in MO-OOA is much higher than that in NO3-OA and in pure ammonium nitrate, indicating the formation of organic nitrates. The nitrogen-enriched OA (NOA factor contains ~25% of acidic inorganic salts, suggesting the formation of secondary OA via acid-base reactions of amines. The size distributions of OA factors derived from the size-resolved mass spectra show distinct diurnal evolving behaviors but overall a progressing evolution from smaller to larger particle mode as the oxidation degree of OA increases. Our results demonstrate that PMF analysis of the unified aerosol mass spectral matrix which contains both

  12. Highly informative multiclass profiling of lipids by ultra-high performance liquid chromatography - Low resolution (quadrupole) mass spectrometry by using electrospray ionization and atmospheric pressure chemical ionization interfaces.

    Science.gov (United States)

    Beccaria, Marco; Inferrera, Veronica; Rigano, Francesca; Gorynski, Krzysztof; Purcaro, Giorgia; Pawliszyn, Janusz; Dugo, Paola; Mondello, Luigi

    2017-08-04

    A simple, fast, and versatile method, using an ultra-high performance liquid chromatography system coupled with a low resolution (single quadrupole) mass spectrometer was optimized to perform multiclass lipid profiling of human plasma. Particular attention was made to develop a method suitable for both electrospray ionization and atmospheric pressure chemical ionization interfaces (sequentially in positive- and negative-ion mode), without any modification of the chromatographic conditions (mobile phase, flow-rate, gradient, etc.). Emphasis was given to the extrapolation of the structural information based on the fragmentation pattern obtained using atmospheric pressure chemical ionization interface, under each different ionization condition, highlighting the complementary information obtained using the electrospray ionization interface, of support for related molecule ions identification. Furthermore, mass spectra of phosphatidylserine and phosphatidylinositol obtained using the atmospheric pressure chemical ionization interface are reported and discussed for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Next-generation technologies for spatial proteomics: Integrating ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR imaging mass spectrometry for protein analysis.

    Science.gov (United States)

    Spraggins, Jeffrey M; Rizzo, David G; Moore, Jessica L; Noto, Michael J; Skaar, Eric P; Caprioli, Richard M

    2016-06-01

    MALDI imaging mass spectrometry is a powerful analytical tool enabling the visualization of biomolecules in tissue. However, there are unique challenges associated with protein imaging experiments including the need for higher spatial resolution capabilities, improved image acquisition rates, and better molecular specificity. Here we demonstrate the capabilities of ultra-high speed MALDI-TOF and high mass resolution MALDI FTICR IMS platforms as they relate to these challenges. High spatial resolution MALDI-TOF protein images of rat brain tissue and cystic fibrosis lung tissue were acquired at image acquisition rates >25 pixels/s. Structures as small as 50 μm were spatially resolved and proteins associated with host immune response were observed in cystic fibrosis lung tissue. Ultra-high speed MALDI-TOF enables unique applications including megapixel molecular imaging as demonstrated for lipid analysis of cystic fibrosis lung tissue. Additionally, imaging experiments using MALDI FTICR IMS were shown to produce data with high mass accuracy (z 5000) for proteins up to ∼20 kDa. Analysis of clear cell renal cell carcinoma using MALDI FTICR IMS identified specific proteins localized to healthy tissue regions, within the tumor, and also in areas of increased vascularization around the tumor. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Simultaneous quantification of amino acids and Amadori products in foods through ion-pairing liquid chromatography-high-resolution mass spectrometry.

    Science.gov (United States)

    Troise, Antonio Dario; Fiore, Alberto; Roviello, Giovanni; Monti, Simona Maria; Fogliano, Vincenzo

    2015-01-01

    The formation of the Amadori products (APs) is the first key step of Maillard reaction. Only few papers have dealt with simultaneous quantitation of amino acids and corresponding APs (1-amino-1-deoxy-2-ketose). Chromatographic separation of APs is affected by several drawbacks mainly related to their poor retention in conventional reversed phase separation. In this paper, a method for the simultaneous quantification of amino acids and their respective APs was developed combining high-resolution mass spectrometry with ion-pairing liquid chromatography. The limit of detection was 0.1 ng/mL for tryptophan, valine and arginine, while the limit of quantification ranged from 2 to 5 ng/mL according to the specific sensitivity of each analyte. The relative standard deviation % was lower than 10 % and the coefficient of correlation was higher than 0.99 for each calibration curve. The method was applied to milk, milk-based products, raw and processed tomato. Among the analyzed products, the most abundant amino acid was glutamic acid (16,646.89 ± 1,385.40 µg/g) and the most abundant AP was fructosyl-arginine in tomato puree (774.82 ± 10.01 µg/g). The easiness of sample preparation coupled to the analytical performances of the proposed method introduced the possibility to use the pattern of free amino acids and corresponding APs in the evaluation of the quality of raw food as well as the extent of thermal treatments in different food products.

  15. A fast mass spring model solver for high-resolution elastic objects

    Science.gov (United States)

    Zheng, Mianlun; Yuan, Zhiyong; Zhu, Weixu; Zhang, Guian

    2017-03-01

    Real-time simulation of elastic objects is of great importance for computer graphics and virtual reality applications. The fast mass spring model solver can achieve visually realistic simulation in an efficient way. Unfortunately, this method suffers from resolution limitations and lack of mechanical realism for a surface geometry model, which greatly restricts its application. To tackle these problems, in this paper we propose a fast mass spring model solver for high-resolution elastic objects. First, we project the complex surface geometry model into a set of uniform grid cells as cages through *cages mean value coordinate method to reflect its internal structure and mechanics properties. Then, we replace the original Cholesky decomposition method in the fast mass spring model solver with a conjugate gradient method, which can make the fast mass spring model solver more efficient for detailed surface geometry models. Finally, we propose a graphics processing unit accelerated parallel algorithm for the conjugate gradient method. Experimental results show that our method can realize efficient deformation simulation of 3D elastic objects with visual reality and physical fidelity, which has a great potential for applications in computer animation.

  16. New design for a time-of-flight mass spectrometer with a liquid beam laser desorption ion source for the analysis of biomolecules

    International Nuclear Information System (INIS)

    Charvat, A.; Lugovoj, E.; Faubel, M.; Abel, B.

    2004-01-01

    We describe a novel liquid beam mass spectrometer, based on a recently discovered nanosecond laser desorption phenomenon, [W. Kleinekofort, J. Avdiev, and B. Brutschy, Int. J. Mass Ion. Processes 152, 135 (1996)] which allows the liquid-to-vacuum transfer, and subsequent mass analysis of pre-existing ions and ionic associates from liquid microjets of aqueous solutions. The goal of our novel technical approach is to establish a system with good mass resolution that implements improvements on critical components that make the system more reliable and easier to operate. For laser desorption pulsed dye-laser difference frequency mixing is used that provides tunable infrared light near the absorption maximum of liquid water around 3 μm. Different types of liquid beam glass nozzles (convergent capillary and aperture plate nozzles) are investigated and characterized. Starting from theoretical considerations of hydrodynamic drag forces on micrometer size droplets in supersonic rarefied gas flows we succeeded in capturing efficiently the liquid beam in a liquid beam recycling trap operating at the vapor pressure of liquid water. For improving the pollution resistance, the liquid jet high vacuum ion source region is spatially separated from the reflectron time-of-flight mass spectrometer (TOF-MS) working behind a gate valve in an ultrahigh vacuum environment. A simple (simulation optimized) ion optics is employed for the ion transfer from the source to the high vacuum region. This new feature is also mostly responsible for the improved mass resolution. With the present tandem-TOF-MS setup a resolution of m/Δm≅1800 for the low and m/Δm≅700 in the high mass region has been obtained for several biomolecules of different mass and complexity (amino acids, insulin, and cytochrome c)

  17. High-resolution grazing-incidence grating spectrometer for temperature measurements of low-Z ions emitting in the 100–300 Å spectral band

    Energy Technology Data Exchange (ETDEWEB)

    Widmann, K., E-mail: widmann1@llnl.gov; Beiersdorfer, P.; Magee, E. W. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Boyle, D. P.; Kaita, R.; Majeski, R. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08543 (United States)

    2014-11-15

    We have constructed a high-resolution grazing-incidence spectrometer designed for measuring the ion temperature of low-Z elements, such as Li{sup +} or Li{sup 2+}, which radiate near 199 Å and 135 Å, respectively. Based on measurements at the Livermore Electron Beam Ion Trap we have shown that the instrumental resolution is better than 48 mÅ at the 200 Å setting and better than 40 mÅ for the 135-Å range. Such a high spectral resolution corresponds to an instrumental limit for line-width based temperature measurements of about 45 eV for the 199 Å Li{sup +} and 65 eV for the 135 Å Li{sup 2+} lines. Recently obtained survey spectra from the Lithium Tokamak Experiment at the Princeton Plasma Physics Laboratory show the presence of these lithium emission lines and the expected core ion temperature of approximately 70 eV is sufficiently high to demonstrate the feasibility of utilizing our high-resolution spectrometer as an ion-temperature diagnostic.

  18. 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer Greatly Expands Mass Spectrometry Toolbox

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, Jared B.; Lin, Tzu-Yung; Leach, Franklin E.; Tolmachev, Aleksey V.; Tolić, Nikola; Robinson, Errol W.; Koppenaal, David W.; Paša-Tolić, Ljiljana

    2016-10-12

    We provide the initial performance evaluation of a 21 Tesla Fourier transform ion cyclotron resonance mass spectrometer operating at the Environmental Molecular Sciences Laboratory at Pacific Northwest National Laboratory. The spectrometer constructed for the 21T system employs a commercial dual linear ion trap mass spectrometer coupled to a FTICR spectrometer designed and built in-house. Performance gains from moving to higher magnetic field strength are exemplified by the measurement of peptide isotopic fine structure, complex natural organic matter mixtures, and large proteins. Accurate determination of isotopic fine structure was demonstrated for doubly charged substance P with minimal spectral averaging, and 8,158 molecular formulas assigned to Suwannee River Fulvic Acid standard with RMS error of 10 ppb. We also demonstrated superior performance for intact proteins; namely, broadband isotopic resolution of the entire charge state distribution of apotransferrin (78 kDa) and facile isotopic resolution of monoclonal antibody under a variety of acquisition parameters (e.g. 6 s time-domains with absorption mode processing yielded resolution of approximately 1M at m/z =2,700).

  19. Electrostatic mass spectrometer for concurrent mass-, energy- and angle-resolved measurements

    International Nuclear Information System (INIS)

    Golikov, Yu.K.; Krasnova, N.K.

    1999-01-01

    A new electron-optical scheme is considered. An energy- and mass-analyser with angular resolution are combined in one device, in which a time-of-flight principle of mass separation is used. The tool is created on the basis of electrostatic field of quasi-conical systems possessing the high-energy dispersion and high-angular resolution. A regime of simultaneous angular and energy resolution is found. If there is an ion-pulsed source then the ion groups of equal mass will be registered at the same time at a position-sensitive detector located at the edge of the field. Real parameters of the suggested scheme are calculated

  20. Fe- and Cu-complex formation with artificial ligands investigated by ultra-high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS: Implications for natural metal-organic complex studies

    Directory of Open Access Journals (Sweden)

    Hannelore Waska

    2016-07-01

    Full Text Available In recent years, electrospray-ionization mass spectrometry (ESI-MS has been increasingly used to complement the bulk determination of metal-ligand equilibria, for example via competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV. However, ESI-MS speciation analyses may be impacted by instrumental artefacts such as reduction reactions, fragmentation, and adduct formation at the ESI source, changes in the ionization efficiencies of the detected species in relation to sample matrix, and peak overlaps in response to increasing sample complexity. In our study, equilibria of the known artificial ligands citrate, ethylenediaminetetraacetic acid (EDTA, 1-nitroso-2-naphthol (NN, and salicylaldoxime (SA with iron (Fe and copper (Cu were investigated by ultra-high resolution ESI-MS, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS, under a variety of sample matrix and ionization settings. The acquired mass spectra were compared with metal-ligand equilibrium data from the literature as well as an adapted speciation model. Overall, the mass spectra produced representative species mentioned in previous reports and predicted by the speciation calculations, such as Fe(Cit, Cu(Cit2, Fe(EDTA, Cu(EDTA, Fe(NN3, and Cu(SA2. The analyses furthermore revealed new species which had been hypothesized but not measured directly using other methods, for example ternary complexes of citrate with Fe and Cu, Cu(SA monomers, and the dimer Fe(SA2. Finally, parallel measurements of a Cu+SA calibration series and a Cu+SA+EDTA competition series indicated that FT-ICR-MS can produce linear responses and low detection limits analogous to those of ACSV. We propose that ultra-high resolution FT-ICR-MS can be used as a representative tool to study interactions of trace metals with artificial as well as natural, unknown ligands at the molecular level.

  1. Direct trace analysis of metals and alloys in a quadrupole ion-trap mass spectrometer

    CERN Document Server

    Song, K S; Yang, M; Cha, H K; Lee, J M; Lee, G H

    1999-01-01

    An ion-trap mass spectrometer adopting a quadrupole ion-trap and laser ablation/ionization method was constructed. The developed system was tested for composition analysis of some metals (Cu, stainless), and alloys (hastalloy C, mumetal) by mass spectrometry. Samples were analyzed by using laser ablation from a sample probe tip followed by a mass analysis with the quadrupole ion-trap. The quadrupole ion-trap was modified to enable laser ablation by a XeCl excimer laser pulse that passed radially through the ring electrode. A mass scan of the produced ions was performed in the mass selective instability mode wherein trapped ions were successively detected by increasing the rf voltage through the ring electrode. Factors affecting the mass resolution, such as pressure of buffer gas and ablation laser power, are discussed.

  2. Phospholipid Topography of Whole-Body Sections of the Anopheles stephensi Mosquito, Characterized by High-Resolution Atmospheric-Pressure Scanning Microprobe Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging.

    Science.gov (United States)

    Khalil, Saleh M; Römpp, Andreas; Pretzel, Jette; Becker, Katja; Spengler, Bernhard

    2015-11-17

    High-resolution atmospheric-pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) has been employed to study the molecular anatomical structure of rodent malaria vector Anopheles stephensi mosquitoes. A dedicated sample preparation method was developed which suits both, the special tissue properties of the sample and the requirements of high-resolution MALDI imaging. Embedding in 5% carboxymethylcellulose (CMC) was used to maintain the tissue integrity of the whole mosquitoes, being very soft, fragile, and difficult to handle. Individual lipid compounds, specifically representing certain cell types, tissue areas, or organs, were detected and imaged in 20 μm-thick whole-body tissue sections at a spatial resolution of 12 μm per image pixel. Mass spectrometric data and information quality were based on a mass resolution of 70,000 (at m/z 200) and a mass accuracy of better than 2 ppm in positive-ion mode on an orbital trapping mass spectrometer. A total of 67 imaged lipids were assigned by database search and, in a number of cases, identified via additional MS/MS fragmentation studies directly from tissue. This is the first MSI study at 12 μm spatial resolution of the malaria vector Anopheles. The study provides insights into the molecular anatomy of Anopheles stephensi and the distribution and localization of major classes of glycerophospholipids and sphingolipids. These data can be a basis for future experiments, investigating, e.g., the metabolism of Plasmodium-infected and -uninfected Anopheles mosquitoes.

  3. Heavy-ion accelerator mass spectrometry with a 'small' accelerator

    International Nuclear Information System (INIS)

    Steier, P.; Golser, R.; Priller, A.; Vockenhuber, C.; Irlweck, K.; Kutschera, W.; Lichtenstein, V.

    2001-01-01

    Full text: VERA, the Vienna environmental research accelerator, is based on a 3-MV pelletron tandem accelerator and is designed to allow the transport of ions of all elements, from the lightest to the heaviest. The VERA heavy ion program tries to establish measurement methods which work for the long-lived radionuclides where suppression of isobars is not required. Among these are 129 I, 210 Pb, 236 U and all heavier ions where no stable isobars exist. To suppress neighboring masses, the resolution of VERA was increased, both by improving the ion optics of existing elements and by installing a new electrostatic separator after the analyzing magnet. Interfering ions which pass all beam filters are identified with a high-resolution time-of-flight system, using a 0.5 μg/cm 2 DLC (diamond-like carbon) foil in the start detector, which substantially reduces beam straggling. Compared to heavy ion AMS at large tandem accelerators (TV ≥ 8 MV) and for cases where stable isobar interference is absent, it is possible to offset the disadvantage of lower ion energy. Moreover, the more compact facilities like VERA achieve higher stability and reliability and provide advanced computer control. This promises even higher precision and sensitivity for a larger number of samples, which is a prerequisite for research on natural-occurring heavy radioisotopes at environmental levels. First results on the measurement of 210 Pb (half-life 22 a) and 236 U (23 Ma) encourages us to push towards even heavier radionuclides (e.g. 224 Pu, 81 Ma). (author)

  4. Characterisation of an ion source on the Helix MC Plus noble gas mass spectrometer - pressure dependent mass discrimination

    Science.gov (United States)

    Zhang, X.

    2017-12-01

    Characterisation of an ion source on the Helix MC Plusnoble gas mass spectrometer - pressure dependent mass discrimination Xiaodong Zhang* dong.zhang@anu.edu.au Masahiko Honda Masahiko.honda@anu.edu.au Research School of Earth Sciences, The Australian National University, Canberra, Australia To obtain reliable measurements of noble gas elemental and isotopic abundances in a geological sample it is essential that the mass discrimination (instrument-induced isotope fractionation) of the mass spectrometer remain constant over the working range of noble gas partial pressures. It is known, however, that there are pressure-dependent variations in sensitivity and mass discrimination in conventional noble gas mass spectrometers [1, 2, 3]. In this study, we discuss a practical approach to ensuring that the pressure effect in the Helix MC Plus high resolution, multi-collector noble gas mass spectrometer is minimised. The isotopic composition of atmospheric Ar was measured under a range of operating conditions to test the effects of different parameters on Ar mass discrimination. It was found that the optimised ion source conditions for pressure independent mass discrimination for Ar were different from those for maximised Ar sensitivity. The optimisation can be achieved by mainly adjusting the repeller voltage. It is likely that different ion source settings will be required to minimise pressure-dependent mass discrimination for different noble gases. A recommended procedure for tuning an ion source to reduce pressure dependent mass discrimination will be presented. References: Honda M., et al., Geochim. Cosmochim. Acta, 57, 859 -874, 1993. Burnard P. G., and Farley K. A., Geochemistry Geophysics Geosystems, Volume 1, 2000GC00038, 2000. Mabry J., et al., Journal of Analytical Atomic Spectrometry, 27, 1012 - 1017, 2012.

  5. High mass star formation to the extremes: NGC 3603 at high angular resolution in the near-infrared

    International Nuclear Information System (INIS)

    Nuernberger, Dieter E A

    2008-01-01

    High angular resolution observations play a decisive role for our understanding of high mass star formation processes, both within our Galaxy and in extragalactic starburst regions. We take the Galactic starburst template NGC 3603 as paradigm and report here on high angular resolution JHK s L' observations of the enigmatic, highly reddened sources IRS 9A-C in the NGC 3603 region, which were performed with NACO at ESO's Very Large Telescope Yepun. These broad-band imaging data strongly support the classification of IRS 9A-C as high mass protostellar candidates. We also confirm unambiguously the membership of IRS 9A-C with the NGC 3603 region as gas and dust is seen to be stripped off from their circumstellar envelopes by strong stellar winds, originating from the high mass main sequence stars of the nearby OB cluster. The orientation of these gas and dust streamers coincides with that of a very faint, only marginally detected mini-pillar protruding from the adjacent molecular clump NGC 3603 MM 2. The L' data show extended envelopes around IRS 9A-C and reveal sub-structures therein which are indicative for non-spherically distributed material. It seems obvious that protostellar mass outflows are at work to clear cavities along the polar axes of the central protostar, and / or that circumstellar disks are taking shape.

  6. Resolving mass flux at high spatial and temporal resolution using GRACE intersatellite measurements

    DEFF Research Database (Denmark)

    Rowlands, D. D.; Luthcke, S. B.; Klosko, S. M.

    2005-01-01

    resolution. Using 4° × 4° blocks at 10-day intervals, we estimate the mass of surplus or deficit water over a 52° × 60° grid centered on the Amazon basin for July 2003. We demonstrate that the recovered signals are coherent and correlate well with the expected hydrological signal....... the estimation of static monthly parameters. Through an analysis of the GRACE data residuals, we show that the fundamental temporal and spatial resolution of the GRACE data is 10 days and 400 km. We present an approach similar in concept to altimetric methods that recovers submonthly mass flux at a high spatial...

  7. Evaluation of high-resolution mass spectrometry for urine toxicology screening in a pain management setting.

    Science.gov (United States)

    Crews, Bridgit O; Pesce, Amadeo J; West, Robert; Nguyen, Hugh; Fitzgerald, Robert L

    2012-01-01

    To evaluate liquid chromatography-high-resolution mass spectrometry (LC-HR-MS) for urine toxicology screening, 29 analytes were quantitated in 152 urine specimens from patients with chronic pain using two unique mass spectrometry platforms. De-identified specimens were quantitated in April of 2011 by liquid chromatography-triple quadrupole mass spectrometry (LC-MS-MS) and by full-scan LC-HR-MS at Millennium Laboratories. Considering LC-MS-MS as the reference method, false positive results were identified in 19 specimens measured by LC-HR-MS. Application of relative retention times using deuterium labeled internal standards improved the rate of false positive detection to only five specimens, with four occurring for the same analyte. Ultra-high-resolution mass spectrometry (R = 100,000 at m/z 200) showed no improvement over high-resolution mass spectrometry (R = 10,000 at m/z 200) in the number of false positives detected. Quantitative results measured by LC-MS-MS and LC-HR-MS showed good agreement over four orders of dynamic range. This study demonstrates that LC-HR-MS is a suitable platform for toxicology screening for a pain management population and that quantitative accuracy and sensitivity are comparable to that achieved with LC-MS-MS. The specificity of LC-HR-MS is improved by the addition of deuterium labeled internal standards and the implementation of relative retention time matching.

  8. Ion transfer from an atmospheric pressure ion funnel into a mass spectrometer with different interface options: Simulation-based optimization of ion transmission efficiency.

    Science.gov (United States)

    Mayer, Thomas; Borsdorf, Helko

    2016-02-15

    We optimized an atmospheric pressure ion funnel (APIF) including different interface options (pinhole, capillary, and nozzle) regarding a maximal ion transmission. Previous computer simulations consider the ion funnel itself and do not include the geometry of the following components which can considerably influence the ion transmission into the vacuum stage. Initially, a three-dimensional computer-aided design (CAD) model of our setup was created using Autodesk Inventor. This model was imported to the Autodesk Simulation CFD program where the computational fluid dynamics (CFD) were calculated. The flow field was transferred to SIMION 8.1. Investigations of ion trajectories were carried out using the SDS (statistical diffusion simulation) tool of SIMION, which allowed us to evaluate the flow regime, pressure, and temperature values that we obtained. The simulation-based optimization of different interfaces between an atmospheric pressure ion funnel and the first vacuum stage of a mass spectrometer require the consideration of fluid dynamics. The use of a Venturi nozzle ensures the highest level of transmission efficiency in comparison to capillaries or pinholes. However, the application of radiofrequency (RF) voltage and an appropriate direct current (DC) field leads to process optimization and maximum ion transfer. The nozzle does not hinder the transfer of small ions. Our high-resolution SIMION model (0.01 mm grid unit(-1) ) under consideration of fluid dynamics is generally suitable for predicting the ion transmission through an atmospheric-vacuum system for mass spectrometry and enables the optimization of operational parameters. A Venturi nozzle inserted between the ion funnel and the mass spectrometer permits maximal ion transmission. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  9. High-resolution compact Johann crystal spectrometer with the Livermore electron beam ion trap

    International Nuclear Information System (INIS)

    Robbins, D.L.; Chen, H.; Beiersdorfer, P.; Faenov, A.Ya.; Pikuz, T.A.; May, M.J.; Dunn, J.; Smith, A.J.

    2004-01-01

    A compact high-resolution (λ/Δλ≅10 000) spherically bent crystal spectrometer in the Johann geometry was recently installed and tested on the Lawrence Livermore National Laboratory SuperEBIT electron beam ion trap. The curvature of the mica (002) crystal grating allows for higher collection efficiency compared to the flat and cylindrically bent crystal spectrometers commonly used on the Livermore electron beam ion traps. The spectrometer's Johann configuration enables orientation of its dispersion plane to be parallel to the electron beam propagation. Used in concert with a crystal spectrometer, whose dispersion plane is perpendicular to the electron beam propagation, the polarization of x-ray emission lines can be measured

  10. Liquid chromatography with high resolution mass spectrometry for identification of organic contaminants in fish fillet: screening and quantification assessment using two scan modes for data acquisition.

    Science.gov (United States)

    Munaretto, Juliana S; May, Marília M; Saibt, Nathália; Zanella, Renato

    2016-07-22

    This study proposed a strategy to identify and quantify 182 organic contaminants from different chemical classes, as for instance pesticides, veterinary drug and personal care products, in fish fillet using liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-QToF/MS). For this purpose, two different scan methods (full scan and all ions MS/MS) were evaluated to assess the best option for screening analysis in spiked fish fillet samples. In general, full scan acquisition was found to be more reliable (84%) in the automatic identification and quantification when compared to all ions MS/MS with 72% of the compounds detected. Additionally, a qualitative automatic search showed a mass accuracy error below 5ppm for 77% of the compounds in full scan mode compared to only 52% in all ions MS/MS scan. However, all ions MS/MS provides fragmentation information of the target compounds. Undoubtedly, structural information of a wide number of compounds can be obtained using high resolution mass spectrometry (HRMS), but it is necessary thoroughly assess it, in order to choose the best scan mode. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The new high-resolution IRMS MAT253 ULTRA at Utrecht University

    Science.gov (United States)

    Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

    2017-04-01

    In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas

  12. High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry.

    Science.gov (United States)

    Fan, Ruo-Jing; Zhang, Fang; Chen, Xiu-Ping; Qi, Wan-Shu; Guan, Qing; Sun, Tuan-Qi; Guo, Yin-Long

    2017-04-08

    The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%-12.3% for intra-day and 0.9%-7.8% for inter-day) and good accuracy (91%-109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. MASH Suite: a user-friendly and versatile software interface for high-resolution mass spectrometry data interpretation and visualization.

    Science.gov (United States)

    Guner, Huseyin; Close, Patrick L; Cai, Wenxuan; Zhang, Han; Peng, Ying; Gregorich, Zachery R; Ge, Ying

    2014-03-01

    The rapid advancements in mass spectrometry (MS) instrumentation, particularly in Fourier transform (FT) MS, have made the acquisition of high-resolution and high-accuracy mass measurements routine. However, the software tools for the interpretation of high-resolution MS data are underdeveloped. Although several algorithms for the automatic processing of high-resolution MS data are available, there is still an urgent need for a user-friendly interface with functions that allow users to visualize and validate the computational output. Therefore, we have developed MASH Suite, a user-friendly and versatile software interface for processing high-resolution MS data. MASH Suite contains a wide range of features that allow users to easily navigate through data analysis, visualize complex high-resolution MS data, and manually validate automatically processed results. Furthermore, it provides easy, fast, and reliable interpretation of top-down, middle-down, and bottom-up MS data. MASH Suite is convenient, easily operated, and freely available. It can greatly facilitate the comprehensive interpretation and validation of high-resolution MS data with high accuracy and reliability.

  14. Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2009-04-01

    Full Text Available Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS. Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO only, sulfur (S containing CHOS compounds, nitrogen (N containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

  15. Multiplex Mass Spectrometric Imaging with Polarity Switching for Concurrent Acquisition of Positive and Negative Ion Images

    Science.gov (United States)

    Korte, Andrew R.; Lee, Young Jin

    2013-06-01

    We have recently developed a multiplex mass spectrometry imaging (MSI) method which incorporates high mass resolution imaging and MS/MS and MS3 imaging of several compounds in a single data acquisition utilizing a hybrid linear ion trap-Orbitrap mass spectrometer (Perdian and Lee, Anal. Chem. 82, 9393-9400, 2010). Here we extend this capability to obtain positive and negative ion MS and MS/MS spectra in a single MS imaging experiment through polarity switching within spiral steps of each raster step. This methodology was demonstrated for the analysis of various lipid class compounds in a section of mouse brain. This allows for simultaneous imaging of compounds that are readily ionized in positive mode (e.g., phosphatidylcholines and sphingomyelins) and those that are readily ionized in negative mode (e.g., sulfatides, phosphatidylinositols and phosphatidylserines). MS/MS imaging was also performed for a few compounds in both positive and negative ion mode within the same experimental set-up. Insufficient stabilization time for the Orbitrap high voltage leads to slight deviations in observed masses, but these deviations are systematic and were easily corrected with a two-point calibration to background ions.

  16. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Science.gov (United States)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2012-02-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25-0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this

  17. Profiling of integral membrane proteins and their post translational modifications using high-resolution mass spectrometry

    Science.gov (United States)

    Souda, Puneet; Ryan, Christopher M.; Cramer, William A.; Whitelegge, Julian

    2011-01-01

    Integral membrane proteins pose challenges to traditional proteomics approaches due to unique physicochemical properties including hydrophobic transmembrane domains that limit solubility in aqueous solvents. A well resolved intact protein molecular mass profile defines a protein’s native covalent state including post-translational modifications, and is thus a vital measurement toward full structure determination. Both soluble loop regions and transmembrane regions potentially contain post-translational modifications that must be characterized if the covalent primary structure of a membrane protein is to be defined. This goal has been achieved using electrospray-ionization mass spectrometry (ESI-MS) with low-resolution mass analyzers for intact protein profiling, and high-resolution instruments for top-down experiments, toward complete covalent primary structure information. In top-down, the intact protein profile is supplemented by gas-phase fragmentation of the intact protein, including its transmembrane regions, using collisionally activated and/or electroncapture dissociation (CAD/ECD) to yield sequence-dependent high-resolution MS information. Dedicated liquid chromatography systems with aqueous/organic solvent mixtures were developed allowing us to demonstrate that polytopic integral membrane proteins are amenable to ESI-MS analysis, including top-down measurements. Covalent post-translational modifications are localized regardless of their position in transmembrane domains. Top-down measurements provide a more detail oriented high-resolution description of post-transcriptional and post-translational diversity for enhanced understanding beyond genomic translation. PMID:21982782

  18. Frequency-scanning MALDI linear ion trap mass spectrometer for large biomolecular ion detection.

    Science.gov (United States)

    Lu, I-Chung; Lin, Jung Lee; Lai, Szu-Hsueh; Chen, Chung-Hsuan

    2011-11-01

    This study presents the first report on the development of a matrix-assisted laser desorption ionization (MALDI) linear ion trap mass spectrometer for large biomolecular ion detection by frequency scan. We designed, installed, and tested this radio frequency (RF) scan linear ion trap mass spectrometer and its associated electronics to dramatically extend the mass region to be detected. The RF circuit can be adjusted from 300 to 10 kHz with a set of operation amplifiers. To trap the ions produced by MALDI, a high pressure of helium buffer gas was employed to quench extra kinetic energy of the heavy ions produced by MALDI. The successful detection of the singly charged secretory immunoglobulin A ions indicates that the detectable mass-to-charge ratio (m/z) of this system can reach ~385 000 or beyond.

  19. Detection of Type A Trichothecene Di-Glucosides Produced in Corn by High-Resolution Liquid Chromatography-Orbitrap Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Hitoshi Nagashima

    2013-03-01

    Full Text Available The existence of di-glucosylated derivative of T-2 toxin in plant (corn powder was confirmed for the first time in addition to that of HT-2 toxin. These masked mycotoxins (mycotoxin glucosides were identified as T-2 toxin-di-glucoside (T2GlcGlc and HT-2 toxin-di-glucoside (HT2GlcGlc based on accurate mass measurements of characteristic ions and fragmentation patterns using high-resolution liquid chromatography-Orbitrap mass spectrometric (LC-Orbitrap MS analysis. Although the absolute structure of T2GlcGlc was not clarified, two glucose molecules were suggested to be conjugated at 3-OH position in tandem when considering the structure of T-2 toxin. On the other hand, the specification of the structure seems to be more complicated in the case of HT2GlcGlc, since HT-2 toxin has two possible positions (at 3-OH and 4-OH to be glusocylated. In addition, 15-monoacetoxyscirpenol-glucoside (MASGlc was also detected in the identical sample.

  20. Nontargeted Screening Method for Illegal Additives Based on Ultrahigh-Performance Liquid Chromatography-High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Fu, Yanqing; Zhou, Zhihui; Kong, Hongwei; Lu, Xin; Zhao, Xinjie; Chen, Yihui; Chen, Jia; Wu, Zeming; Xu, Zhiliang; Zhao, Chunxia; Xu, Guowang

    2016-09-06

    Identification of illegal additives in complex matrixes is important in the food safety field. In this study a nontargeted screening strategy was developed to find illegal additives based on ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). First, an analytical method for possible illegal additives in complex matrixes was established including fast sample pretreatment, accurate UHPLC separation, and HRMS detection. Second, efficient data processing and differential analysis workflow were suggested and applied to find potential risk compounds. Third, structure elucidation of risk compounds was performed by (1) searching online databases [Metlin and the Human Metabolome Database (HMDB)] and an in-house database which was established at the above-defined conditions of UHPLC-HRMS analysis and contains information on retention time, mass spectra (MS), and tandem mass spectra (MS/MS) of 475 illegal additives, (2) analyzing fragment ions, and (3) referring to fragmentation rules. Fish was taken as an example to show the usefulness of the nontargeted screening strategy, and six additives were found in suspected fish samples. Quantitative analysis was further carried out to determine the contents of these compounds. The satisfactory application of this strategy in fish samples means that it can also be used in the screening of illegal additives in other kinds of food samples.

  1. Total mass difference statistics algorithm: a new approach to identification of high-mass building blocks in electrospray ionization Fourier transform ion cyclotron mass spectrometry data of natural organic matter.

    Science.gov (United States)

    Kunenkov, Erast V; Kononikhin, Alexey S; Perminova, Irina V; Hertkorn, Norbert; Gaspar, Andras; Schmitt-Kopplin, Philippe; Popov, Igor A; Garmash, Andrew V; Nikolaev, Evgeniy N

    2009-12-15

    The ultrahigh-resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrum of natural organic matter (NOM) contains several thousand peaks with dozens of molecules matching the same nominal mass. Such a complexity poses a significant challenge for automatic data interpretation, in which the most difficult task is molecular formula assignment, especially in the case of heavy and/or multielement ions. In this study, a new universal algorithm for automatic treatment of FTICR mass spectra of NOM and humic substances based on total mass difference statistics (TMDS) has been developed and implemented. The algorithm enables a blind search for unknown building blocks (instead of a priori known ones) by revealing repetitive patterns present in spectra. In this respect, it differs from all previously developed approaches. This algorithm was implemented in designing FIRAN-software for fully automated analysis of mass data with high peak density. The specific feature of FIRAN is its ability to assign formulas to heavy and/or multielement molecules using "virtual elements" approach. To verify the approach, it was used for processing mass spectra of sodium polystyrene sulfonate (PSS, M(w) = 2200 Da) and polymethacrylate (PMA, M(w) = 3290 Da) which produce heavy multielement and multiply-charged ions. Application of TMDS identified unambiguously monomers present in the polymers consistent with their structure: C(8)H(7)SO(3)Na for PSS and C(4)H(6)O(2) for PMA. It also allowed unambiguous formula assignment to all multiply-charged peaks including the heaviest peak in PMA spectrum at mass 4025.6625 with charge state 6- (mass bias -0.33 ppm). Application of the TMDS-algorithm to processing data on the Suwannee River FA has proven its unique capacities in analysis of spectra with high peak density: it has not only identified the known small building blocks in the structure of FA such as CH(2), H(2), C(2)H(2)O, O but the heavier unit at 154.027 amu. The latter was

  2. A compact high resolution electrospray ionization ion mobility spectrometer.

    Science.gov (United States)

    Reinecke, T; Kirk, A T; Ahrens, A; Raddatz, C-R; Thoben, C; Zimmermann, S

    2016-04-01

    Electrospray is a commonly used ionization method for the analysis of liquids. An electrospray is a dispersed nebular of charged droplets produced under the influence of a strong electrical field. Subsequently, ions are produced in a complex process initiated by evaporation of neutral solvent molecules from these droplets. We coupled an electrospray ionization source to our previously described high resolution ion mobility spectrometer with 75 mm drift tube length and a drift voltage of 5 kV. When using a tritium source for chemical gas phase ionization, a resolving power of R=100 was reported for this setup. We replaced the tritium source and the field switching shutter by an electrospray needle, a desolvation region with variable length and a three-grid shutter for injecting ions into the drift region. Preliminary measurements with tetraalkylammonium halides show that the current configuration with the electrospray ionization source maintains the resolving power of R=100. In this work, we present the characterization of our setup. One major advantage of our setup is that the desolvation region can be heated separately from the drift region so that the temperature in the drift region stays at room temperature even up to desolvation region temperatures of 100 °C. We perform parametric studies for the investigation of the influence of temperature on solvent evaporation with different ratios of water and methanol in the solvent for different analyte substances. Furthermore, the setup is operated in negative mode and spectra of bentazon with different solvents are presented. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Novel strategy for the determination of illegal adulterants in health foods and herbal medicines using high-performance liquid chromatography with high-resolution mass spectrometry.

    Science.gov (United States)

    Wang, Zhe; Wu, Caisheng; Wang, Gangli; Zhang, Qingsheng; Zhang, Jinlan

    2015-03-01

    The detection, confirmation, and quantification of multiple illegal adulterants in health foods and herbal medicines by using a single analytical method are a challenge. This paper reports on a new strategy to meet this challenge by employing high-performance liquid chromatography coupled with high-resolution mass spectrometry and a mass spectral tree similarity filter technique. This analytical method can rapidly collect high-resolution, high-accuracy, optionally multistage mass data for compounds in samples. After a preliminary screening by retention time and high-resolution mass spectral data, known illegal adulterants can be detected. The mass spectral tree similarity filter technique has been applied to rapidly confirm these adulterants and simultaneously discover unknown ones. By using full-scan mass spectra as stem and data-dependent subsequent stage mass spectra to form branches, mass spectrometry data from detected compounds are converted into mass spectral trees. The known or unknown illegal adulterants in the samples are confirmed or discovered based on the similarity between their mass spectral trees and those of the references in a library, and they are finally quantified against standard curves. This new strategy has been tested by using 50 samples, and the illegal adulterants were rapidly and effectively detected, confirmed and quantified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A novel ToF-SIMS operation mode for sub 100 nm lateral resolution: Application and performance

    International Nuclear Information System (INIS)

    Kubicek, Markus; Holzlechner, Gerald; Opitz, Alexander K.; Larisegger, Silvia; Hutter, Herbert; Fleig, Jürgen

    2014-01-01

    A novel operation mode for time of flight-secondary ion mass spectrometry (ToF-SIMS) is described for a TOF.SIMS 5 instrument with a Bi-ion gun. It features sub 100 nm lateral resolution, adjustable primary ion currents and the possibility to measure with high lateral resolution as well as high mass resolution. The adjustment and performance of the novel operation mode are described and compared to established ToF-SIMS operation modes. Several examples of application featuring novel scientific results show the capabilities of the operation mode in terms of lateral resolution, accuracy of isotope analysis of oxygen, and combination of high lateral and mass resolution. The relationship between high lateral resolution and operation of SIMS in static mode is discussed.

  5. High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

    Science.gov (United States)

    Swearingen, Kristian E; Moritz, Robert L

    2012-10-01

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

  6. A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry

    International Nuclear Information System (INIS)

    Yang, Min; Zhou, Zhe; Guo, De-an

    2015-01-01

    Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the "3"4S isotopic ion is drastically affected by "1"3C_2 and "1"8O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ("1"2C_x"1H_y"1"6O_z"3"2S"1"3C_2"1"8O, "1"2C_x_+_2"1H_y"1"6O_z_+_1"3"4S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS"n). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. - Highlights: • We provide a new strategy for specifically screening of sulfurous compounds. • The fine isotopic pattern filter (FIPF) bases on separation of "1"3C_2+"1"8O and "3"4S. • Ultra high resolution mass (100,000 FWHM @ 400 m/z) is essential for FIPF. • IPF is applied to study the unique components of TCM for the first time. • New sulfurous components

  7. Gold finger formation studied by high-resolution mass spectrometry and in silico methods

    NARCIS (Netherlands)

    Laskay, Ü.A.; Garino, C.; Tsybin, Y.O.; Salassa, L.; Casini, A.

    2015-01-01

    High-resolution mass spectrometry and quantum mechanics/molecular mechanics studies were employed for characterizing the formation of two gold finger (GF) domains from the reaction of zinc fingers (ZF) with gold complexes. The influence of both the gold oxidation state and the ZF coordination sphere

  8. Quantification of PAHs and oxy-PAHs on airborne particulate matter in Chiang Mai, Thailand, using gas chromatography high resolution mass spectrometry

    Science.gov (United States)

    Walgraeve, Christophe; Chantara, Somporn; Sopajaree, Khajornsak; De Wispelaere, Patrick; Demeestere, Kristof; Van Langenhove, Herman

    2015-04-01

    An analytical method using gas chromatography high resolution mass spectrometry was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs (of which 4 diketones, 3 ketones, 4 aldehydes and one anhydride) on atmospheric particulate matter with an aerodynamic diameter less than 10 μm (PM10). The magnetic sector mass spectrometer was run in multiple ion detection mode (MID) with a mass resolution above 10 000 (10% valley definition) and allows for a selective accurate mass detection of the characteristic ions of the target analytes. Instrumental detection limits between 0.04 pg and 1.34 pg were obtained for the PAHs, whereas for the oxy-PAHs they ranged between 0.08 pg and 2.13 pg. Pressurized liquid extraction using dichloromethane was evaluated and excellent recoveries ranging between 87% and 98% for the PAHs and between 74% and 110% for 10 oxy-PAHs were obtained, when the optimum extraction temperature of 150 °C was applied. The developed method was finally used to determine PAHs and oxy-PAHs concentration levels from particulate matter samples collected in the wet season at 4 different locations in Chiang Mai, Thailand (n = 72). This study brings forward the first concentration levels of oxy-PAHs in Thailand. The median of the sum of the PAHs and oxy-PAHs concentrations was 3.4 ng/m3 and 1.1 ng/m3 respectively, which shows the importance of the group of the oxy-PAHs as PM10 constituents. High molecular weight PAHs contributed the most to the ∑PAHs. For example, benzo[ghi]perylene was responsible for 30-44% of the ∑PAHs. The highest contribution to ∑oxy-PAHs came from 1,8-napthalic anhydride (26-78%), followed by anthracene-9,10-dione (4-27%) and 7H-benzo[de]anthracene-7-one (6-26%). Indications of the degradation of PAHs and/or formation of oxy-PAHs were observed.

  9. Diesel characterization by high-resolution mass spectrometry - gas chromatography

    International Nuclear Information System (INIS)

    Baldrich, C.A

    1998-01-01

    High-resolution mass spectrometry-gas chromatography is combined with the HC22 method in order to obtain detailed information about the chemical composition of diesel and the distribution of different compound types in terms of its final boiling temperature from a single analysis. The total time elapsed from sample injection and signal processing to obtain final results is 90 minutes. This fact makes this methodology a new and very important tool for the decision making process concerning the most suitable final boiling temperature and the type of treatment of the product in order to obtain diesel that fulfills the international standards. The consistency and repeatability of the experimental results are demonstrated

  10. Determination of fusarium mycotoxins in wheat, maize and animal feed using on-line clean-up with high resolution mass spectrometry.

    Science.gov (United States)

    Ates, E; Mittendorf, K; Stroka, J; Senyuva, H

    2013-01-01

    An automated method involving on-line clean-up and analytical separation in a single run using TurboFlow™ reversed phase liquid chromatography coupled to a high resolution mass spectrometer has been developed for the simultaneous determination of deoxynivalenol, T2 toxin, HT2 toxin, zearalenone and fumonisins B1 and B2 in maize, wheat and animal feed. Detection was performed in full scan mode at a resolution of R = 100,000 full width at half maximum with high energy collision cell dissociation for the determination of fragment ions with a mass accuracy below 5 ppm. The extract from homogenised samples, after blending with a 0.1% aqueous mixture of 0.1% formic acid/acetonitrile (43:57) for 45 min, was injected directly onto the TurboFlow™ (TLX) column for automated on-line clean-up followed by analytical separation and accurate mass detection. The TurboFlow™ column enabled specific binding of target mycotoxins, whereas higher molecular weight compounds, like fats, proteins and other interferences with different chemical properties, were removed to waste. Single laboratory method validation was performed by spiking blank materials with mycotoxin standards. The recovery and repeatability was determined by spiking at three concentration levels (50, 100 and 200% of legislative limits) with six replicates. Average recovery, relative standard deviation and intermediate precision values were 71 to 120%, 1 to 19% and 4 to 19%, respectively. The method accuracy was confirmed with certified reference materials and participation in proficiency testing.

  11. Study of extraterrestrial material by means of a high sensitive mass spectrometer, 1

    International Nuclear Information System (INIS)

    Arai, O.; Kaneko, K.; Kobayashi, K.; Shimamura, T.

    1975-01-01

    In this report it is described about a high sensitive mass spectrometer for measurement of isotopic abundance of extraterrestrial material. Detecting isotopic anomalies in extraterrestrial matter induced by cosmic ray or solar wind irradiation, we can obtain many informations about interplanetary and/or intersteller space. For this purpose we reform the mass spectrometer of Low Energy Physics Division of INS to improve the sensitivity and the resolution. In section I--VI some improvements of the mass spectrometer (vacuum system, ion source, collector etc.) are described. In section VII--X newly developed ion counting system is discussed. (auth.)

  12. Cs+ ion source for secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Bentz, B.L.; Weiss, H.; Liebl, H.

    1981-12-01

    Various types of cesium ionization sources currently used in secondary ion mass spectrometry are briefly reviewed, followed by a description of the design and performance of a novel, thermal surface ionization Cs + source developed in this laboratory. The source was evaluated for secondary ion mass spectrometry applications using the COALA ion microprobe mass analyzer. (orig.)

  13. High-resolution Kendrick Mass Defect Analysis of Poly(ethylene oxide)-based Non-ionic Surfactants and Their Degradation Products.

    Science.gov (United States)

    Fouquet, Thierry; Shimada, Haruo; Maeno, Katsuyuki; Ito, Kanako; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

    2017-09-01

    Matrix assisted laser desorption ionization (MALDI) high-resolution mass spectrometry (HRMS) and the recently introduced high-resolution Kendrick mass defect (HRKMD) analysis are combined to thoroughly characterize non-ionic surfactants made of a poly(ethylene oxide) (PEO) core capped by esters of fatty acids. A PEO monostearate surfactant is first analyzed as a proof of principle of the HRKMD analysis conducted with a fraction of EO as the base unit (EO/X with X being an integer) in lieu of EO for a regular KMD analysis. Data visualization is greatly enhanced and the distributions detected in the MALDI mass spectrum are assigned to a pristine (H, OH)-PEO as well as mono- and di-esterified PEO chains with palmitate and stearate end-groups in HRKMD plots computed with EO/45. The MALDI-HRMS/HRKMD analysis is then successfully applied to the more complex case of ethoxylated hydrogenated castor oil (EHCO) found to contain a large number of hydrogenated ricinoleate moieties (up to 14) in its HRKMD plot computed with EO/43, departing from the expected triglyceride structure. The exhaustiveness of the MALDI-HRMS/HRKMD strategy is validated by comparing the so-obtained fingerprints with results from alternative techniques (electrospray ionization MS, size exclusion and liquid adsorption chromatography, ion mobility spectrometry). Finally, aged non-ionic surfactants formed upon hydrolytic degradation are analyzed by MALDI-HRMS/HRKMD to easily assign the degradation products and infer the associated degradation routes. In addition to the hydrolysis of the ester groups observed for EHCO, chain scissions and new polar end-groups are observed in the HRKMD plot of PEO monostearate arising from a competitive oxidative ageing.

  14. HIGH ANGULAR RESOLUTION OBSERVATIONS OF FOUR CANDIDATE BLAST HIGH-MASS STARLESS CORES

    International Nuclear Information System (INIS)

    Olmi, Luca; Poventud, Carlos M.; Araya, Esteban D.; Chapin, Edward L.; Gibb, Andrew; Hofner, Peter; Martin, Peter G.

    2010-01-01

    We discuss high angular resolution observations of ammonia toward four candidate high-mass starless cores (HMSCs). The cores were identified by the Balloon-borne Large Aperture Submillimeter Telescope (BLAST) during its 2005 survey of the Vulpecula region where 60 compact sources were detected simultaneously at 250, 350, and 500 μm. Four of these cores, with no IRAS-PSC or MSX counterparts, were mapped with the NRAO Very Large Array and observed with the Effelsberg 100 m telescope in the NH 3 (1,1) and (2,2) spectral lines. Our observations indicate that the four cores are cold (T k -1 . The four BLAST cores appear to be colder and more quiescent than other previously observed HMSC candidates, suggesting an earlier stage of evolution.

  15. A novel ToF-SIMS operation mode for sub 100 nm lateral resolution: Application and performance.

    Science.gov (United States)

    Kubicek, Markus; Holzlechner, Gerald; Opitz, Alexander K; Larisegger, Silvia; Hutter, Herbert; Fleig, Jürgen

    2014-01-15

    A novel operation mode for time of flight-secondary ion mass spectrometry (ToF-SIMS) is described for a TOF.SIMS 5 instrument with a Bi-ion gun. It features sub 100 nm lateral resolution, adjustable primary ion currents and the possibility to measure with high lateral resolution as well as high mass resolution. The adjustment and performance of the novel operation mode are described and compared to established ToF-SIMS operation modes. Several examples of application featuring novel scientific results show the capabilities of the operation mode in terms of lateral resolution, accuracy of isotope analysis of oxygen, and combination of high lateral and mass resolution. The relationship between high lateral resolution and operation of SIMS in static mode is discussed.

  16. Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

    OpenAIRE

    Kourtchev, I; Godoi, RHM; Connors, S; Levine, JG; Archibald, AT; Godoi, AFL; Paralovo, SL; Barbosa, CGG; Souza, RAF; Manzi, AO; Seco, R; Sjostedt, S; Park, J-H; Guenther, A; Kim, S

    2016-01-01

    The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM$_{2.5}$ aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagr...

  17. In house validation of a high resolution mass spectrometry Orbitrap-based method for multiple allergen detection in a processed model food.

    Science.gov (United States)

    Pilolli, Rosa; De Angelis, Elisabetta; Monaci, Linda

    2018-02-13

    In recent years, mass spectrometry (MS) has been establishing its role in the development of analytical methods for multiple allergen detection, but most analyses are being carried out on low-resolution mass spectrometers such as triple quadrupole or ion traps. In this investigation, performance provided by a high resolution (HR) hybrid quadrupole-Orbitrap™ MS platform for the multiple allergens detection in processed food matrix is presented. In particular, three different acquisition modes were compared: full-MS, targeted-selected ion monitoring with data-dependent fragmentation (t-SIM/dd2), and parallel reaction monitoring. In order to challenge the HR-MS platform, the sample preparation was kept as simple as possible, limited to a 30-min ultrasound-aided protein extraction followed by clean-up with disposable size exclusion cartridges. Selected peptide markers tracing for five allergenic ingredients namely skim milk, whole egg, soy flour, ground hazelnut, and ground peanut were monitored in home-made cookies chosen as model processed matrix. Timed t-SIM/dd2 was found the best choice as a good compromise between sensitivity and accuracy, accomplishing the detection of 17 peptides originating from the five allergens in the same run. The optimized method was validated in-house through the evaluation of matrix and processing effects, recoveries, and precision. The selected quantitative markers for each allergenic ingredient provided quantification of 60-100 μg ingred /g allergenic ingredient/matrix in incurred cookies.

  18. A high-resolution x-ray spectrometer for a kaon mass measurement

    Energy Technology Data Exchange (ETDEWEB)

    Phelan, Kevin, E-mail: kevin.phelan@oeaw.ac.at [Stefan Meyer Institute for Subatomic Physics of The Austrian Academy of Sciences, Boltzmanngasse 3, 1090 Vienna (Austria); Suzuki, Ken; Zmeskal, Johann [Stefan Meyer Institute for Subatomic Physics of The Austrian Academy of Sciences, Boltzmanngasse 3, 1090 Vienna (Austria); Tortorella, Daniele [Payr Engineering GmbH, Wiederschwing 25, A-9564 Patergassen (Austria); Bühler, Matthias; Hertrich, Theo [Low Temperature Solutions UG, Bahnhofstraße 21, D-85737 Ismaning (Germany)

    2017-02-11

    The ASPECT consortium (Adaptable Spectrometer Enabled by Cryogenic Technology) is currently constructing a generalised cryogenic platform for cryogenic detector work which will be able to accommodate a wide range of sensors. The cryogenics system is based on a small mechanical cooler with a further adiabatic demagnetisation stage and will work with cryogenic detectors at sub-Kelvin temperatures. The commercial aim of the consortium is to produce a compact, user-friendly device with an emphasis on reliability and portability which can easily be transported for specialised on-site work, such as beam-lines or telescope facilities. The cryogenic detector platform will accommodate a specially developed cryogenic sensor, either a metallic magnetic calorimeter or a magnetic penetration-depth thermometer. The detectors will be designed to work in various temperatures regions with an emphasis on optimising the various detector resolutions for specific temperatures. One resolution target is of about 10 eV at the energies range typically created in kaonic atoms experiments (soft x-ray energies). A following step will see the introduction of continuous, high-power, sub-Kelvin cooling which will bring the cryogenic basis for a high resolution spectrometer system to the market. The scientific goal of the project will produce an experimental set-up optimised for kaon-mass measurements performing high-resolution x-ray spectroscopy on a beam-line provided foreseeably by the J-PARC (Tokai, Japan) or DAΦNE (Frascati, Italy) facilities.

  19. Wide-Scope Screening Method for Multiclass Veterinary Drug Residues in Fish, Shrimp, and Eel Using Liquid Chromatography-Quadrupole High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Turnipseed, Sherri B; Storey, Joseph M; Lohne, Jack J; Andersen, Wendy C; Burger, Robert; Johnson, Aaron S; Madson, Mark R

    2017-08-30

    A screening method for veterinary drug residues in fish, shrimp, and eel using LC with a high-resolution MS instrument has been developed and validated. The method was optimized for over 70 test compounds representing a variety of veterinary drug classes. Tissues were extracted by vortex mixing with acetonitrile acidified with 2% acetic acid and 0.2% p-toluenesulfonic acid. A centrifuged portion of the extract was passed through a novel solid phase extraction cartridge designed to remove interfering matrix components from tissue extracts. The eluent was then evaporated and reconstituted for analysis. Data were collected with a quadrupole-Orbitrap high-resolution mass spectrometer using both nontargeted and targeted acquisition methods. Residues were detected on the basis of the exact mass of the precursor and a product ion along with isotope pattern and retention time matching. Semiquantitative data analysis compared MS 1 signal to a one-point extracted matrix standard at a target testing level. The test compounds were detected and identified in salmon, tilapia, catfish, shrimp, and eel extracts fortified at the target testing levels. Fish dosed with selected analytes and aquaculture samples previously found to contain residues were also analyzed. The screening method can be expanded to monitor for an additional >260 veterinary drugs on the basis of exact mass measurements and retention times.

  20. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Directory of Open Access Journals (Sweden)

    M. F. Heringa

    2012-02-01

    Full Text Available Organic aerosol (OA represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm mass. Secondary organic aerosol (SOA is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS and compared to SOA from α-pinene.

    The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production.

    Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25–0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions.

    The HR data of the four sources could be clustered and separated using

  1. Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Poad, Berwyck L.; Zheng, Xueyun; Mitchell, Todd A.; Smith, Richard D.; Baker, Erin M.; Blanksby, Stephen J.

    2017-12-21

    One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.

  2. High-Resolution Liquid Chromatography Tandem Mass Spectrometry Enables Large Scale Molecular Characterization of Dissolved Organic Matter

    Directory of Open Access Journals (Sweden)

    Daniel Petras

    2017-12-01

    Full Text Available Dissolved organic matter (DOM is arguably one of the most complex exometabolomes on earth, and is comprised of thousands of compounds, that together contribute more than 600 × 1015 g carbon. This reservoir is primarily the product of interactions between the upper ocean's microbial food web, yet abiotic processes that occur over millennia have also modified many of its molecules. The compounds within this reservoir play important roles in determining the rate and extent of element exchange between inorganic reservoirs and the marine biosphere, while also mediating microbe-microbe interactions. As such, there has been a widespread effort to characterize DOM using high-resolution analytical methods including nuclear magnetic resonance spectroscopy (NMR and mass spectrometry (MS. To date, molecular information in DOM has been primarily obtained through calculated molecular formulas from exact mass. This approach has the advantage of being non-targeted, accessing the inherent complexity of DOM. Molecular structures are however still elusive and the most commonly used instruments are costly. More recently, tandem mass spectrometry has been employed to more precisely identify DOM components through comparison to library mass spectra. Here we describe a data acquisition and analysis workflow that expands the repertoire of high-resolution analytical approaches available to access the complexity of DOM molecules that are amenable to electrospray ionization (ESI MS. We couple liquid chromatographic separation with tandem MS (LC-MS/MS and a data analysis pipeline, that integrates peak extraction from extracted ion chromatograms (XIC, molecular formula calculation and molecular networking. This provides more precise structural characterization. Although only around 1% of detectable DOM compounds can be annotated through publicly available spectral libraries, community-wide participation in populating and annotating DOM datasets could rapidly increase the

  3. Liquid chromatography-high resolution mass spectrometric methods for the surveillance monitoring of cyanotoxins in freshwaters.

    Science.gov (United States)

    Bogialli, Sara; Bortolini, Claudio; Di Gangi, Iole Maria; Di Gregorio, Federica Nigro; Lucentini, Luca; Favaro, Gabriella; Pastore, Paolo

    2017-08-01

    A comprehensive risk management on human exposure to cyanotoxins, whose production is actually unpredictable, is limited by reliable analytical tools for monitoring as many toxic algal metabolites as possible. Two analytical approaches based on a LC-QTOF system for target analysis and suspect screening of cyanotoxins in freshwater were presented. A database with 369 compounds belonging to cyanobacterial metabolites was developed and used for a retrospective data analysis based on high resolution mass spectrometry (HRMS). HRMS fragmentation of the suspect cyanotoxin precursor ions was subsequently performed for correctly identifying the specific variants. Alternatively, an automatic tandem HRMS analysis tailored for cyanotoxins was performed in a single chromatographic run, using the developed database as a preferred precursor ions list. Twenty-five extracts of surface and drinking waters contaminated by cyanobacteria were processed. The identification of seven uncommon microcystins (M(O)R, MC-FR, MSer 7 -YR, D-Asp 3 MSer 7 -LR, MSer 7 -LR, dmAdda-LR and dmAdda-YR) and 6 anabaenopeptins (A, B, F, MM850, MM864, oscyllamide Y) was reported. Several isobaric variants, fully separated by chromatography, were pointed out. The developed methods are proposed to be used by environmental and health agencies for strengthening the surveillance monitoring of cyanotoxins in water. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Current use of high-resolution mass spectrometry in drug screening relevant to clinical and forensic toxicology and doping control.

    Science.gov (United States)

    Ojanperä, Ilkka; Kolmonen, Marjo; Pelander, Anna

    2012-05-01

    Clinical and forensic toxicology and doping control deal with hundreds or thousands of drugs that may cause poisoning or are abused, are illicit, or are prohibited in sports. Rapid and reliable screening for all these compounds of different chemical and pharmaceutical nature, preferably in a single analytical method, is a substantial effort for analytical toxicologists. Combined chromatography-mass spectrometry techniques with standardised reference libraries have been most commonly used for the purpose. In the last ten years, the focus has shifted from gas chromatography-mass spectrometry to liquid chromatography-mass spectrometry, because of progress in instrument technology and partly because of the polarity and low volatility of many new relevant substances. High-resolution mass spectrometry (HRMS), which enables accurate mass measurement at high resolving power, has recently evolved to the stage that is rapidly causing a shift from unit-resolution, quadrupole-dominated instrumentation. The main HRMS techniques today are time-of-flight mass spectrometry and Orbitrap Fourier-transform mass spectrometry. Both techniques enable a range of different drug-screening strategies that essentially rely on measuring a compound's or a fragment's mass with sufficiently high accuracy that its elemental composition can be determined directly. Accurate mass and isotopic pattern acts as a filter for confirming the identity of a compound or even identification of an unknown. High mass resolution is essential for improving confidence in accurate mass results in the analysis of complex biological samples. This review discusses recent applications of HRMS in analytical toxicology.

  5. High-resolution, three-step resonance ionization mass spectrometry of gadolinium

    International Nuclear Information System (INIS)

    Blaum, K.; Wendt, K.; Bushaw, B.A.; Noertershaeuser, W.

    2001-01-01

    High-resolution resonance ionization mass spectrometry has been used to measure triple-resonance autoionization (AI) spectra of gadolinium. Al resonances as narrow as 10 MHz have been observed and isotope shifts and hyperfine structure have been measured in selected AI states. The strongest AI state observed at 49663.576 cm-1 with a photoionization cross section of >3.6x10 -15 cm 2 was found to have an overall detection efficiency of >3x10 -5 , allowing application to a number of ultratrace determination problems. Analytical measurements with a diode-laser-based system have been successfully performed on bio-medical tissue samples

  6. Mass analyzer ``MASHA'' high temperature target and plasma ion source

    Science.gov (United States)

    Semchenkov, A. G.; Rassadov, D. N.; Bekhterev, V. V.; Bystrov, V. A.; Chizov, A. Yu.; Dmitriev, S. N.; Efremov, A. A.; Guljaev, A. V.; Kozulin, E. M.; Oganessian, Yu. Ts.; Starodub, G. Ya.; Voskresensky, V. M.; Bogomolov, S. L.; Paschenko, S. V.; Zelenak, A.; Tikhonov, V. I.

    2004-05-01

    A new separator and mass analyzer of super heavy atoms (MASHA) has been created at the FLNR JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10-3. First experiments with the FEBIAD plasma ion source have been done and give an efficiency of ionization of up to 20% for Kr with a low flow test leak (6 particle μA). We suppose a magnetic field optimization, using the additional electrode (einzel lens type) in the extracting system, and an improving of the vacuum conditions in order to increase the ion source efficiency.

  7. Mass analyzer 'MASHA' high temperature target and plasma ion source

    International Nuclear Information System (INIS)

    Semchenkov, A.G.; Rassadov, D.N.; Bekhterev, V.V.; Bystrov, V.A.; Chizov, A.Yu.; Dmitriev, S.N.; Efremov, A.A.; Guljaev, A.V.; Kozulin, E.M.; Oganessian, Yu.Ts.; Starodub, G.Ya.; Voskresensky, V.M.; Bogomolov, S.L.; Paschenko, S.V.; Zelenak, A.; Tikhonov, V.I.

    2004-01-01

    A new separator and mass analyzer of super heavy atoms (MASHA) has been created at the FLNR JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 -3 . First experiments with the FEBIAD plasma ion source have been done and give an efficiency of ionization of up to 20% for Kr with a low flow test leak (6 particle μA). We suppose a magnetic field optimization, using the additional electrode (einzel lens type) in the extracting system, and an improving of the vacuum conditions in order to increase the ion source efficiency

  8. Microscope mode secondary ion mass spectrometry imaging with a Timepix detector.

    NARCIS (Netherlands)

    Kiss, A.; Jungmann, JH; Smith, D.F.; Heeren, R.M.A.

    2013-01-01

    In-vacuum active pixel detectors enable high sensitivity, highly parallel time- and space-resolved detection of ions from complex surfaces. For the first time, a Timepix detector assembly was combined with a secondary ion mass spectrometer for microscope mode secondary ion mass spectrometry (SIMS)

  9. High-resolution X-ray spectra from low-temperature, highly charged ions

    International Nuclear Information System (INIS)

    Beiersdorfer, P.

    1996-09-01

    The electron beam ion traps (EBIT) at Livermore were designed for studying the x-ray emission of highly charged ions produced and excited by a monoenergetic electron beam. The precision with which the x-ray emission can be analyzed has recently been increased markedly when it became possible to decouple the temperature of the ions from the energy of the electron beam by several orders of magnitude. By adjusting the trap parameters, ion temperatures as low as 15.8±4.4 eV for Ti 20+ and 59.4±9.9 eV for Cs 45+ were achieved. These temperatures were more than two orders of magnitude lower than the energy of the multi-keV electron beam used for the production and excitation of the ions. A discussion of the techniques used to produce and study low-temperature highly charged ions is presented in this progress report. The low ion temperatures enabled measurements heretofore impossible. As an example, a direct observation of the natural line width of fast electric dipole allowed x-ray transitions is described. From the observed natural line width and b making use of the time-energy relations of the uncertainty principle we were able to determine a radiative transition rate of 1.65 fs for the 2p-3d resonance transition in neonlike Cs 45+ . A brief discussion of other high-precision measurements enabled by our new technique is also given

  10. High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry

    International Nuclear Information System (INIS)

    Fan, Ruo-Jing; Zhang, Fang; Chen, Xiu-Ping; Qi, Wan-Shu; Guan, Qing; Sun, Tuan-Qi; Guo, Yin-Long

    2017-01-01

    The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%–12.3% for intra-day and 0.9%–7.8% for inter-day) and good accuracy (91%–109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. - Highlights: • The separation power of DTIMS-MS enhanced peak capacity, spectral clarity, and specificity of benzil labeled GCs and UCs. • Short-column LC for on-line desalting increased the throughput with a measurement cycle of 5.0 min. • CCS and accurate mass as a pair of qualifiers were used for the profiling and identification of GCs and UCs. • An integral abundance arising from 3-D ion features (RT, DT, m/z) was used as a novel quantifier for quantitation. • The developed method was applied to screen and quantify the GCs and UCs in human thyroid tissues.

  11. High-throughput screening and quantitation of guanidino and ureido compounds using liquid chromatography-drift tube ion mobility spectrometry-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Fan, Ruo-Jing [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Zhang, Fang, E-mail: fzhang@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Chen, Xiu-Ping; Qi, Wan-Shu [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China); Guan, Qing [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center, Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Sun, Tuan-Qi, E-mail: tuanqisun@163.com [Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center, Shanghai 200032 (China); Department of Oncology, Shanghai Medical College, Fudan University, Shanghai 200032 (China); Guo, Yin-Long, E-mail: ylguo@sioc.ac.cn [National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China)

    2017-04-08

    The present work focused on the high-throughput screening and quantitation of guanidino compounds (GCs) and ureido compounds (UCs) in human thyroid tissues. The strategy employed benzylic rearrangement stable isotope labeling (BRSIL) for the sample preparation and then detection using liquid chromatography-drift tube ion mobility spectrometry-quadrupole time of flight mass spectrometry (LC-DTIMS-QTOF MS). A short reversed-phase LC realized an on-line desalting and a measurement cycle of 5.0 min. DTIMS separation enhanced the better specificity and selectivity for the benzil labeled GCs and UCs. The elevated mass resolution of QTOF MS enabled measure of the characteristic ions at accurate mass in MS and tandem MS spectra. Collision cross section (CCS) from DTIMS and accurate mass from QTOF MS were used as two qualifiers for the profiling and identification of GCs and UCs. In addition, an integral abundance arising from 3-D ion features (retention time, drift time, m/z) was applied to quantify the GCs and UCs in human thyroid tissues. The quantitative validation indicated good linearity (coefficient values ≥ 0.9981), good precision (1.0%–12.3% for intra-day and 0.9%–7.8% for inter-day) and good accuracy (91%–109%). The results demonstrated that the developed BRSIL coupled with LC-DTIMS-QTOF MS can be a powerful analysis platform to investigate GCs and UCs in human thyroid tissues. - Highlights: • The separation power of DTIMS-MS enhanced peak capacity, spectral clarity, and specificity of benzil labeled GCs and UCs. • Short-column LC for on-line desalting increased the throughput with a measurement cycle of 5.0 min. • CCS and accurate mass as a pair of qualifiers were used for the profiling and identification of GCs and UCs. • An integral abundance arising from 3-D ion features (RT, DT, m/z) was used as a novel quantifier for quantitation. • The developed method was applied to screen and quantify the GCs and UCs in human thyroid tissues.

  12. High Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) for Mass Spectrometry-Based Proteomics

    Science.gov (United States)

    Swearingen, Kristian E.; Moritz, Robert L.

    2013-01-01

    SUMMARY High field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, we review recent developments in LC-FAIMS-MS and its application to MS-based proteomics. PMID:23194268

  13. High-resolution spectral analysis of light from neutral beams and ion source plasmas

    International Nuclear Information System (INIS)

    McNeill, D.H.; Kim, J.

    1980-05-01

    The spectral distributions of Balmer alpha emission from 7- and 22-cm-diam neutral hydrogen beams have been measured with a Fabry-Perot interferometer to obtain information on the beam energy, divergence, and species composition. Results of these measurements are compared with other data on the beam properties to evaluate high-resolution spectroscopy as a beam diagnostic technique. Measurements on ion source plasmas and on beam-produced background plasmas yield average neutral atom energies of approximately 0.3 and 2.5 eV, respectively

  14. Time-of-flight secondary ion mass spectrometry with energetic cluster ion impact ionization for highly sensitive chemical structure characterization

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, K., E-mail: k.hirata@aist.go.jp [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K.; Narumi, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)

    2013-11-01

    Energetic cluster ions with energies of the order of sub MeV or greater were applied to time-of-flight (TOF) secondary ion (SI) mass spectrometry. This gave various advantages including enhancement of SIs required for chemical structure characterization and prevention of charging effects in SI mass spectra for organic targets. We report some characteristic features of TOF SI mass spectrometry using energetic cluster ion impact ionization and discuss two future applications of it.

  15. A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Min [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China); Zhou, Zhe [ThermoFisher Scientific China Co., Ltd, No 6 Building, 27 Xinjinqiao Road, Shanghai 201206 (China); Guo, De-an, E-mail: daguo@simm.ac.cn [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China)

    2015-09-24

    Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the {sup 34}S isotopic ion is drastically affected by {sup 13}C{sub 2} and {sup 18}O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ({sup 12}C{sub x}{sup 1}H{sub y}{sup 16}O{sub z}{sup 32}S{sup 13}C{sub 2}{sup 18}O, {sup 12}C{sub x+2}{sup 1}H{sub y}{sup 16}O{sub z+1}{sup 34}S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS{sup n}). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. - Highlights: • We provide a new strategy for specifically screening of sulfurous compounds. • The fine isotopic pattern filter (FIPF) bases on separation of {sup 13}C{sub 2}+{sup 18}O and {sup 34}S. • Ultra high resolution mass (100,000 FWHM @ 400 m/z) is essential

  16. Screening new psychoactive substances in urban wastewater using high resolution mass spectrometry.

    Science.gov (United States)

    González-Mariño, Iria; Gracia-Lor, Emma; Bagnati, Renzo; Martins, Claudia P B; Zuccato, Ettore; Castiglioni, Sara

    2016-06-01

    Analysis of drug residues in urban wastewater could complement epidemiological studies in detecting the use of new psychoactive substances (NPS), a continuously changing group of drugs hard to monitor by classical methods. We initially selected 52 NPS potentially used in Italy based on seizure data and consumption alerts provided by the Antidrug Police Department and the National Early Warning System. Using a linear ion trap-Orbitrap high resolution mass spectrometer, we designed a suspect screening and a target method approach and compared them for the analysis of 24 h wastewater samples collected at the treatment plant influents of four Italian cities. This highlighted the main limitations of these two approaches, so we could propose requirements for future research. A library of MS/MS spectra of 16 synthetic cathinones and 19 synthetic cannabinoids, for which analytical standards were acquired, was built at different collision energies and is available on request. The stability of synthetic cannabinoids was studied in analytical standards and wastewater, identifying the best analytical conditions for future studies. To the best of our knowledge, these are the first stability data on NPS. Few suspects were identified in Italian wastewater samples, in accordance with recent epidemiological data reporting a very low prevalence of use of NPS in Italy. This study outlines an analytical approach for NPS identification and measurement in urban wastewater and for estimating their use in the population.

  17. Ion Mass Determination

    DEFF Research Database (Denmark)

    2010-01-01

    An apparatus (100) is described for determining the mass of ions, the apparatus configured to hold a plasma (101 ) having a plasma potential. The apparatus (100) comprises an electrode (102) having a surface extending in a surface plane and an insulator (104) interfacing with the electrode (102......, and a processing unit (108) configured to interpret the detected impact locations in terms of the mass of the impacting ions....

  18. High-resolution ion-implanted silicon detectors

    International Nuclear Information System (INIS)

    von Borany, J.; Schmidt, B.

    1985-01-01

    An account is given of the properties of silicon detectors developed at the Central Institute of Nuclear Research of the Academy of Sciences of the German Democratic Republic (Rossendorf) and made by a special planar technology using ion implantation, anodic oxidation, thermal oxidation in an oxygen atmosphere containing HCl, and annealing by pulses of 10--20 msec duration. The resolution for α particles of 5.5 MeV energy was 11.2 keV (active area A 2 ). The detectors were characterized by a low intrinsic noise (< or =5 keV), so that they could be used for spectrometry of low-energy electrons (E/sub e/< or =250 keV). In a certain range of energies (E/sub x/ = 15--60 keV) it was possible to use these detectors for spectrometry of x rays at room temperature. Examples and results of applications of detectors in radiation chemistry (investigations of backscattering of particles and nuclear reaction spectroscopy) are given. The feasibility of annealing of radiation defects in such detectors after irradiation with a large dose of charged particles is considered

  19. Angle resolved mass spectrometry of positive ions transmitted through high aspect ratio channels in a radio frequency discharge

    NARCIS (Netherlands)

    Stoffels - Adamowicz, E.; Stoffels, W.W.; Tachibana, K.; Imai, S.

    1997-01-01

    The behavior of positive ions in high aspect ratio structures, relevant to the reactive ion etching of deep trenches, has been studied by means of energy resolved mass spectrometry. High aspect ratio trenches are simulated by capillary plates with various aspect ratios. Angle resolved measurements

  20. Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

    DEFF Research Database (Denmark)

    Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka

    2017-01-01

    Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identi......Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could...... be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for Me......V Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples...

  1. Ultra-high performance supercritical fluid chromatography hyphenated to atmospheric pressure chemical ionization high resolution mass spectrometry for the characterization of fast pyrolysis bio-oils.

    Science.gov (United States)

    Crepier, Julien; Le Masle, Agnès; Charon, Nadège; Albrieux, Florian; Duchene, Pascal; Heinisch, Sabine

    2018-06-01

    Extensive characterization of complex mixtures requires the combination of powerful analytical techniques. A Supercritical Fluid Chromatography (SFC) method was previously developed, for the specific case of fast pyrolysis bio oils, as an alternative to gas chromatography (GC and GC × GC) or liquid chromatography (LC and LC × LC), both separation methods being generally used prior to mass spectrometry (MS) for the characterization of such complex matrices. In this study we investigated the potential of SFC hyphenated to high resolution mass spectrometry (SFC-HRMS) for this characterization using Negative ion Atmospheric Pressure Chemical ionization ((-)APCI) for the ionization source. The interface between SFC and (-)APCI/HRMS was optimized from a mix of model compounds with the objective of maximizing the signal to noise ratio. The main studied parameters included both make-up flow-rate and make-up composition. A methodology for the treatment of APCI/HRMS data is proposed. This latter allowed for the identification of molecular formulae. Both SFC-APCI/HRMS method and data processing method were applied to a mixture of 36 model compounds, first analyzed alone and then spiked in a bio-oil. In both cases, 19 compounds could be detected. Among them 9 could be detected in a fast pyrolysis bio-oil by targeted analysis. The whole procedure was applied to the characterization of a bio-oil using helpful representations such as mass-plots, van Krevelen diagrams and heteroatom class distributions. Finally the results were compared with those obtained with a Fourier Transform ion-cyclotron resonance mass spectrometer (FT-ICR/MS). Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Final Report - Advanced Ion Trap Mass Spectrometry Program - Oak Ridge National Laboratory - Sandia National Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, W.B.

    2002-12-18

    nonlinear resonances contributed to poor mass resolution and sensitivity and to erratic ion ejection behavior. To correct for these nonlinear effects, the geometry of the toroid ion trap analyzer has been modified to create an asymmetric torus, as first suggested by computer simulations that predicted significantly improved performance and unit mass resolution for this geometry. A reduced-sized version (one-fifth scale) has been fabricated but was not tested within the scope of this project. Chapter 3 describes groundbreaking progress toward the use of ion-ion chemistry to control the charge state of ions formed by the electrospray ionization process, which in turn enables precision analysis of whole proteins. In addition, this technique may offer the unique possibility of a priori identification of unknown biological material when employed with existing proteomics and genomic databases. Ion-ion chemistry within the ion trap was used to reduce the ions in highly charged states to states of +1 and +2 charges. Reduction in charge greatly simplifies identification of molecular weights of fragments from large biological molecules. This technique enables the analysis of whole proteins as biomarkers for the detection and identification of all three classes of biological weapons (bacteria, toxins, and viruses). In addition to methods development, tests were carried out with samples of tap water, local creek water, and soil (local red clay) spiked with melittin (bee venom), cholera toxin, and virus MS2. All three analytes were identified in tap water and soil; however, all three were problematic for detection in creek water at concentrations of 1 nM. More development of methods is needed.

  3. The hypertrehalosemic neuropeptides of cicadas are structural isomers-evidence by ion mobility mass spectrometry.

    Science.gov (United States)

    König, Simone; Marco, Heather; Gäde, Gerd

    2017-11-01

    It has been known for more than 20 years that the neurosecretory glands of the cicadas, the corpora cardiaca, synthesize two isobaric peptides with hypertrehalosemic activity. Both decapeptides have exactly the same amino acid sequence (pGlu-Val-Asn-Phe-Ser-Pro-Ser-Trp-Gly-Asn-NH 2 ) and mass but differ in their retention time in reversed-phase liquid chromatography. A synthetic peptide with the same sequence elutes together with the second more hydrophobic peptide peak of the natural cicada extract. It is not clear what modification is causing the described observations. Therefore, in the current study, ion mobility separation in conjunction with high-resolution mass spectrometry was used to investigate this phenomenon as it was sensitive to changes in conformation. It detected different drift times in buffer gas for both the intact peptides and some of their fragment ions. Based on the ion mobility and fragment ion intensity of the corresponding ions, it is concluded that the region Pro 6 -Ser 7 -Trp 8 contains a structural feature differing from the L-amino acids present in the known peptide. Whether the conformer is the result of racemization or other biochemical processes needs to be further investigated.

  4. Non-targeted glycosidic profiling of international wines using neutral loss-high resolution mass spectrometry.

    Science.gov (United States)

    Barnaba, C; Dellacassa, E; Nicolini, G; Nardin, T; Serra, M; Larcher, R

    2018-07-06

    Many metabolites naturally occur as glycosides, since sugar moieties can be crucial for their biological activity and increase their water solubility. In the plant kingdom they may occur as glycosides or sugar esters, depending on precursor chemical structure, and in wine they have traditionally attracted attention due to their organoleptic properties, such as astringency and bitterness, and because they affect the colour and aroma of wines. A new approach directed at detailed description of glycosides in a large selection of monovarietal wines (8 samples each of Pinot Blanc, Muller Thurgau, Riesling, Traminer, Merlot, Pinot Noir and Cabernet Sauvignon) was developed by combining high performance liquid chromatography with high resolution tandem mass spectrometry. Analytical separation was performed on an Accucore™ Polar Premium LC column, while mass analysis was performed in negative ion mode with an non-targeted screening approach, using a Full MS/AIF/NL dd-MS 2 experiment at a resolving power of 140,000 FWHM. Over 280 glycoside-like compounds were detected, of which 133 (including low-molecular weight phenols, flavonoids and monoterpenols) were tentatively identified in the form of pentose (6), deoxyhexose (17), hexose (73), hexose-pentose (16), hexose-deoxyhexose (7), dihexose (5) and hexose ester (9) derivatives. It was not possible to univocally define the corresponding chemical structure for the remaining 149 glycosides. Non-parametric statistical analysis showed it was possible to well characterise the glycosylated profile of all red and Traminer wines, while the identified glycosides were almost entirely lacking in Pinot Blanc, Riesling and Muller Thurgau wines. Also Tukey's Honestly Significant Difference test (p wines from each other according to their glycosylated profile. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. Calorimetric low - temperature detectors for high resolution X-ray spectroscopy on stored highly stripped heavy ions

    International Nuclear Information System (INIS)

    Bleile, A.; Egelhof, P.; Kraft, S.; Meier, H.J.; Shrivastava, A.; Weber, M.; McCammon, D.; Stahle, C.K.

    2001-09-01

    The accurate determination of the Lamb shift in heavy hydrogen-like ions provides a sensitive test of quantum electrodynamics in very strong Coulomb fields, not accessible otherwise. For the investigation of the Lyman-α transitions in 208 Pb 81+ or 238 U 91+ with sufficient accuracy, a high resolution calorimetric detector for hard X-rays (E ≤ 100 keV) is presently being developed. The detector modules consist of arrays of silicon thermistors and of X-ray absorbers made of high-Z material to optimize the absorption efficiency. The detectors are housed in a specially designed 3 He/ 4 He dilution refrigerator with a side arm which fits to the internal target geometry of the storage ring ESR at GSI Darmstadt. The detector performance presently achieved is already close to fulfill the demands of the Lamb shift experiment. For a prototype detector pixel with a 0.2 mm 2 x 47 μm Pb absorber an energy resolution of ΔE FWHM = 65 eV is obtained for 60 keV X-rays. (orig.)

  6. Enhanced depth and mass resolution with HIRBS

    International Nuclear Information System (INIS)

    Yang, Q.; O'Connor, D.J.

    1992-01-01

    The extension of Rutherford backscattering spectrometry (RBS) to heavier mass projectiles (HIRBS) has been limited, as these projectiles cause much more radiation damage in the detectors and curtail their lifetime. Despite this limitation interest in the use of heavier projectiles continues as there are several significant benefits which can accrue from their use. To properly understand the interaction of heavy ions with solids a systematic study of the energy loss and straggling of MeV heavy ions has been conducted and an empirical expression for these terms has been obtained. This expression has allowed the development of a realistic computer simulation which accurately predicts the energy spectra for a wide range of energies, projectiles and targets. In parallel with that study, measurements of the depth resolution of Si/Ge multilayer films using 4-6 MeV C projectiles have been used to verify the simulation. (orig.)

  7. A High-Resolution Model of Water Mass Transformation and Transport in the Weddell Sea

    Science.gov (United States)

    Hazel, J.; Stewart, A.

    2016-12-01

    The ocean circulation around the Antarctic margins has a pronounced impact on the global ocean and climate system. One of these impacts includes closing the global meridional overturning circulation (MOC) via formation of dense Antarctic Bottom Water (AABW), which ventilates a large fraction of the subsurface ocean. AABW is also partially composed of modified Circumpolar Deep Water (CDW), a warm, mid-depth water mass whose transport towards the continent has the potential to induce rapid retreat of marine-terminating glaciers. Previous studies suggest that these water mass exchanges may be strongly influenced by high-frequency processes such as downslope gravity currents, tidal flows, and mesoscale/submesoscale eddy transport. However, evaluating the relative contributions of these processes to near-Antarctic water mass transports is hindered by the region's relatively small scales of motion and the logistical difficulties in taking measurements beneath sea ice.In this study we develop a regional model of the Weddell Sea, the largest established source of AABW. The model is forced by an annually-repeating atmospheric state constructed from the Antarctic Mesoscale Prediction System data and by annually-repeating lateral boundary conditions constructed from the Southern Ocean State Estimate. The model incorporates the full Filchner-Ronne cavity and simulates the thermodynamics and dynamics of sea ice. To analyze the role of high-frequency processes in the transport and transformation of water masses, we compute the model's overturning circulation, water mass transformations, and ice sheet basal melt at model horizontal grid resolutions ranging from 1/2 degree to 1/24 degree. We temporally decompose the high-resolution (1/24 degree) model circulation into components due to mean, eddy and tidal flows and discuss the geographical dependence of these processes and their impact on water mass transformation and transport.

  8. Identification of amines in wintertime ambient particulate material using high resolution aerosol mass spectrometry

    Science.gov (United States)

    Bottenus, Courtney L. H.; Massoli, Paola; Sueper, Donna; Canagaratna, Manjula R.; VanderSchelden, Graham; Jobson, B. Thomas; VanReken, Timothy M.

    2018-05-01

    Significant amounts of amines were detected in fine particulate matter (PM) during ambient wintertime conditions in Yakima, WA, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Positive matrix factorization (PMF) of the organic aerosol (OA) signal resulted in a six-factor solution that included two previously unreported amine OA factors. The contributions of the amine factors were strongly episodic, but the concentration of the combined amine factors was as high as 10-15 μg m-3 (2-min average) during those episodes. In one occasion, the Amine-II component was 45% of total OA signal. The Amine-I factor was dominated by spectral peaks at m/z 86 (C5H12N+) and m/z 100 (C6H14N+), while the Amine-II factor was dominated by spectral peaks at m/z 58 (C3H8N+ and C2H6N2+) and m/z 72 (C4H10N+ and C3H8N2+). The ions dominating each amine factor showed distinct time traces, suggesting different sources or formation processes. Investigation into the chemistry of the amine factors suggests a correlation with inorganic anions for Amine-I, but no evidence that the Amine-II was being neutralized by the same inorganic ions. We also excluded the presence of organonitrates (ON) in the OA. The presence of C2H4O2+ at m/z 60 (a levoglucosan fragment) in the Amine-I spectrum suggests some influence of biomass burning emissions (more specifically residential wood combustion) in this PMF factor, but wind direction suggested that the most likely sources of these amines were agricultural activities and feedlots to the S-SW of the site.

  9. The Ring Counter (RCo): A high resolution IC-Si-CsI(Tl) device for heavy ion reaction studies at 10-30 MeV/A

    International Nuclear Information System (INIS)

    Moroni, A.; Bruno, M.; Bardelli, L.; Barlini, S.; Brambilla, S.; Casini, G.; Cavaletti, R.; Chiari, M.; Cortesi, A.; D'Agostino, M.; De Sanctis, J.; Geraci, E.; Giordano, G.; Giussani, A.; Gramegna, F.; Guiot, B.; Kravchuk, V.; Lanchais, A.; Margagliotti, G.V.; Nannini, A.; Ordine, A.; Piantelli, S.; Vannini, G.; Vannucci, L.

    2006-01-01

    An annular detector (Ring Counter, RCo) is presented, which has been designed and built to detect and identify in mass and charge light charged particles and fragments with very low energy thresholds and high energy resolution. It complements the GARFIELD apparatus, operating at INFN Laboratori Nazionali di Legnaro, to detect the forward emitted products of nuclear heavy ion reactions. It consists of eight sectors of a three-stage telescope, each one formed by an ionization chamber followed by eight strips of a silicon detector and by two CsI(Tl) scintillators. Construction features and performances are described and discussed in details

  10. Copper L X-ray spectra measured by a high resolution ion-induced X-ray spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Ryohei; Hamaguchi, Dai; Kageyama, Hiroyoshi [Kyoto Inst. of Tech. (Japan); and others

    1997-03-01

    High resolution L X-ray emission spectra of Cu have been measured by 0.75 MeV/u H, He, and F, 0.73 MeV/u Ar, 0.64 MeV/u Si, and 0.073 MeV/u Si ion impacts with a crystal spectrometer. The X-ray transition energies in the Cu target for L{iota}, L{eta}, L{alpha}{sub 1,2}, L{beta}{sub 1}, and L{beta}{sub 3,4} diagram lines induced by light ion impacts are determined, which are in good agreement with those given in the reference. The difference in L X-ray emission spectra produced by H, He, F, Si, and Ar ions are considered and the L{alpha}{sub 1,2} and L{beta}{sub 1} emission spectra are compared with the calculated ones based on the multiconfiguration Dirac-Fock method. (author)

  11. Analysis of organic compounds by secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS)

    International Nuclear Information System (INIS)

    Ewinger, H.P.

    1993-05-01

    This study is about the use of secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS) as analytical techniques with depth resolution in determining organic components in environmental solid microparticles. The first application of plasma SNMS to organic compounds revealed the spectra to be composed mainly of signals from the atoms of all participating elements, such as C, H, O, N, S, P, and Cl. In addition, signals produced by multi-atomic clusters can be detected, such as CH, C 2 , CH 2 , C 2 H, and C 3 , as well as signals indicating the presence of organic compounds with hetero elements, such as OH, NH, and CN. Their intensity decreases very markedly with increasing numbers of atoms. Among the signals from bi-atomic clusters, those coming from elements with large mass differences are most intense. The use of plasma SNMS with organic compounds has shown that, except for spurious chemical reactions induced by ion bombardment and photodesorption by the photons of the plasma, it is possible to analyze with resolution in depth, elements of organic solids. A more detailed molecular characterization of organic compounds is possible by means of SIMS on the basis of multi-atomic fragments and by comparison with suitable signal patterns. (orig./BBR) [de

  12. High-resolution scanning near-field EBIC microscopy: Application to the characterisation of a shallow ion implanted p+-n silicon junction

    International Nuclear Information System (INIS)

    Smaali, K.; Faure, J.; El Hdiy, A.; Troyon, M.

    2008-01-01

    High-resolution electron beam induced current (EBIC) analyses were carried out on a shallow ion implanted p + -n silicon junction in a scanning electron microscope (SEM) and a scanning probe microscope (SPM) hybrid system. With this scanning near-field EBIC microscope, a sample can be conventionally imaged by SEM, its local topography investigated by SPM and high-resolution EBIC image simultaneously obtained. It is shown that the EBIC imaging capabilities of this combined instrument allows the study of p-n junctions with a resolution of about 20 nm

  13. Computer programmes for high current ion trajectories in a magnetic sector-type mass separator

    International Nuclear Information System (INIS)

    Nakai, Akira

    1988-01-01

    According to theoretical calculations previously proposed by the author, a new programme 'MALT' for electronic computers has been developed for numerical calculations of ion trajectories of a high current ion beam traversing a magnetic sector-type mass separator. In the programme, both effects of the fringing field and the space charge are taken into account in an analytical way, so that numerical calculations can be done straightforwardly. Furthermore, it becomes also possible to analyze and cotrol the trajectories of the high current ion beam. The programme MALT contains several subroutine programmes which are separated individually for the convenience of various calculations with respect to the high current ion beam. To demonstrate the calculations by the use of these subroutine programmes, a main programme for the calculation of the trajectories in the whole region of the separator is shown, which also makes it possible to draw the traces of the trajectories. The trajectories calculated by the proposed programme have been compared with the images of the ion beams recorded on novel dry plates developed by the author: the comparison enables us to evaluate the effective space charge and the effective space charge potential, and to analyze the behaviour of the beam of neutral particles accompanying the ion beam. (author)

  14. Improving depth resolutions in positron beam spectroscopy by concurrent ion-beam sputtering

    Science.gov (United States)

    John, Marco; Dalla, Ayham; Ibrahim, Alaa M.; Anwand, Wolfgang; Wagner, Andreas; Böttger, Roman; Krause-Rehberg, Reinhard

    2018-05-01

    The depth resolution of mono-energetic positron annihilation spectroscopy using a positron beam is shown to improve by concurrently removing the sample surface layer during positron beam spectroscopy. During ion-beam sputtering with argon ions, Doppler-broadening spectroscopy is performed with energies ranging from 3 keV to 5 keV allowing for high-resolution defect studies just below the sputtered surface. With this technique, significantly improved depth resolutions could be obtained even at larger depths when compared to standard positron beam experiments which suffer from extended positron implantation profiles at higher positron energies. Our results show that it is possible to investigate layered structures with a thickness of about 4 microns with significantly improved depth resolution. We demonstrated that a purposely generated ion-beam induced defect profile in a silicon sample could be resolved employing the new technique. A depth resolution of less than 100 nm could be reached.

  15. Prediction of collision cross section and retention time for broad scope screening in gradient reversed-phase liquid chromatography-ion mobility-high resolution accurate mass spectrometry.

    Science.gov (United States)

    Mollerup, Christian Brinch; Mardal, Marie; Dalsgaard, Petur Weihe; Linnet, Kristian; Barron, Leon Patrick

    2018-03-23

    Exact mass, retention time (RT), and collision cross section (CCS) are used as identification parameters in liquid chromatography coupled to ion mobility high resolution accurate mass spectrometry (LC-IM-HRMS). Targeted screening analyses are now more flexible and can be expanded for suspect and non-targeted screening. These allow for tentative identification of new compounds, and in-silico predicted reference values are used for improving confidence and filtering false-positive identifications. In this work, predictions of both RT and CCS values are performed with machine learning using artificial neural networks (ANNs). Prediction was based on molecular descriptors, 827 RTs, and 357 CCS values from pharmaceuticals, drugs of abuse, and their metabolites. ANN models for the prediction of RT or CCS separately were examined, and the potential to predict both from a single model was investigated for the first time. The optimized combined RT-CCS model was a four-layered multi-layer perceptron ANN, and the 95th prediction error percentiles were within 2 min RT error and 5% relative CCS error for the external validation set (n = 36) and the full RT-CCS dataset (n = 357). 88.6% (n = 733) of predicted RTs were within 2 min error for the full dataset. Overall, when using 2 min RT error and 5% relative CCS error, 91.9% (n = 328) of compounds were retained, while 99.4% (n = 355) were retained when using at least one of these thresholds. This combined prediction approach can therefore be useful for rapid suspect/non-targeted screening involving HRMS, and will support current workflows. Copyright © 2018 Elsevier B.V. All rights reserved.

  16. Isobar Separation in a Multiple-Reflection Time-of-Flight Mass Spectrometer by Mass-Selective Re-Trapping

    Science.gov (United States)

    Dickel, Timo; Plaß, Wolfgang R.; Lippert, Wayne; Lang, Johannes; Yavor, Mikhail I.; Geissel, Hans; Scheidenberger, Christoph

    2017-06-01

    A novel method for (ultra-)high-resolution spatial mass separation in time-of-flight mass spectrometers is presented. Ions are injected into a time-of-flight analyzer from a radio frequency (rf) trap, dispersed in time-of-flight according to their mass-to-charge ratios and then re-trapped dynamically in the same rf trap. This re-trapping technique is highly mass-selective and after sufficiently long flight times can provide even isobaric separation. A theoretical treatment of the method is presented and the conditions for optimum performance of the method are derived. The method has been implemented in a multiple-reflection time-of-flight mass spectrometer and mass separation powers (FWHM) in excess of 70,000, and re-trapping efficiencies of up to 35% have been obtained for the protonated molecular ion of caffeine. The isobars glutamine and lysine (relative mass difference of 1/4000) have been separated after a flight time of 0.2 ms only. Higher mass separation powers can be achieved using longer flight times. The method will have important applications, including isobar separation in nuclear physics and (ultra-)high-resolution precursor ion selection in multiple-stage tandem mass spectrometry. [Figure not available: see fulltext.

  17. High Resolution Scanning Ion Microscopy

    NARCIS (Netherlands)

    Castaldo, V.

    2011-01-01

    The structure of the thesis is the following. The first chapter is an introduction to scanning microscopy, where the path that led to the Focused Ion Beam (FIB) is described and the main differences between electrons and ion beams are highlighted. Chapter 2 is what is normally referred to (which I

  18. Background-free beta-decay half-life measurements by in-trap decay and high-resolution MR-ToF mass analysis

    Science.gov (United States)

    Wolf, R. N.; Atanasov, D.; Blaum, K.; Kreim, S.; Lunney, D.; Manea, V.; Rosenbusch, M.; Schweikhard, L.; Welker, A.; Wienholtz, F.; Zuber, K.

    2016-06-01

    In-trap decay in ISOLTRAP's radiofrequency quadrupole (RFQ) ion beam cooler and buncher was used to determine the lifetime of short-lived nuclides. After various storage times, the remaining mother nuclides were mass separated from accompanying isobaric contaminations by the multi-reflection time-of-flight mass separator (MR-ToF MS), allowing for a background-free ion counting. A feasibility study with several online measurements shows that the applications of the ISOLTRAP setup can be further extended by exploiting the high resolving power of the MR-ToF MS in combination with in-trap decay and single-ion counting.

  19. Multiresidue analysis of 22 sulfonamides and their metabolites in animal tissues using quick, easy, cheap, effective, rugged, and safe extraction and high resolution mass spectrometry (hybrid linear ion trap-Orbitrap).

    Science.gov (United States)

    Abdallah, H; Arnaudguilhem, C; Jaber, F; Lobinski, R

    2014-08-15

    A new high performance liquid chromatography-high resolution mass spectrometry (HPLC-HRMS) method was developed for a simultaneous multi-residue analysis of 22 sulfonamides (SAs) and their metabolites in edible animal (pig, beef, sheep and chicken) tissues. Sample preparation was optimized on the basis of the "QuEChERS" protocol. The analytes were identified using their LC retention times and accurate mass; the identification was further confirmed by multi-stage high mass accuracy (Pig kidney" with ǀ Z-scoreǀpig, beef, sheep, and chicken) allowing the simultaneous quantification of target sulfonamides at concentration levels above the MRL/2 and the identification of untargeted compounds such as N(4)-acetyl metabolites using multi-stage high mass accuracy mass spectrometry. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Structural Characterization of Laboratory Made Tholins by IRMPD Action Spectroscopy and Ultrahigh Resolution Mass Spectrometry

    Science.gov (United States)

    Thissen, R.; Somogyi, A.; Vuitton, V.; Bégué, D.; Lemaire, J.; Steinmetz, V.

    2011-10-01

    The complex organic material that is found on the surface and within the haze layer of Titan is attributed to chemistry occurring in its thick N2/CH4 atmosphere. Although several groups are producing in various laboratory setting the socalled tholins which have been investigated by using analytical methods including UV/Vis, fluorescence, IR, and MS1-5, these very complex organic mixtures still hold many unanswered questions, especially related to the potentiality for their prebiotic chemistry. In addition to tholins characterization and analysis, we recently investigated quantitatively the hydrolysis kinetics of tholins in pure and NH3 containing water at different temperatures.7-8 Our groups at UJF (Grenoble) and at U of Arizona (Tucson) have been collaborating on mass spectral analyses of tholins samples for several years.9 Here, we report our most recent results on the structural characterization of tholins by infrared multiphoton dissociation (IRMPD) action spectroscopy10 and ultrahigh resolution MS. IRMPD action spectroscopy is a recently developed technique that uses IR photons of variable wavelengths to activate ions trapped inside an ion trap. When photons are absorbed at a given wavelength, the selected ion fragments and this fragmentation is monitored as a function of wavelength, analog to an absorption spectrum (impossible to record otherwise because of the much reduced density). This technique can, therefore, be used to determine IR spectra of ions in the gas phase, and provides with very acute structural information. IRMPD action spectroscopy is often used to distinguish between structural isomers of isobaric ions. The drawback is that it requests for high power lasers. Only two Free Electron Lasers (FEL) are available in the world and allow to record spectra with reasonable resolution (20-25 cm-1). IRMPD action spectra of selected ions from tholins will be presented and discussed together with observed fragmentation processes that reveal structural

  1. Practical aspects of trapped ion mass spectrometry, 5 applications of ion trapping devices

    CERN Document Server

    March, Raymond E

    2009-01-01

    Examines ion/neutral and ion/ion reactions, ion spectroscopy, and the structural characterization of proteins and peptides using quadropole ion trap mass spectrometry, Fourier transform - ion cyclotron resonance (FT-ICR) mass spectrometry, and traveling wave ion mobility mass spectrometry.

  2. High-resolution mass spectrometry in toxicology: current status and future perspectives.

    Science.gov (United States)

    Maurer, H H; Meyer, Markus R

    2016-09-01

    This paper reviews high-resolution mass spectrometry (HRMS) approaches using time-of-flight or Orbitrap techniques for research and application in various toxicology fields, particularly in clinical toxicology and forensic toxicology published since 2013 and referenced in PubMed. In the introduction, an overview on applications of HRMS in various toxicology fields is given with reference to current review articles. Papers concerning HRMS in metabolism, screening, and quantification of pharmaceuticals, drugs of abuse, and toxins in human body samples are critically reviewed. Finally, a discussion on advantages as well as limitations and future perspectives of these methods is included.

  3. Argentation chromatography coupled to ultrahigh-resolution mass spectrometry for the separation of a heavy crude oil.

    Science.gov (United States)

    Molnárné Guricza, Lilla; Schrader, Wolfgang

    2017-02-10

    Simplification of highly complex mixtures such as crude oil by using chromatographic methods makes it possible to get more detailed information about the composition of the analyte. Separation by argentation chromatography can be achieved based on the interaction of different strength between the silver ions (Ag + ) immobilized through a spacer on the silica gel surface and the π-bonds of the analytes. Heavy crude oils contain compounds with a high number of heteroatoms (N, O, S) and a high degree of unsaturation thus making them the perfect analyte for argentation chromatography. The direct coupling of argentation chromatography and ultrahigh-resolution mass spectrometry allows to continuously tracking the separation of the many different compounds by retention time and allows sensitive detection on a molecular level. Direct injection of a heavy crude oil into a ultrahigh-resolution mass spectrometer showed components with DBE of up to 25, whereas analytes with DBE of up to 35 could be detected only after separation with argentation chromatography. The reduced complexity achieved by the separation helps increasing the information depth. Copyright © 2016. Published by Elsevier B.V.

  4. Detection of heavy metal ions in drinking water using a high-resolution differential surface plasmon resonance sensor.

    Science.gov (United States)

    Forzani, Erica S; Zhang, Haiqian; Chen, Wilfred; Tao, Nongjian

    2005-03-01

    We have built a high-resolution differential surface plasmon resonance (SPR) sensor for heavy metal ion detection. The sensor surface is divided into a reference and sensing areas, and the difference in the SPR angles from the two areas is detected with a quadrant cell photodetector as a differential signal. In the presence of metal ions, the differential signal changes due to specific binding of the metal ions onto the sensing area coated with properly selected peptides, which provides an accurate real-time measurement and quantification of the metal ions. Selective detection of Cu2+ and Ni2+ in the ppt-ppb range was achieved by coating the sensing surface with peptides NH2-Gly-Gly-His-COOH and NH2-(His)6-COOH. Cu2+ in drinking water was tested using this sensor.

  5. Novel product ions of 2-aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi-stage tandem mass spectrometry.

    Science.gov (United States)

    Johnson, Byron S; Burinsky, David J; Burova, Svetlana A; Davis, Roman; Fitzgerald, Russ N; Matsuoka, Richard T

    2012-05-15

    The 2-aminoaniline scaffold is of significant value to the pharmaceutical industry and is embedded in a number of pharmacophores including 2-aminoanilides and benzimidazoles. A novel application of coordination ion spray mass spectrometry (CIS-MS) for interrogating the silver ion (Ag(+)) complexes of a homologous series of these compounds using multi-stage tandem mass spectrometry is described. Unlike the ubiquitous alkali metal ion complexes, Ag(+) complexes of 2-aminoanilides and benzimidazoles were found to yield [M - H](+) ions in significant abundance via gas-phase elimination of the metal hydride (AgH) resulting in unique product ion cascades. Sample introduction was by liquid chromatography with mass spectrometry analysis performed on a hybrid linear ion trap/orbitrap instrument capable of high-resolution measurements. Rigorous structural characterization by multi-stage tandem mass spectrometry using [M +  H](+), [M - H](-) and [M - H](+) precursor ions derived from ESI and CIS experiments was performed for the homologous series of 2-aminoanilide and benzimidazole compounds. A full tabular comparison of structural information resulting from these product ion cascades was produced. Multi-stage tandem mass spectrometry of [M - H](+) ions resulting from Ag(+) complexes of 2-aminoanilides and benzimidazoles in CIS-MS experiments produced unique product ion cascades that exhibited complementary structural information to that obtained from tandem mass spectrometry of [M  +  H](+) and [M - H](-) ions by electrospray ionization (ESI). These observations may be broadly applicable to other compounds that are observed to form Ag(+) complexes and eliminate AgH. Copyright © 2012 John Wiley & Sons, Ltd.

  6. Development of AMS high resolution injector system

    International Nuclear Information System (INIS)

    Bao Yiwen; Guan Xialing; Hu Yueming

    2008-01-01

    The Beijing HI-13 tandem accelerator AMS high resolution injector system was developed. The high resolution energy achromatic system consists of an electrostatic analyzer and a magnetic analyzer, which mass resolution can reach 600 and transmission is better than 80%. (authors)

  7. Targeting high-performance liquid chromatography-high-resolution mass spectrometry-solid-phase extraction-nuclear magnetic resonance analysis with high-resolution radical scavenging profiles - bioactive secondary metabolites from the endophytic fungus Penicillium namyslowskii

    DEFF Research Database (Denmark)

    Wubshet, Sileshi Gizachew; Nyberg, Nils; Tejesvi, Mysore V.

    2013-01-01

    The high-resolution radical scavenging profile of an extract of the endophytic fungus Penicillium namyslowskii was used to target analysis by high-performance liquid chromatography-high-resolution mass spectrometry-solid-phase extraction-nuclear magnetic resonance spectroscopy, i.e., HPLC...... NMR probe designed for 1.7-mm NMR tubes. To further explore the potential of the above HPLC-HRMS-SPE-NMR platform for analysis of endophytic extracts, six peaks displaying no radical scavenging activity were also analyzed. This allowed unambiguous identification of six metabolites, i...... and griseofulvin, directly from crude extract via HPLC-HRMS-SPE-NMR. Dechlorodehydrogriseofulvin was reported for the first time from nature....

  8. Fragmentation analysis of water-soluble atmospheric organic matter using ultrahigh-resolution FT-ICR mass spectrometry.

    Science.gov (United States)

    Leclair, Jeffrey P; Collett, Jeffrey L; Mazzoleni, Lynn R

    2012-04-17

    Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

  9. Ultrananocrystalline Diamond Membranes for Detection of High-Mass Proteins

    Science.gov (United States)

    Kim, H.; Park, J.; Aksamija, Z.; Arbulu, M.; Blick, R. H.

    2016-12-01

    Mechanical resonators realized on the nanoscale by now offer applications in mass sensing of biomolecules with extraordinary sensitivity. The general idea is that perfect mechanical mass sensors should be of extremely small size to achieve zepto- or yoctogram sensitivity in weighing single molecules similar to a classical scale. However, the small effective size and long response time for weighing biomolecules with a cantilever restricts their usefulness as a high-throughput method. Commercial mass spectrometry (MS), on the other hand, such as electrospray ionization and matrix-assisted laser desorption and ionization (MALDI) time of flight (TOF) and their charge-amplifying detectors are the gold standards to which nanomechanical resonators have to live up to. These two methods rely on the ionization and acceleration of biomolecules and the following ion detection after a mass selection step, such as TOF. The principle we describe here for ion detection is based on the conversion of kinetic energy of the biomolecules into thermal excitation of chemical vapor deposition diamond nanomembranes via phonons followed by phonon-mediated detection via field emission of thermally emitted electrons. We fabricate ultrathin diamond membranes with large lateral dimensions for MALDI TOF MS of high-mass proteins. These diamond membranes are realized by straightforward etching methods based on semiconductor processing. With a minimal thickness of 100 nm and cross sections of up to 400 ×400 μ m2 , the membranes offer extreme aspect ratios. Ion detection is demonstrated in MALDI TOF analysis over a broad range from insulin to albumin. The resulting data in detection show much enhanced resolution as compared to existing detectors, which can offer better sensitivity and overall performance in resolving protein masses.

  10. Picosecond resolution on relativistic heavy ions' time-of-flight measurement

    International Nuclear Information System (INIS)

    Ebran, A.; Taieb, J.; Belier, G.; Chatillon, A.; Laurent, B.; Martin, J.-F.; Pellereau, E.

    2013-01-01

    We developed a time-of-flight measurement system for relativistic heavy ions with a requested resolution of 40 ps Full Width Half Maximum. Such a resolution is mandatory to assign the correct mass number to every fission fragment, identified using the Bρ-ToF-ΔE method with the recoil spectrometer designed for the SOFIA experiment—which hold very recently at GSI. To achieve such a performance, fast plastic scintillators read-out by dedicated photomultiplier tubes were chosen among other possible options. We have led several test-measurements from 2009 to 2011, in order to investigate: the effect of the addition of a quenching molecule in the scintillator's matrix, the influence of the detector's size and the impact of the photomultiplier tube. The contribution of the dedicated electronics is also characterized. Time-of-flight measurements were performed realized with electron pulses and relativistic heavy ions, respectively provided by the LASER driven electron–accelerator (ELSA) at CEA–DAM Ile-de-France and by the SIS18/FRS facility at GSI. The reported results exhibit a time resolution better than 20 ps Full Width Half Maximum reached with the last prototype at GSI with an Uranium beam. These results confirm that the SOFIA experiment should enable the measurement of the relativistic fission fragments' time-of-flight with the requested resolution

  11. Secondary ion mass spectroscopy (SIMS)

    International Nuclear Information System (INIS)

    Naik, P.K.

    1975-01-01

    Secondary Ion Mass Spectrometry (SIMS) which is primarily a method for investigating the chemical composition of the uppermost atomic layer of solid surfaces is explained. In this method, the specimen is bombarded with a primary positive ion beam of small current density monolayer. Positive and negative ions sputtered from the specimen are mass analysed to give the surface chemical composition. The analytical system which consists of a primary ion source, a target manipulator and a mass spectrometer housed in an ultrahigh vacuum system is described. This method can also be used for profile measurements in thin films by using higher current densities of the primary ions. Fields of application such as surface reactions, semiconductors, thin films emission processes, chemistry, metallurgy are touched upon. Various aspects of this method such as the sputtering process, instrumentation, and applications are discussed. (K.B.)

  12. Behaviour of tetraalkylammonium ions in high-field asymmetric waveform ion mobility spectrometry.

    Science.gov (United States)

    Aksenov, Alexander A; Kapron, James T

    2010-05-30

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an ion-filtering technique recently adapted for use with liquid chromatography/mass spectrometry (LC/MS) to remove interferences during analysis of complex matrices. This is the first systematic study of a series of singly charged tetraalkylammonium ions by FAIMS-MS. The compensation voltage (CV) is the DC offset of the waveform which permits the ion to emerge from FAIMS and it was determined for each member of the series under various conditions. The electrospray ionization conditions explored included spray voltage, vaporizer temperature, and sheath and auxiliary gas pressure. The FAIMS conditions explored included carrier gas flow rate, electrode temperature and composition of the carrier gas. Optimum desolvation was achieved using sufficient carrier gas (flow rate > or = 2 L/min) to ensure stable response. Low-mass ions (m/z 100-200) are more susceptible to changes in electrode temperature and gas composition than high mass ions (m/z 200-700). As a result of this study, ions are reliably analyzed using standard FAIMS conditions (dispersion voltage -5000 V, carrier gas flow rate 3 L/min, 50% helium/50%nitrogen, inner electrode temperature 70 degrees C and outer electrode temperature 90 degrees C). Variation of FAIMS conditions may be of great use for the separation of very low mass tetraalkylammonium (TAA) ions from other TAA ions. The FAIMS conditions do not appear to have a major effect on higher mass ions. Copyright 2010 John Wiley & Sons, Ltd.

  13. Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    Farnsworth, Paul B.; Spencer, Ross L.

    2017-08-01

    Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

  14. Long-range transport biomass burning emissions to the Himalayas: insights from high-resolution aerosol mass spectrometer

    Science.gov (United States)

    Xu, J.; Zhang, X.; Liu, Y.; Shichang, K.; Ma, Y.

    2017-12-01

    An intensive measurement was conducted at a remote, background, and high-altitude site (Qomolangma station, QOMS, 4276 m a.s.l.) in the northern Himalayas, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) along with other collocated instruments. The field measurement was performed from April 12 to May 12, 2016 to chemically characterize high time-resolved submicron particulate matter (PM1) and obtain the influence of biomass burning emissions to the Himalayas, frequently transported from south Asia during pre-monsoon season. Two high aerosol loading periods were observed during the study. Overall, the average (± 1σ) PM1 mass concentration was 4.44 (± 4.54) µg m-3 for the entire study, comparable with those observed at other remote sites worldwide. Organic aerosols (OA) was the dominant PM1 species (accounting for 54.3% of total PM1 mass on average) and its contribution increased with the increase of total PM1 mass loading. The average size distributions of PM1 species all peaked at an overlapping accumulation mode ( 500 nm), suggesting that aerosol particles were internally well-mixed and aged during long-range transportations. Positive matrix factorization (PMF) analysis on the high-resolution organic mass spectra identified three distinct OA factors, including a biomass burning related OA (BBOA, 43.7%) and two oxygenated OA (Local-OOA and LRT-OOA; 13.9% and 42.4%) represented sources from local emissions and long-range transportations, respectively. Two polluted air mass origins (generally from the west and southwest of QOMS) and two polluted episodes with enhanced PM1 mass loadings and elevated BBOA contributions were observed, respectively, suggesting the important sources of wildfires from south Asia. One of polluted aerosol plumes was investigated in detail to illustrate the evolution of aerosol characteristics at QOMS driving by different impacts of wildfires, air mass origins, meteorological conditions and

  15. Histamine quantification in human plasma using high resolution accurate mass LC-MS technology.

    Science.gov (United States)

    Laurichesse, Mathieu; Gicquel, Thomas; Moreau, Caroline; Tribut, Olivier; Tarte, Karin; Morel, Isabelle; Bendavid, Claude; Amé-Thomas, Patricia

    2016-01-01

    Histamine (HA) is a small amine playing an important role in anaphylactic reactions. In order to identify and quantify HA in plasma matrix, different methods have been developed but present several disadvantages. Here, we developed an alternative method using liquid chromatography coupled with an ultra-high resolution and accurate mass instrument, Q Exactive™ (Thermo Fisher) (LCHRMS). The method includes a protein precipitation of plasma samples spiked with HA-d4 as internal standard (IS). LC separation was performed on a C18 Accucore column (100∗2.1mm, 2.6μm) using a mobile phase containing nonafluoropentanoic acid (3nM) and acetonitrile with 0.1% (v/v) formic acid on gradient mode. Separation of analytes was obtained within 10min. Analysis was performed from full scan mode and targeted MS2 mode using a 5ppm mass window. Ion transitions monitored for targeted MS2 mode were 112.0869>95.0607m/z for HA and 116.1120>99.0855m/z for HA-d4. Calibration curves were obtained by adding standard calibration dilution at 1 to 180nM in TrisBSA. Elution of HA and IS occurred at 4.1min. The method was validated over a range of concentrations from 1nM to 100nM. The intra- and inter-run precisions were <15% for quality controls. Human plasma samples from 30 patients were analyzed by LCHRMS, and the results were highly correlated with those obtained using the gold standard radioimmunoassay (RIA) method. Overall, we demonstrate here that LCHRMS is a sensitive method for histamine quantification in biological human plasmas, suitable for routine use in medical laboratories. In addition, LCHRMS is less time-consuming than RIA, avoids the use of radioactivity, and could then be considered as an alternative quantitative method. Copyright © 2015 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  16. Construction, characterization and applications of a compact mass-resolved low-energy ion beam system

    International Nuclear Information System (INIS)

    Lau, W.M.; Feng, X.; Bello, I.; Sant, S.; Foo, K.K.; Lawson, R.P.W.

    1991-01-01

    A compact mass-resolved low-energy ion beam system has been constructed in which ions are extracted from a Colutron ion source, focused by an einzel lens, mass-selected by a Wien filter, refocused by a second einzel lens into an ultrahigh vacuum target chamber, and finally decelerated with a five-electrode lens. The design of the deceleration lens was assisted by computer simulation including space-charge effects with an ion trajectory software (CHDEN). The system performance has been characterized with a quadrupole mass spectrometer and an energy analyzer along the beam axis. For example, argon ions can be transported at keV and decelerated to 10 eV with an energy spread of ±0.5 eV. The total current measured by a Faraday cage at the exit of the deceleration lens in the energy range of 10-200 eV is about 1-5 μA. The ion current density was higher than 100 μA/cm 2 at 50 eV but decreased to 10-20 μA/cm 2 at 10 eV. The mass resolution was estimated to be 40 under the present operation configuration. The system has been used to produce interesting results in both ion beam etching and deposition. (orig.)

  17. Double-diffractive processes in high-resolution missing-mass experiments at the Tevatron

    International Nuclear Information System (INIS)

    Khoze, V.A.; Martin, A.D.

    2001-01-01

    We evaluate, in a model-independent way, the signal-to-background ratio for Higgs→b anti b detection in exclusive double-diffractive events at the Tevatron and the LHC. For the missing-mass approach to be able to identify the Higgs boson, it will be necessary to use a central jet detector and to tag b quark jets. The signal is predicted to be very small at the Tevatron, but observable at the LHC. However we note that the background, that is double-diffractive dijet production, may serve as a unique gluon factory. We also give estimates for the double-diffractive production of χ c and χ b mesons at the Tevatron. We emphasize that a high-resolution missing-mass measurement, on its own, is insufficient to identify rare processes. (orig.)

  18. Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

    Science.gov (United States)

    Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka; Marković, Nikola; Anghelone, Marta; Stoytschew, Valentin; Jakšić, Milko

    2017-09-01

    Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples were not embedded in the resin as is usually done when imaging of paint samples using different techniques in the field of cultural heritage.

  19. Orbitrap-based mass analyser for in-situ characterization of asteroids: ILMA, Ion Laser Mass Analyser

    Science.gov (United States)

    Briois, C.; Cotti, H.; Thirkell, L.; Space Orbitrap Consortium[K. Aradj, French; Bouabdellah, A.; Boukrara, A.; Carrasco, N.; Chalumeau, G.; Chapelon, O.; Colin, F.; Coll, P.; Engrand, C.; Grand, N.; Kukui, A.; Lebreton, J.-P.; Pennanech, C.; Szopa, C.; Thissen, R.; Vuitton, V.; Zapf], P.; Makarov, A.

    2014-07-01

    Since about a decade the boundaries between comets and carbonaceous asteroids are fading [1,2]. No doubt that the Rosetta mission should bring a new wealth of data on the composition of comets. But as promising as it may look, the mass resolving power of the mass spectrometers onboard (so far the best on a space mission) will only be able to partially account for the diversity of chemical structures present. ILMA (Ion-Laser Mass Analyser) is a new generation high mass resolution LDI-MS (Laser Desorption-Ionization Mass Spectrometer) instrument concept using the Orbitrap technique, which has been developed in the frame of the two Marco Polo & Marco Polo-R proposals to the ESA Cosmic Vision program. Flagged by ESA as an instrument concept of interest for the mission in 2012, it has been under study for a few years in the frame of a Research and Technology (R&T) development programme between 5 French laboratories (LPC2E, IPAG, LATMOS, LISA, CSNSM) [3,4], partly funded by the French Space Agency (CNES). The work is undertaken in close collaboration with the Thermo Fisher Scientific Company, which commercialises Orbitrap-based laboratory instruments. The R&T activities are currently concentrating on the core elements of the Orbitrap analyser that are required to reach a sufficient maturity level for allowing design studies of future space instruments. A prototype is under development at LPC2E and a mass resolution (m/Δm FWHM) of 100,000 as been obtained at m/z = 150 for a background pressure of 10^{-8} mbar. ILMA would be a key instrument to measure the molecular, elemental and isotopic composition of objects such as carbonaceous asteroids, comets, or other bodies devoid of atmosphere such as the surface of an icy satellite, the Moon, or Mercury.

  20. Quantitative analysis of 39 polybrominated diphenyl ethers by isotope dilution GC/low-resolution MS.

    Science.gov (United States)

    Ackerman, Luke K; Wilson, Glenn R; Simonich, Staci L

    2005-04-01

    A GC/low-resolution MS method for the quantitative isotope dilution analysis of 39 mono- to heptabrominated diphenyl ethers was developed. The effects of two different ionization sources, electron impact (EI) and electron capture negative ionization (ECNI), and the effects of their parameters on production of high-mass fragment ions [M - xH - yBr](-) specific to PBDEs were investigated. Electron energy, emission current, source temperature, ECNI system pressure, and choice of ECNI reagent gases were optimized. Previously unidentified enhancement of PBDE high-mass fragment ion [M - xH - yBr](-) abundance was achieved. Electron energy had the largest impact on PBDE high-mass fragment ion abundance for both the ECNI and EI sources. By monitoring high-mass fragment ions of PBDEs under optimized ECNI source conditions, quantitative isotope dilution analysis of 39 PBDEs was conducted using nine (13)C(12) labeled PBDEs on a low-resolution MS with low picogram to femtogram instrument detection limits.

  1. Cold-target recoil-ion momentum-spectroscopy: First results and future perspectives of a novel high resolution technique for the investigation of collision induced many-particle reactions

    International Nuclear Information System (INIS)

    Ullrich, J.; Doerner, R.; Mergel, V.; Jagutzki, O.; Spielberger, L.; Schmidt-Boecking, H.

    1994-09-01

    In order to investigate many-particle reaction dynamics in atomic collisions a novel high-resolution technique has been developed, which determines the momentum and the charge state of the slowly recoiling target ions. Using a very cold, thin, and localized supersonic gas jet target a momentum resolution of better than 0.05 a.u. is obtained by measuring the recoil-ion time-of-flight and the recoil-ion trajectory. Because of the very high detection efficiency of nearly 100% this technique is well suited for many-particle coincidence measurements in ionizing collisions. First experimental results for fast ion and electron impact on helium targets are presented. Future applications in atomic collision physics and related areas are discussed. (orig.)

  2. Ion exchange currents in vacuum accelerator tubes

    International Nuclear Information System (INIS)

    Eastham, D.A.; Thorn, R.

    1978-01-01

    Ion exchange currents (microdischarges) have been observed in short lengths of accelerator tube. The occurrence of these discharges can be related to the trajectories of ions in the tube. High-resolution mass spectra of the negative and positive ion components have been obtained. (author)

  3. Identification of triacylglycerol using automated annotation of high resolution multistage mass spectral trees.

    Science.gov (United States)

    Wang, Xiupin; Peng, Qingzhi; Li, Peiwu; Zhang, Qi; Ding, Xiaoxia; Zhang, Wen; Zhang, Liangxiao

    2016-10-12

    High complexity of identification for non-target triacylglycerols (TAGs) is a major challenge in lipidomics analysis. To identify non-target TAGs, a powerful tool named accurate MS(n) spectrometry generating so-called ion trees is used. In this paper, we presented a technique for efficient structural elucidation of TAGs on MS(n) spectral trees produced by LTQ Orbitrap MS(n), which was implemented as an open source software package, or TIT. The TIT software was used to support automatic annotation of non-target TAGs on MS(n) ion trees from a self-built fragment ion database. This database includes 19108 simulate TAG molecules from a random combination of fatty acids and corresponding 500582 self-built multistage fragment ions (MS ≤ 3). Our software can identify TAGs using a "stage-by-stage elimination" strategy. By utilizing the MS(1) accurate mass and referenced RKMD, the TIT software can discriminate unique elemental composition candidates. The regiospecific isomers of fatty acyl chains will be distinguished using MS(2) and MS(3) fragment spectra. We applied the algorithm to the selection of 45 TAG standards and demonstrated that the molecular ions could be 100% correctly assigned. Therefore, the TIT software could be applied to TAG identification in complex biological samples such as mouse plasma extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Comparison of linear intrascan and interscan dynamic ranges of Orbitrap and ion-mobility time-of-flight mass spectrometers.

    Science.gov (United States)

    Kaufmann, Anton; Walker, Stephan

    2017-11-30

    The linear intrascan and interscan dynamic ranges of mass spectrometers are important in metabolome and residue analysis. A large linear dynamic range is mandatory if both low- and high-abundance ions have to be detected and quantitated in heavy matrix samples. These performance criteria, as provided by modern high-resolution mass spectrometry (HRMS), were systematically investigated. The comparison included two generations of Orbitraps, and an ion mobility quadrupole time-of-flight (QTOF) system In addition, different scan modes, as provided by the utilized instruments, were investigated. Calibration curves of different compounds covering a concentration range of five orders of magnitude were measured to evaluate the linear interscan dynamic range. The linear intrascan dynamic range and the resulting mass accuracy were evaluated by repeating these measurements in the presence of a very intense background. Modern HRMS instruments can show linear dynamic ranges of five orders of magnitude. Often, however, the linear dynamic range is limited by the detection capability (sensitivity and selectivity) and by the electrospray ionization. Orbitraps, as opposed to TOF instruments, show a reduced intrascan dynamic range. This is due to the limited C-trap and Orbitrap capacity. The tested TOF instrument shows poorer mass accuracies than the Orbitraps. In contrast, hyphenation with an ion-mobility device seems not to affect the linear dynamic range. The linear dynamic range of modern HRMS instrumentation has been significantly improved. This also refers to the virtual absence of systematic mass shifts at high ion abundances. The intrascan dynamic range of the current Orbitrap technology may still be a limitation when analyzing complex matrix extracts. On the other hand, the linear dynamic range is not only limited by the detector technology, but can also be shortened by peripheral devices, where the ionization and transfer of ions take place. Copyright © 2017 John Wiley

  5. Triple aldose reductase/α-glucosidase/radical scavenging high-resolution profiling combined with high-performance liquid chromatography – high-resolution mass spectrometry – solid-phase extraction – nuclear magnetic resonance spectroscopy for identification of antidiabetic constituents in crude, extract of Radix Scutellariae

    DEFF Research Database (Denmark)

    Tahtah, Yousof; Kongstad, Kenneth Thermann; Wubshet, Sileshi Gizachew

    2015-01-01

    high-performance liquid chromatography – high-resolution mass spectrometry – solid-phase extraction – nuclear magnetic resonance spectroscopy. The only α-glucosidase inhibitor was baicalein, whereas main aldose reductase inhibitors in the crude extract were baicalein and skullcapflavone II, and main....../α-glucosidase/radical scavenging high-resolution inhibition profile - allowing proof of concept with Radix Scutellariae crude extract as a polypharmacological herbal drug. The triple bioactivity high-resolution profiles were used to pinpoint bioactive compounds, and subsequent structure elucidation was performed with hyphenated...

  6. Application of characteristic ion filtering with ultra-high performance liquid chromatography quadrupole time of flight tandem mass spectrometry for rapid detection and identification of chemical profiling in Eucommia ulmoides Oliv.

    Science.gov (United States)

    He, Mingzhen; Jia, Jia; Li, Junmao; Wu, Bei; Huang, Wenping; Liu, Mi; Li, Yan; Yang, Shilin; Ouyang, Hui; Feng, Yulin

    2018-06-15

    Efficient targeted identification of chemical constituents from traditional Chinese medicine is still a major challenge. In this study, we used a characteristic ion filtering strategy to characterize compounds of Eucommia ulmoides Oliv. by ultra-high performance liquid chromatography quadrupole time of flight tandem mass spectrometry (UHPLC-ESI-Q-TOF-MS/MS). By using the ion filtering approach, target constituents of Eucommia ulmoides Oliv. were easily tentatively identified from the enormous LC/MS data set. The strategy consisted of the following three steps: 1) To establishing a characteristic ion database by diagnostic product ions or neutral loss fragments; 2) To evaluate the structural information of the compounds by high-resolution diagnostic characteristic ion filtering; 3) To confirm the different classes by chemical profiling according to their MS/MS spectra. In this study, characteristic ions are summarized as five major groups of compounds in Eucommia ulmoides Oliv. In total, 113 compounds were tentatively identified, including 23 potentially novel compounds. The results form a foundation for the quality control and chemical basis of Eucommia ulmoides Oliv. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    Science.gov (United States)

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-06

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

  8. Procedure and apparatus for controlling the ion energy in a mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Fies, W J; Reeher, J R; Story, M S; Smith, R D

    1977-03-03

    The invention relates to a process and apparatus for adjusting the energy of ions of different masses in a mass spectrometer. Specifically, it concerns a mass spectrometer having a gas inlet and ionisation space. A multipole mass filter includes several electrodes. A focusing system connects the ionisation space and the mass filter. Provision is made for applying to the electrodes a mass adjusting voltage combining a high frequency voltage and a d.c. voltage of increasing amplitude, so that the ions of a pre-determined mass can be selected. This system also includes a device connected to the electrodes, sensitive to the mass adjusting voltage and enabling the energy of the ions to be adjusted to that of the selected ions, depending on the mass of the ions, by modifying the difference in potential between the ionisation volume and the mean potential of the electrodes .

  9. Classification of wine by determination of bioactive phenolic compounds using high resolution mass spectrometry

    OpenAIRE

    Ivanova, Violeta; Dimovska, Violeta; Mitrev, Sasa; Gulaboski, Rubin; Bogeva, Elena; Petruseva, Dragana; Causon, Tim; Hann, Stephan

    2016-01-01

    In this project proposal, metabolomic fingerprinting of wine samples will be examined using high performance liquid chromatography combined with ion mobility quadruple time-of-flight mass spectrometry (HPLC–IMS-QTOF-MS) for the first time. Bioactive compounds in wines from various red and white varieties produced in Macedonia and Austria from different wine regions and different vintages will be determined for the first time using a non-targeted fingerprinting approach on this analytical plat...

  10. Structural Characterisation of Acetogenins from Annona muricata by Supercritical Fluid Chromatography Coupled to High-Resolution Tandem Mass Spectrometry.

    Science.gov (United States)

    Laboureur, Laurent; Bonneau, Natacha; Champy, Pierre; Brunelle, Alain; Touboul, David

    2017-11-01

    Acetogenins are plant polyketides known to be cytotoxic and proposed as antitumor candidates. They are also suspected to be alimentary neurotoxins. Their occurrence as complex mixtures renders their dereplication and structural identification difficult using liquid chromatography coupled to tandem mass spectrometry and efforts are required to improve the methodology. To develop a supercritical fluid chromatography (SFC) high-resolution tandem mass spectrometry method, involving lithium post-column cationisation, for the structural characterisation of Annonaceous acetogenins in crude extracts. The seeds of Annona muricata L. were extracted with methanol. Supercritical fluid chromatography of the extract, using a 2-ethylpyridine stationary phase column, was monitored using a high-resolution quadrupole time-of-flight mass spectrometer. Lithium iodide was added post-column in the make-up solvent. For comparison, the same extract was analysed using high-pressure liquid chromatography coupled to the same mass spectrometer, with a column based on solid core particles. Sensitivity was similar for both HPLC and SFC approaches. Retention behaviour and fragmentation pathways of three different isomer groups are described. A previously unknown group of acetogenins was also evidenced for the first time. The use of SFC-MS/MS allows the reduction of the time of analysis, of environmental impact and an increase in the chromatographic resolution, compared to liquid chromatography. This new methodology enlightened a new group of acetogenins, isomers of montanacin-D. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  11. Otolith oxygen isotopes measured by high-precision secondary ion mass spectrometry reflect life history of a yellowfin sole (Limanda aspera).

    Science.gov (United States)

    Matta, Mary Elizabeth; Orland, Ian J; Ushikubo, Takayuki; Helser, Thomas E; Black, Bryan A; Valley, John W

    2013-03-30

    The oxygen isotope ratio (δ(18)O value) of aragonite fish otoliths is dependent on the temperature and the δ(18)O value of the ambient water and can thus reflect the environmental history of a fish. Secondary ion mass spectrometry (SIMS) offers a spatial-resolution advantage over conventional acid-digestion techniques for stable isotope analysis of otoliths, especially given their compact nature. High-precision otolith δ(18)O analysis was conducted with an IMS-1280 ion microprobe to investigate the life history of a yellowfin sole (Limanda aspera), a Bering Sea species known to migrate ontogenetically. The otolith was cut transversely through its core and one half was roasted to eliminate organic contaminants. Values of δ(18)O were measured in 10-µm spots along three transects (two in the roasted half, one in the unroasted half) from the core toward the edge. Otolith annual growth zones were dated using the dendrochronology technique of crossdating. Measured values of δ(18)O ranged from 29.0 to 34.1‰ (relative to Vienna Standard Mean Ocean Water). Ontogenetic migration from shallow to deeper waters was reflected in generally increasing δ(18)O values from age-0 to approximately age-7 and subsequent stabilization after the expected onset of maturity at age-7. Cyclical variations of δ(18)O values within juvenile otolith growth zones, up to 3.9‰ in magnitude, were caused by a combination of seasonal changes in the temperature and the δ(18)O value of the ambient water. The ion microprobe produced a high-precision and high-resolution record of the relative environmental conditions experienced by a yellowfin sole that was consistent with population-level studies of ontogeny. Furthermore, this study represents the first time that crossdating has been used to ensure the dating accuracy of δ(18)O measurements in otoliths. Copyright © 2013 John Wiley & Sons, Ltd.

  12. High resolution techniques using scanning proton microprobe (SPM)

    International Nuclear Information System (INIS)

    Cholewa, M.; Saint, A.; Prawer, S.; Laird, J.S.; Legge, G.J.F.; Bardos, R.A.; Moorhead, G.F.; Taylor, G.N.; Stuart, S.A.; Howard, J.

    1994-01-01

    The very high resolution (down to 50 nm) achieved with low beam currents (fA) in a scanning ion microprobe have lead to many nondestructive techniques of microanalysis. This paper discusses recent developments and applications in the use of 3-D STIM (scanning transmission ion microscopy) Tomography, channeling STIM and IBIC (ion beam induced charge). (orig.)

  13. Picosecond resolution on relativistic heavy ions' time-of-flight measurement

    Energy Technology Data Exchange (ETDEWEB)

    Ebran, A., E-mail: adeline.ebran@cea.fr; Taieb, J., E-mail: julien.taieb@cea.fr; Belier, G.; Chatillon, A.; Laurent, B.; Martin, J.-F.; Pellereau, E.

    2013-11-11

    We developed a time-of-flight measurement system for relativistic heavy ions with a requested resolution of 40 ps Full Width Half Maximum. Such a resolution is mandatory to assign the correct mass number to every fission fragment, identified using the Bρ-ToF-ΔE method with the recoil spectrometer designed for the SOFIA experiment—which hold very recently at GSI. To achieve such a performance, fast plastic scintillators read-out by dedicated photomultiplier tubes were chosen among other possible options. We have led several test-measurements from 2009 to 2011, in order to investigate: the effect of the addition of a quenching molecule in the scintillator's matrix, the influence of the detector's size and the impact of the photomultiplier tube. The contribution of the dedicated electronics is also characterized. Time-of-flight measurements were performed realized with electron pulses and relativistic heavy ions, respectively provided by the LASER driven electron–accelerator (ELSA) at CEA–DAM Ile-de-France and by the SIS18/FRS facility at GSI. The reported results exhibit a time resolution better than 20 ps Full Width Half Maximum reached with the last prototype at GSI with an Uranium beam. These results confirm that the SOFIA experiment should enable the measurement of the relativistic fission fragments' time-of-flight with the requested resolution.

  14. Orbitrap technology for comprehensive metabolite-based liquid chromatographic–high resolution-tandem mass spectrometric urine drug screening – Exemplified for cardiovascular drugs

    International Nuclear Information System (INIS)

    Helfer, Andreas G.; Michely, Julian A.; Weber, Armin A.; Meyer, Markus R.; Maurer, Hans H.

    2015-01-01

    LC–high resolution (HR)-MS well established in proteomics has become more and more important in bioanalysis of small molecules over the last few years. Its high selectivity and specificity provide best prerequisites for its use in broad screening approaches. Therefore, Orbitrap technology was tested for developing a general metabolite-based LC–HR-MS/MS screening approach for urinalysis of drugs necessary in clinical and forensic toxicology. After simple urine precipitation, the drugs and their metabolites were separated within 10 min and detected by a Q-Exactive mass spectrometer in full scan with positive/negative switching, and subsequent data dependent acquisition (DDA) mode. Identification criteria were the presence of accurate precursor ions, isotopic patterns, five most intense fragment ions, and comparison with full HR-MS/MS library spectra. The current library contains over 1900 parent drugs and 1200 metabolites. The method was validated for typical drug representatives and metabolites concerning recovery, matrix effects, process efficiency, and limits showed acceptable results. The applicability was tested first for cardiovascular drugs, which should be screened for in poisoning cases and for medication adherence of hypertension patients. The novel LC–HR-MS/MS method allowed fast, simple, and robust urine screening, particularly for cardiovascular drugs showing the usefulness of Orbitrap technology for drug testing. - Highlights: • First study on the application of Orbitrap technology for comprehensive drug screening in clinical and forensic toxicology. • Simple workup, sufficient separation, and powerful screening and identification using modern high resolution MS. • Validation of the assay according to guidelines for qualitative approaches. • Elucidation of the power of new data evaluation software in combination with a new reference drug and metabolite library. • Great relevance for science and practice in clinical and forensic

  15. Orbitrap technology for comprehensive metabolite-based liquid chromatographic–high resolution-tandem mass spectrometric urine drug screening – Exemplified for cardiovascular drugs

    Energy Technology Data Exchange (ETDEWEB)

    Helfer, Andreas G.; Michely, Julian A.; Weber, Armin A.; Meyer, Markus R.; Maurer, Hans H., E-mail: hans.maurer@uks.eu

    2015-09-03

    LC–high resolution (HR)-MS well established in proteomics has become more and more important in bioanalysis of small molecules over the last few years. Its high selectivity and specificity provide best prerequisites for its use in broad screening approaches. Therefore, Orbitrap technology was tested for developing a general metabolite-based LC–HR-MS/MS screening approach for urinalysis of drugs necessary in clinical and forensic toxicology. After simple urine precipitation, the drugs and their metabolites were separated within 10 min and detected by a Q-Exactive mass spectrometer in full scan with positive/negative switching, and subsequent data dependent acquisition (DDA) mode. Identification criteria were the presence of accurate precursor ions, isotopic patterns, five most intense fragment ions, and comparison with full HR-MS/MS library spectra. The current library contains over 1900 parent drugs and 1200 metabolites. The method was validated for typical drug representatives and metabolites concerning recovery, matrix effects, process efficiency, and limits showed acceptable results. The applicability was tested first for cardiovascular drugs, which should be screened for in poisoning cases and for medication adherence of hypertension patients. The novel LC–HR-MS/MS method allowed fast, simple, and robust urine screening, particularly for cardiovascular drugs showing the usefulness of Orbitrap technology for drug testing. - Highlights: • First study on the application of Orbitrap technology for comprehensive drug screening in clinical and forensic toxicology. • Simple workup, sufficient separation, and powerful screening and identification using modern high resolution MS. • Validation of the assay according to guidelines for qualitative approaches. • Elucidation of the power of new data evaluation software in combination with a new reference drug and metabolite library. • Great relevance for science and practice in clinical and forensic

  16. Evaluation and optimization of high-performance liquid chromatography coupled with high-resolution mass spectrometry for phospholipid quantitation.

    Science.gov (United States)

    Fu, Mingkun; Xu, Wei; Lu, Qing; Pan, Guoyu; Varga, Csanad

    2014-04-15

    High-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC/HRMS) provides an attractive alternative to the traditional triple quadrupole mass spectrometry selected reaction monitoring (SRM) methodology in the field of quantitation. An LTQ Orbitrap Velos mass spectrometer coupled with a Shimadzu UHPLC system was used. A mass extraction window (MEW) was defined to mathematically correlate with mass resolving power (MRP). Five MRP measurement conditions at 7500, 15,000, 30,000, 60,000, and 100,000, and five MEW widths at 10%, 20%, 50%, and 100% of ±1000000/MRP, and were utilized as the experimental conditions. Comparison of profile and centroid algorithms was evaluated as well. Selection of pH 8.5 buffer, C4 column, 20% IPA, and 10 ppm H3 PO4 , minimized hydrophobic and silanol interactions to enhance separation. Narrowing the MEW minimized background noise, while over-narrowing the MEW gave signal loss due to mass accuracy deviation. The mass accuracy deviation was larger for lower MRP measurements especially with centriod data, and hence a profile algorithm was recommended. The post-ionization signal suppression was observed with low MRP and was further confirmed with the analysis of multi-level linearity. It was found that the HPLC/HRMS method with conditions of 20% ±1000000/MRP as MEW, 30,000 or 60,000 MRP, and profile algorithm, provide optimum results for quantitation of seven model phospholipids. Copyright © 2014 John Wiley & Sons, Ltd.

  17. High-resolution soft X-ray spectroscopy of 2.3 keV/u N sup 7 sup + ions through a microcapillary target

    CERN Document Server

    Iwai, Y; Kanai, Y; Oyama, H; Ando, K; Masuda, H; Nishio, K; Nakao, M; Tamamura, T; Komaki, K; Yamazaki, Y

    2002-01-01

    X-rays emitted from 2.3 keV/u sup 1 sup 5 N sup 7 sup + ions transmitted through a highly ordered Ni microcapillary were measured with a high-resolution soft X-ray spectrometer. The highly ordered microcapillary has recently become available employing a nano-lithographic technique. A transmission ratio and charge state distribution of ions through the microcapillary target were found to be consistent with theoretical predictions. A preliminary analysis showed that a series of X-rays from np-1s transitions with n as high as 8 were identified, which is consistent with the classical over barrier model.

  18. Ion detection in mass spectrometry

    International Nuclear Information System (INIS)

    Bolbach, Gerard

    2016-03-01

    This course aims at providing some elements for a better understanding of ion detectors used in mass spectrometers, of their operations, and of their limitations. A first part addresses the functions and properties of an ideal detector, how to detect ions in gas phase, and particle detectors and ion detectors used in mass spectrometry. The second part proposes an overview of currently used detectors with respect to their operation principle: detection from the ion charge (Faraday cylinder), detection by inductive effects (FTICR, Fourier Transform Ion Cyclotron Resonance), and detection by secondary electron emission. The third part discusses the specificities of secondary electron emission. The fourth one addresses operating modes and parameters related to detectors. The sixth part proposes a prospective view on future detectors by addressing the following issues: cryo-detector, inductive effect and charge detectors, ion detection and nano materials

  19. Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Directory of Open Access Journals (Sweden)

    R. M. Dickhut

    2008-09-01

    Full Text Available Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223 component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia and 78% (New York of these peaks were assigned molecular formulas using only carbon (C, hydrogen (H, oxygen (O, nitrogen (N, and sulfur (S as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC.

  20. Site-specific glycosylation of donkey milk lactoferrin investigated by high-resolution mass spectrometry

    DEFF Research Database (Denmark)

    Gallina, Serafina; Saletti, Rosaria; Cunsolo, Vincenzo

    2016-01-01

    A comprehensive monosaccharide composition of the N-glycans of donkey milk lactoferrin, isolated by ion exchange chromatography from an individual milk sample, was obtained by means of chymotryptic digestion, TiO2 and HILIC enrichment, reversed-phase high-performance liquid chromatography......, electrospray mass spectrometry, and high collision dissociation fragmentation. The results obtained allowed identifying 26 different glycan structures, including high mannose, complex and hybrid N-glycans, linked to the protein backbone via an amide bond to asparagine residues located at the positions 137, 281...... and 476. Altogether, the N-glycan structures determined revealed that most of the N-glycans identified in donkey milk lactoferrin are neutral complex/hybrid. Indeed, 10 neutral non-fucosylated complex/hybrid N-glycans and 4 neutral fucosylated complex/hybrid N-glycans were found. In addition, two high...

  1. Static secondary ion mass spectrometry for organic and inorganic molecular analysis in solids

    International Nuclear Information System (INIS)

    Ham, Rita van; Vaeck, Luc van; Adriaens, Annemie; Adams, Freddy

    2003-01-01

    The use of mass spectra in secondary ion mass spectrometry (S-SIMS) to characterise the molecular composition of inorganic and organic analytes at the surface of solid samples is investigated. Methodological aspects such as mass resolution, mass accuracy, precision and accuracy of isotope abundance measurements, influence of electron flooding and sample morphology are addressed to assess the possibilities and limitations that the methodology can offer to support the structural assignment of the detected ions. The in-sample and between-sample reproducibility of relative peak intensities under optimised conditions is within 10%, but experimental conditions and local hydration, oxidation or contamination can drastically affect the mass spectra. As a result, the use of fingerprinting for identification becomes compromised. Therefore, the preferred way of interpretation becomes the deductive structural approach, based on the use of the empirical desorption-ionisation model. This approach is shown to allow the molecular composition of inorganic and organic components at the surface of solids to be characterised. Examples of inorganic speciation and identification of organic additives with unknown composition in inorganic salt mixtures are given. The methodology is discussed in terms of foreseen developments with respect to the use of polyatomic primary ions

  2. Fingerprints of flower absolutes using supercritical fluid chromatography hyphenated with high resolution mass spectrometry.

    Science.gov (United States)

    Santerre, Cyrille; Vallet, Nadine; Touboul, David

    2018-06-02

    Supercritical fluid chromatography hyphenated with high resolution mass spectrometry (SFC-HRMS) was developed for fingerprint analysis of different flower absolutes commonly used in cosmetics field, especially in perfumes. Supercritical fluid chromatography-atmospheric pressure photoionization-high resolution mass spectrometry (SFC-APPI-HRMS) technique was employed to identify the components of the fingerprint. The samples were separated with a porous graphitic carbon (PGC) Hypercarb™ column (100 mm × 2.1 mm, 3 μm) by gradient elution using supercritical CO 2 and ethanol (0.0-20.0 min (2-30% B), 20.0-25.0 min (30% B), 25.0-26.0 min (30-2% B) and 26.0-30.0 min (2% B)) as mobile phase at a flow rate of 1.5 mL/min. In order to compare the SFC fingerprints between five different flower absolutes: Jasminum grandiflorum absolutes, Jasminum sambac absolutes, Narcissus jonquilla absolutes, Narcissus poeticus absolutes, Lavandula angustifolia absolutes from different suppliers and batches, the chemometric procedure including principal component analysis (PCA) was applied to classify the samples according to their genus and their species. Consistent results were obtained to show that samples could be successfully discriminated. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Environmental Chemistry Compound Identification Using High Resolution Mass Spectrometry Data Integrated to the EPA Chemistry Dashboard (EAS)

    Science.gov (United States)

    There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chromatograph...

  4. The study towards high intensity high charge state laser ion sources.

    Science.gov (United States)

    Zhao, H Y; Jin, Q Y; Sha, S; Zhang, J J; Li, Z M; Liu, W; Sun, L T; Zhang, X Z; Zhao, H W

    2014-02-01

    As one of the candidate ion sources for a planned project, the High Intensity heavy-ion Accelerator Facility, a laser ion source has been being intensively studied at the Institute of Modern Physics in the past two years. The charge state distributions of ions produced by irradiating a pulsed 3 J/8 ns Nd:YAG laser on solid targets of a wide range of elements (C, Al, Ti, Ni, Ag, Ta, and Pb) were measured with an electrostatic ion analyzer spectrometer, which indicates that highly charged ions could be generated from low-to-medium mass elements with the present laser system, while the charge state distributions for high mass elements were relatively low. The shot-to-shot stability of ion pulses was monitored with a Faraday cup for carbon target. The fluctuations within ±2.5% for the peak current and total charge and ±6% for pulse duration were demonstrated with the present setup of the laser ion source, the suppression of which is still possible.

  5. Symposium on fast atom and ion induced mass spectrometry of nonvolatile organic solids

    International Nuclear Information System (INIS)

    McNeal, C.J.

    1982-01-01

    The mechanisms of molecular and fragment ion production and the various parameters affecting ion yields were discussed by 6 invited speakers from Europe, Canada, and the US at this symposium. The work reported was almost equally divided between that using low-energy (keV) primary ion (or atom) beams, e.g. fast atom bombardment mass spectrometry (FABMS) and secondary ion mass spectrometry (SIMS) and that using high energy (MeV) particles, e.g. heavy ion induced mass spectrometry (HIIDMS) and 252 Cf-plasma desorption mass spectrometry ( 252 Cf-PDMS). Both theoretical foundations and observed experimental results for both techniques are included

  6. Mass resolution for lepton pairs at Isabelle

    International Nuclear Information System (INIS)

    Baltay, C.; Paige, F.E.

    1978-01-01

    Experiments measuring e + e - and μ + μ-pairs will be the principal way of searching at ISABELLE for the Z 0 and for vector mesons made from new heavy quark-antiquark (Q anti Q ) pairs. Although the best possible mass resolution is clearly of benefit in such experiments, excessive resolution would lead to an unnecessarily large detector. It is believed that a mass resolution of a few percent is appropriate in searching both for the Z 0 and for new Q anti Q states. However, there are some interesting experiments which would require much better mass resolution, of order 1/4% FWHM. 9 references

  7. Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Mann, Benjamin F; Chen, Hongmei; Herndon, Elizabeth M; Chu, Rosalie K; Tolic, Nikola; Portier, Evan F; Roy Chowdhury, Taniya; Robinson, Errol W; Callister, Stephen J; Wullschleger, Stan D; Graham, David E; Liang, Liyuan; Gu, Baohua

    2015-01-01

    Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between -1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

  8. Comparison of secondary ion emission induced in silicon oxide by MeV and KeV ion bombardment

    International Nuclear Information System (INIS)

    Allali, H.; Nsouli, B.; Thomas, J.P.; Szymczak, W.; Wittmaack, K.

    1993-09-01

    The surface and near-surface composition of SiO 2 layers, has been investigated by negative secondary ion emission mass spectrometry (SIMS) using MeV and KeV ion bombardment in combination with time-of-flight (TOF) mass analysis. The spectra recorded in the mass range 0-100 u are dominated by surface impurities, notably hydrocarbons and silicon polyanions incorporating H and OH entities. The characteristic (fragmentation) patterns are quite different for light and high-velocity ion impact. In high-velocity TOF-SIMS analysis of P-doped layers, prepared by chemical vapour deposition (CVD), the mass lines at 63 and 79 u are very prominent and appear to correlate with the phosphorus concentration (PO 2 and PO 3 , respectively). It is shown, however, that for unambiguous P analysis one has to use dynamic SIMS or high mass resolution. (author) 11 refs., 5 figs

  9. Assessment of meat authenticity using bioinformatics, targeted peptide biomarkers and high-resolution mass spectrometry.

    Science.gov (United States)

    Ruiz Orduna, Alberto; Husby, Erik; Yang, Charles T; Ghosh, Dipankar; Beaudry, Francis

    2015-01-01

    In recent years a significant increase of food fraud has been observed, ranging from false label claims to the use of additives and fillers to increase profitability. Recently in 2013 horse and pig DNAs were detected in beef products sold from several retailers. Mass spectrometry (MS) has become the workhorse in protein research, and the detection of marker proteins could serve for both animal species and tissue authentication. Meat species authenticity is performed in this paper using a well-defined proteogenomic annotation, carefully chosen surrogate tryptic peptides and analysis using a hybrid quadrupole-Orbitrap MS. Selected mammalian meat samples were homogenised and proteins were extracted and digested with trypsin. The samples were analysed using a high-resolution MS. Chromatography was achieved using a 30-min linear gradient along with a BioBasic C8 100 × 1 mm column at a flow rate of 75 µl min(-1). The MS was operated in full-scan high resolution and accurate mass. MS/MS spectra were collected for selected proteotypic peptides. Muscular proteins were methodically analysed in silico in order to generate tryptic peptide mass lists and theoretical MS/MS spectra. Following a comprehensive bottom-up proteomic analysis, we detected and identified a proteotypic myoglobin tryptic peptide (120-134) for each species with observed m/z below 1.3 ppm compared with theoretical values. Moreover, proteotypic peptides from myosin-1, myosin-2 and β-haemoglobin were also identified. This targeted method allowed comprehensive meat speciation down to 1% (w/w) of undesired product.

  10. Analysis of volatile thiols in alcoholic beverages by simultaneous derivatization/extraction and liquid chromatography-high resolution mass spectrometry.

    Science.gov (United States)

    Vichi, Stefania; Cortés-Francisco, Nuria; Caixach, Josep

    2015-05-15

    A simultaneous derivatization/extraction method followed by liquid chromatography-electrospray-high resolution mass spectrometry for the determination of volatile thiols in hydroalcoholic matrixes was optimized and used to identify and quantify volatile thiols in wine and beer samples. The method was evaluated in terms of sensitivity, precision, accuracy and selectivity. The experimental LOQs of eleven thiols tested ranged between 0.01 ng/L and 10 ng/L. Intra-day relative standard deviation (RSD) was in general lower than 10% and inter-day RSD ranged between 10% and 30%. Recovery in the model and real matrixes ranged from 45% to 129%. The method was then applied for the analysis of four white wines and six beers. Five out of the eleven reference thiols were identified and quantified in the samples analyzed. The non-target approach, carried out by monitoring the diagnostic ion at m/z 275.9922 [C13H10ONSe](+) in the fragmentation spectrum, allowed detecting, in the same samples, fourteen non-target thiols. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Targeted metabolite profile of food bioactive compounds by Orbitrap high resolution mass spectrometry: The 'FancyTiles' approach

    NARCIS (Netherlands)

    Troise, A.D.; Ferracane, R.; Palermo, M.; Fogliano, V.

    2014-01-01

    In this paper a new targeted metabolic profile approach using Orbitrap high resolution mass spectrometry was described. For each foodmatrix various classes of bioactive compounds and some specificmetabolites of interest were selected on the basis of the existing knowledge creating an easy-to-read

  12. Project for a high resolution magnetic spectrometer for heavy ions

    International Nuclear Information System (INIS)

    Birien, P.; Valero, S.

    1981-05-01

    The energy loss spectrometer presented in this report has an energy resolution of 2x10 -4 with the full solid angle of 5 msr. The maximum magnetic rigidity of the particles analysed is 2.88 Tesla-meters on the optical axis and the total acceptance in energy is 14%. Experiments with reaction angles near 0 0 are possible. Kinematic compensation is adapted to heavy ion physics. In this report, we have paid special attention to the simplicity of the construction and of the use of this spectrometer by experimentalists. This report is addressed both to non-specialists and to future users as well [fr

  13. Radiocarbon detection by ion charge exchange mass spectrometry

    International Nuclear Information System (INIS)

    Hotchkis, Michael; Wei, Tao

    2007-01-01

    A method for detection of radiocarbon at low levels is described and the results of tests are presented. We refer to this method as ion charge exchange mass spectrometry (ICE-MS). The ICE-MS instrument is a two stage mass spectrometer. In the first stage, molecular interferences which would otherwise affect radiocarbon detection at mass 14 are eliminated by producing high charge state ions directly in the ion source (charge state ≥2). 14 N interference is eliminated in the second stage by converting the beam to negative ions in a charge exchange cell. The beam is mass-analysed at each stage. We have built a test apparatus consisting of an electron cyclotron resonance ion source and a pair of analysing magnets with a charge exchange cell in between, followed by an electrostatic analyser to improve the signal to background ratio. With this apparatus we have measured charge exchange probabilities for (C n+ → C - ) from 4.5 to 40.5 keV (n = 1-3). We have studied the sources of background including assessment of limits for nitrogen interference by searching for negative ions from charge exchange of 14 N ions. Our system has been used to detect 14 C in enriched samples of CO 2 gas with 14 C/ 12 C isotopic ratio down to the 10 -9 level. Combined with a measured sample consumption rate of 4 ng/s, this corresponds to a capability to detect transient signals containing only a few μBq of 14 C activity, such as may be obtained from chromatographic separation. The method will require further development to match the sensitivity of AMS with a gas ion source; however, even in its present state its sensitivity is well suited to tracer studies in biomedical research and drug development

  14. A comprehensive high-resolution mass spectrometry approach for characterization of metabolites by combination of ambient ionization, chromatography and imaging methods.

    Science.gov (United States)

    Berisha, Arton; Dold, Sebastian; Guenther, Sabine; Desbenoit, Nicolas; Takats, Zoltan; Spengler, Bernhard; Römpp, Andreas

    2014-08-30

    An ideal method for bioanalytical applications would deliver spatially resolved quantitative information in real time and without sample preparation. In reality these requirements can typically not be met by a single analytical technique. Therefore, we combine different mass spectrometry approaches: chromatographic separation, ambient ionization and imaging techniques, in order to obtain comprehensive information about metabolites in complex biological samples. Samples were analyzed by laser desorption followed by electrospray ionization (LD-ESI) as an ambient ionization technique, by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging for spatial distribution analysis and by high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS) for quantitation and validation of compound identification. All MS data were acquired with high mass resolution and accurate mass (using orbital trapping and ion cyclotron resonance mass spectrometers). Grape berries were analyzed and evaluated in detail, whereas wheat seeds and mouse brain tissue were analyzed in proof-of-concept experiments. In situ measurements by LD-ESI without any sample preparation allowed for fast screening of plant metabolites on the grape surface. MALDI imaging of grape cross sections at 20 µm pixel size revealed the detailed distribution of metabolites which were in accordance with their biological function. HPLC/ESI-MS was used to quantify 13 anthocyanin species as well as to separate and identify isomeric compounds. A total of 41 metabolites (amino acids, carbohydrates, anthocyanins) were identified with all three approaches. Mass accuracy for all MS measurements was better than 2 ppm (root mean square error). The combined approach provides fast screening capabilities, spatial distribution information and the possibility to quantify metabolites. Accurate mass measurements proved to be critical in order to reliably combine data from different MS

  15. Surface charge compensation for a highly charged ion emission microscope

    International Nuclear Information System (INIS)

    McDonald, J.W.; Hamza, A.V.; Newman, M.W.; Holder, J.P.; Schneider, D.H.G.; Schenkel, T.

    2003-01-01

    A surface charge compensation electron flood gun has been added to the Lawrence Livermore National Laboratory (LLNL) highly charged ion (HCI) emission microscope. HCI surface interaction results in a significant charge residue being left on the surface of insulators and semiconductors. This residual charge causes undesirable aberrations in the microscope images and a reduction of the Time-Of-Flight (TOF) mass resolution when studying the surfaces of insulators and semiconductors. The benefits and problems associated with HCI microscopy and recent results of the electron flood gun enhanced HCI microscope are discussed

  16. Sub-keV secondary ion mass spectrometry depth profiling: comparison of sample rotation and oxygen flooding

    International Nuclear Information System (INIS)

    Liu, R.; Wee, A.T.S.

    2004-01-01

    Following the increasingly stringent requirements in the characterization of sub-micron IC devices, an understanding of the various factors affecting ultra shallow depth profiling in secondary ion mass spectrometry (SIMS) has become crucial. Achieving high depth resolution (of the order of 1 nm) is critical in the semiconductor industry today, and various methods have been developed to optimize depth resolution. In this paper, we will discuss ultra shallow SIMS depth profiling using B and Ge delta-doped Si samples using low energy 0.5 keV O 2 + primary beams. The relationship between depth resolution of the delta layers and surface topography measured by atomic force microscopy (AFM) is studied. The effect of oxygen flooding and sample rotation, used to suppress surface roughening is also investigated. Oxygen flooding was found to effectively suppress roughening and gives the best depth resolution for B, but sample rotation gives the best resolution for Ge. Possible mechanisms for this are discussed

  17. Radiocarbon positive-ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, Stewart P.H.T.; Shanks, Richard P. [Scottish Universities Environmental Research Centre (SUERC), Scottish Enterprise Technology Park, East Kilbride G75 0QF (United Kingdom); Donzel, Xavier; Gaubert, Gabriel [Pantechnik S.A., 13 Rue de la Résistance, 14400 Bayeux (France)

    2015-10-15

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  18. Radiocarbon positive-ion mass spectrometry

    International Nuclear Information System (INIS)

    Freeman, Stewart P.H.T.; Shanks, Richard P.; Donzel, Xavier; Gaubert, Gabriel

    2015-01-01

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  19. Super TOF secondary ion mass spectroscopy using very highly charged primary ions up to Th70+

    International Nuclear Information System (INIS)

    Briere, M.A.; Schenkel, T.; Schneider, D.

    1995-01-01

    The LLNL Electron Beam Ion Trap (EBIT) has made low emittance beams of slow highly charged ions available for ion-solid interaction studies. Such interactions feature the dominance of electronic over collisional effects, and the shock waves generated by the ionized target atoms can desorb large numbers of large molecular species from the surface. This paper presents the first systematic study of the sputtering process due to the incidence of slow very highly charged ions; Th 70+ ions are extracted from EBIT at 7 keV * q and directed onto thin SiO 2 films on Si. Results suggest secondary ion yields of up to 25 per incident ion for Th 70+ (secondary ion yield is increased over that for singly or moderately charged ions). Correlations of the negative, positive, and negative cluster ion yields show promise for application of highly charged ion induced sputtering for enhanced sensitivity and quantitative (absolute) SIMS analysis of deep submicron scale surface layers and polymeric and biomolecular material analysis

  20. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Science.gov (United States)

    Dickel, T.; Plaß, W. R.; Ayet San Andres, S.; Ebert, J.; Geissel, H.; Haettner, E.; Hornung, C.; Miskun, I.; Pietri, S.; Purushothaman, S.; Reiter, M. P.; Rink, A.-K.; Scheidenberger, C.; Weick, H.; Dendooven, P.; Diwisch, M.; Greiner, F.; Heiße, F.; Knöbel, R.; Lippert, W.; Moore, I. D.; Pohjalainen, I.; Prochazka, A.; Ranjan, M.; Takechi, M.; Winfield, J. S.; Xu, X.

    2015-05-01

    211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  1. High-Resolution Energy and Intensity Measurements with CVD Diamond at REX-ISOLDE

    CERN Document Server

    Griesmayer, E; Dobos, D; Wenander, F; Bergoz, J; Bayle, H; Frais-Kölbl, H; Leinweber, J; Aumeyr, T; CERN. Geneva. BE Department

    2009-01-01

    A novel beam instrumentation device for the HIE-REX (High In-tensity and Energy REX) upgrade has been developed and tested at the On-Line Isotope Mass Separator ISOLDE, located at the European Laboratory for Particle Physics (CERN). This device is based on CVD diamond detector technology and is used for measuring the beam intensity, particle counting and measuring the energy spectrum of the beam. An energy resolution of 0.6% was measured at a carbon ion energy of 22.8 MeV. This corresponds to an energy spread of ± 140 keV.

  2. Automated work-flow for processing high-resolution direct infusion electrospray ionization mass spectral fingerprints

    DEFF Research Database (Denmark)

    Hansen, Michael Adsetts Edberg; Smedsgaard, Jørn

    2007-01-01

    an automated data processing pipeline to compare large numbers of fingerprint spectra from direct infusion experiments analyzed by high resolution MS. We describe some of the intriguing problems that have to be addressed. starting with the conversion and pre-processing of the raw data to the final data......The use of mass spectrometry (MS) is pivotal in analyses of the metabolome and presents a major challenge for subsequent data processing. While the last few years have given new high performance instruments, there has not been a comparable development in data processing. In this paper we discuss...

  3. Contribution to high-temperature chromatography and high-temperature-gas-chromatography-mass spectrometry of lipids

    International Nuclear Information System (INIS)

    Aichholz, R.

    1998-04-01

    This thesis describes the use of high temperature gas chromatography for the investigation of unusual triacylglycerols, cyanolipids and bees waxes. The used glass capillary columns were pretreated and coated with tailor made synthesized high temperature stable polysiloxane phases. The selective separation properties of the individual columns were tested with a synthetic lipid mixture. Suitable derivatization procedures for the gaschromatographic analyses of neutral lipids, containing multiple bonds as well as hydroxy-, epoxy-, and carboxyl groups, were developed and optimized. Therefore conjugated olefinic-, conjugated olefinic-acetylenic-, hydroxy-, epoxy-, and conjugated olefinic keto triacylglycerols in miscellaneous plant seed oils as well as hydroxy monoesters, diesters and hydroxy diesters in bees waxes could be analysed directly with high temperature gas chromatography for the first time. In order to elucidate the structures of separated lipid compounds, high temperature gas chromatography was coupled to mass spectrometry and tandem mass spectrometry, respectively. Comparable analytical systems are hitherto not commercial available. Therefore instrumental prerequisites for a comprehensive and detailed analysis of seed oils and bees waxes were established. In GC/MS commonly two ionization methods are used, electron impact ionization and chemical ionization. For the analysis of lipids the first is of limited use only. Due to intensive fragmentation only weak molecular ions are observed. In contrast, the chemical ionization yields in better results. Dominant quasi molecular ions enable an unambiguous determination of the molecular weight. Moreover, characteristic fragment ions provide important indications of certain structural features of the examined compounds. Nevertheless, in some cases the chromatographic resolution was insufficient in order to separate all compounds present in natural lipid mixtures. Owing to the selected detection with mass spectrometry

  4. Screening of plant toxins in food,feed and botanicals using full-scan high-resolution (Orbitrap) mass spectrometry

    NARCIS (Netherlands)

    Mol, J.G.J.; Dam, van R.C.J.; Zomer, P.; Mulder, P.P.J.

    2011-01-01

    A generic method based on LC with full-scan high-resolution (Orbitrap) mass spectrometry (MS) was systematically investigated for the simultaneous detection of a wide range of plant toxins in a variety of food and feed matrices. For a selection of 150 substances, representing various chemical

  5. High-resolution DEMs for High-mountain Asia: A systematic, region-wide assessment of geodetic glacier mass balance and dynamics

    Science.gov (United States)

    Shean, D. E.; Arendt, A. A.; Osmanoglu, B.; Montesano, P.

    2017-12-01

    High Mountain Asia (HMA) constitutes the largest glacierized region outside of the Earth's polar regions. Although available observations are limited, long-term records indicate sustained regional glacier mass loss since 1850, with increased loss in recent decades. Recent satellite data (e.g., GRACE, ICESat-1) show spatially variable glacier mass balance, with significant mass loss in the Himalaya and Hindu Kush and slight mass gain in the Karakoram. We generated 4000 high-resolution digital elevation models (DEMs) from sub-meter commercial stereo imagery (DigitalGlobe WorldView/GeoEye) acquired over glaciers in High-mountain Asia from 2002-present (mostly 2013-present). We produced a regional 8-m DEM mosaic for 2015 and estimated 15-year geodetic mass balance for 40000 glaciers larger than 0.1 km2. We are combining with other regional DEM sources to systematically document the spatiotemporal evolution of glacier mass balance for the entire HMA region. We also generated monthly to interannual DEM and velocity time series for high-priority sites distributed across the region, with >15-20 DEMs available for some locations from 2010-present. These records document glacier dynamics, seasonal snow accumulation/redistribution, and processes that affect glacier mass balance (e.g., ice-cliff retreat, debris cover evolution). These efforts will provide basin-scale assessments of snow/ice melt runoff contributions for model cal/val and downstream water resources applications. We will continue processing all archived and newly available commercial stereo imagery for HMA, and will release all DEMs through the HiMAT DAAC.

  6. A Simple Approach for Obtaining High Resolution, High Sensitivity ¹H NMR Metabolite Spectra of Biofluids with Limited Mass Supply

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Jian Zhi; Rommereim, Donald N.; Wind, Robert A.; Minard, Kevin R.; Sears, Jesse A.

    2006-11-01

    A simple approach is reported that yields high resolution, high sensitivity ¹H NMR spectra of biofluids with limited mass supply. This is achieved by spinning a capillary sample tube containing a biofluid at the magic angle at a frequency of about 80Hz. A 2D pulse sequence called ¹H PASS is then used to produce a high-resolution ¹H NMR spectrum that is free from magnetic susceptibility induced line broadening. With this new approach a high resolution ¹H NMR spectrum of biofluids with a volume less than 1.0 µl can be easily achieved at a magnetic field strength as low as 7.05T. Furthermore, the methodology facilitates easy sample handling, i.e., the samples can be directly collected into inexpensive and disposable capillary tubes at the site of collection and subsequently used for NMR measurements. In addition, slow magic angle spinning improves magnetic field shimming and is especially suitable for high throughput investigations. In this paper first results are shown obtained in a magnetic field of 7.05T on urine samples collected from mice using a modified commercial NMR probe.

  7. Resonance ionization mass spectrometry of ion beam sputtered neutrals for element- and isotope-selective analysis of plutonium in micro-particles

    Energy Technology Data Exchange (ETDEWEB)

    Erdmann, N. [Institute for Transuranium Elements, European Commission Joint Research Centre, Karlsruhe (Germany); Kratz, J.V.; Trautmann, N. [Johannes Gutenberg-University Mainz, Institute of Nuclear Chemistry, Mainz (Germany); Passler, G. [Johannes Gutenberg-University Mainz, Institute of Physics, Mainz (Germany)

    2009-11-15

    Micro-particles containing actinides are of interest for risk assessments of contaminated areas, nuclear forensic analyses, and IAEA as well as Euratom safeguards programs. For their analysis, secondary ion mass spectrometry (SIMS) has been established as the state-of-the-art standard technique. In the case of actinide mixtures within the particles, however, SIMS suffers from isobaric interferences (e.g., {sup 238}U/{sup 238}Pu, {sup 241}Am/{sup 241}Pu). This can be eliminated by applying resonance ionization mass spectrometry which is based on stepwise resonant excitation and ionization of atoms with laser light, followed by mass spectrometric detection of the produced ions, combining high elemental selectivity with the analysis of isotopic compositions. This paper describes the instrumental modifications for coupling a commercial time-of-flight (TOF)-SIMS apparatus with three-step resonant post-ionization of the sputtered neutrals using a high-repetition-rate (kHz) Nd:YAG laser pumped tunable titanium:sapphire laser system. Spatially resolved ion images obtained from actinide-containing particles in TOF-SIMS mode demonstrate the capability for isotopic and spatial resolution. Results from three-step resonant post-ionization of bulk Gd and Pu samples successfully demonstrate the high elemental selectivity of this process. (orig.)

  8. Study of SiO2 surface sputtering by a 250-550 keV He+ ion beam during high-resolution Rutherford backscattering measurements

    International Nuclear Information System (INIS)

    Kusanagi, Susumu; Kobayashi, Hajime

    2006-01-01

    Decreases in oxygen signal intensities in spectra of high-resolution Rutherford backscattering spectrometry (HRBS) were observed during measurements on a 5-nm thick SiO 2 layer on a Si substrate when irradiated by 250-550 keV He + ions. Shifts in an implanted arsenic profile in a 5-nm thick SiO 2 /Si substrate were also observed as a result of He + ion irradiation. These results lead to the conclusion that the SiO 2 surface was sputtered by He + ions in this energy range

  9. A novel ion imager for secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Matsumoto, Kazuya; Miyata, Kenji; Nakamura, Tsutomu

    1993-01-01

    This paper describes a new area detector for secondary ion mass spectrometry (SIMS) ion microscope, and its performance. The operational principle is based on detecting the change in potential of a floating photodiode caused by the ion-induced secondary-electron emission and the incoming ion itself. The experiments demonstrated that 10 1 -10 5 aluminum ions per pixel can be detected with good linear response. Moreover, relative ion sensitivities from hydrogen to lead were constant within a factor of 2. The performance of this area detector provides the potential for detection of kiloelectronvolt ion images with current ion microscopy

  10. High resolution X-ray diffraction studies on unirradiated

    Indian Academy of Sciences (India)

    High-resolution X-ray diffraction technique, employing a three-crystal monochromator–collimator combination is used to study the irradiation induced defects in flux grown Sr-hexaferrite crystals irradiated with 50 MeV Li3+ ion beams at room temperature with a fluence value of 1 × 1014 ions/cm2. The diffraction curves of the ...

  11. Ion trajectories quadrupole mass filters

    International Nuclear Information System (INIS)

    Ursu, D.; Lupsa, N.; Muntean, F.

    1994-01-01

    The present paper aims at bringing some contributions to the understanding of ion motion in quadrupole mass filters. The theoretical treatment of quadrupole mass filter is intended to be a concise derivation of the important physical relationships using Mathieu functions. A simple iterative method of numerical computation has been used to simulate ion trajectories in an ideal quadrupole field. Finally, some examples of calculation are presented with the aid of computer graphics. (Author) 14 Figs., 1 Tab., 20 Refs

  12. Simultaneous ion detection in a mass spectrometer with variable mass dispersion

    International Nuclear Information System (INIS)

    Tuithof, H.H.

    1977-01-01

    This thesis mainly describes the ion-optics of a magnetic mass spectrometer system, especially applied to the projection of a significant part of the mass spectrum onto a flat ion-detector. The complete detector consists of a channeltron electron multiplier array with phosphor screen and a Vidicon-multichannel analyzer combination for simultaneous read-out. In order to optimise the spectral range projected onto the channelplate, by varying the mass dispersion and to rotate the oblique angle of the mass focal plane with respect to the detector surface, the sector magnet has been combined with electrostatic and magnetic quadrupole lenses. This detector will find wide application in the analysis of minute sample quantities, in the recording of extremely short ion events (large molecules) and at collision activation mass-spectrometry studies

  13. Combining a Deconvolution and a Universal Library Search Algorithm for the Nontarget Analysis of Data-Independent Acquisition Mode Liquid Chromatography-High-Resolution Mass Spectrometry Results.

    Science.gov (United States)

    Samanipour, Saer; Reid, Malcolm J; Bæk, Kine; Thomas, Kevin V

    2018-04-17

    Nontarget analysis is considered one of the most comprehensive tools for the identification of unknown compounds in a complex sample analyzed via liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS). Due to the complexity of the data generated via LC-HRMS, the data-dependent acquisition mode, which produces the MS 2 spectra of a limited number of the precursor ions, has been one of the most common approaches used during nontarget screening. However, data-independent acquisition mode produces highly complex spectra that require proper deconvolution and library search algorithms. We have developed a deconvolution algorithm and a universal library search algorithm (ULSA) for the analysis of complex spectra generated via data-independent acquisition. These algorithms were validated and tested using both semisynthetic and real environmental data. A total of 6000 randomly selected spectra from MassBank were introduced across the total ion chromatograms of 15 sludge extracts at three levels of background complexity for the validation of the algorithms via semisynthetic data. The deconvolution algorithm successfully extracted more than 60% of the added ions in the analytical signal for 95% of processed spectra (i.e., 3 complexity levels multiplied by 6000 spectra). The ULSA ranked the correct spectra among the top three for more than 95% of cases. We further tested the algorithms with 5 wastewater effluent extracts for 59 artificial unknown analytes (i.e., their presence or absence was confirmed via target analysis). These algorithms did not produce any cases of false identifications while correctly identifying ∼70% of the total inquiries. The implications, capabilities, and the limitations of both algorithms are further discussed.

  14. Triacylglycerol profiling of microalgae strains for biofuel feedstock by liquid chromatography-high-resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    MacDougall, Karen M.; McNichol, Jesse; McGinn, Patrick J.; O' Leary, Stephen J.B.; Melanson, Jeremy E. [Institute for Marine Biosciences, National Research Council of Canada, Halifax, NS (Canada)

    2011-11-15

    Biofuels from photosynthetic microalgae are quickly gaining interest as a viable carbon-neutral energy source. Typically, characterization of algal feedstock involves breaking down triacylglycerols (TAG) and other intact lipids, followed by derivatization of the fatty acids to fatty acid methyl esters prior to analysis by gas chromatography (GC). However, knowledge of the intact lipid profile could offer significant advantages for discovery stage biofuel research such as the selection of an algal strain or the optimization of growth and extraction conditions. Herein, lipid extracts from microalgae were directly analyzed by ultra-high pressure liquid chromatography-mass spectrometry (UHPLC-MS) using a benchtop Orbitrap mass spectrometer. Phospholipids, glycolipids, and TAGs were analyzed in the same chromatographic run, using a combination of accurate mass and diagnostic fragment ions for identification. Using this approach, greater than 100 unique TAGs were identified over the six algal strains studied and TAG profiles were obtained to assess their potential for biofuel applications. Under the growth conditions employed, Botryococcus braunii and Scenedesmus obliquus yielded the most comprehensive TAG profile with a high abundance of TAGs containing oleic acid. (orig.)

  15. "Dilute-and-inject" multi-target screening assay for highly polar doping agents using hydrophilic interaction liquid chromatography high resolution/high accuracy mass spectrometry for sports drug testing.

    Science.gov (United States)

    Görgens, Christian; Guddat, Sven; Orlovius, Anne-Katrin; Sigmund, Gerd; Thomas, Andreas; Thevis, Mario; Schänzer, Wilhelm

    2015-07-01

    In the field of LC-MS, reversed phase liquid chromatography is the predominant method of choice for the separation of prohibited substances from various classes in sports drug testing. However, highly polar and charged compounds still represent a challenging task in liquid chromatography due to their difficult chromatographic behavior using reversed phase materials. A very promising approach for the separation of hydrophilic compounds is hydrophilic interaction liquid chromatography (HILIC). Despite its great potential and versatile advantages for the separation of highly polar compounds, HILIC is up to now not very common in doping analysis, although most manufacturers offer a variety of HILIC columns in their portfolio. In this study, a novel multi-target approach based on HILIC high resolution/high accuracy mass spectrometry is presented to screen for various polar stimulants, stimulant sulfo-conjugates, glycerol, AICAR, ethyl glucuronide, morphine-3-glucuronide, and myo-inositol trispyrophosphate after direct injection of diluted urine specimens. The usage of an effective online sample cleanup and a zwitterionic HILIC analytical column in combination with a new generation Hybrid Quadrupol-Orbitrap® mass spectrometer enabled the detection of highly polar analytes without any time-consuming hydrolysis or further purification steps, far below the required detection limits. The methodology was fully validated for qualitative and quantitative (AICAR, glycerol) purposes considering the parameters specificity; robustness (rRT  0.99); intra- and inter-day precision at low, medium, and high concentration levels (CV < 20%); limit of detection (stimulants and stimulant sulfo-conjugates < 10 ng/mL; norfenefrine; octopamine < 30 ng/mL; AICAR < 10 ng/mL; glycerol 100 μg/mL; ETG < 100 ng/mL); accuracy (AICAR 103.8-105.5%, glycerol 85.1-98.3% at three concentration levels) and ion suppression/enhancement effects.

  16. Structural analyses of sucrose laurate regioisomers by mass spectrometry techniques

    DEFF Research Database (Denmark)

    Lie, Aleksander; Stensballe, Allan; Pedersen, Lars Haastrup

    2015-01-01

    6- And 6′-O-lauroyl sucrose were isolated and analyzed by matrix-assisted laser desorption/ionisation (MALDI) time-of-flight (TOF) mass spectrometry (MS), Orbitrap high-resolution (HR) MS, and electrospray-ionization (ESI) tandem mass spectrometry (MS/MS). The analyses aimed to explore the physic......6- And 6′-O-lauroyl sucrose were isolated and analyzed by matrix-assisted laser desorption/ionisation (MALDI) time-of-flight (TOF) mass spectrometry (MS), Orbitrap high-resolution (HR) MS, and electrospray-ionization (ESI) tandem mass spectrometry (MS/MS). The analyses aimed to explore.......8, respectively, and Orbitrap HRMS confirmed the mass of [M+Na]+ (m/z 547.2712). ESI-MS/MS on the precursor ion [M+Na]+ resulted in product ion mass spectra showing two high-intensity signals for each sample. 6-O-Lauroyl sucrose produced signals located at m/z 547.27 and m/z 385.21, corresponding to the 6-O...

  17. The Megamaser Cosmology Project. X. High-resolution Maps and Mass Constraints for SMBHs

    Science.gov (United States)

    Zhao, W.; Braatz, J. A.; Condon, J. J.; Lo, K. Y.; Reid, M. J.; Henkel, C.; Pesce, D. W.; Greene, J. E.; Gao, F.; Kuo, C. Y.; Impellizzeri, C. M. V.

    2018-02-01

    We present high-resolution (submas) Very Long Baseline Interferometry maps of nuclear H2O megamasers for seven galaxies. In UGC 6093, the well-aligned systemic masers and high-velocity masers originate in an edge-on, flat disk and we determine the mass of the central supermassive black holes (SMBH) to be M SMBH = 2.58 × 107 M ⊙ (±7%). For J1346+5228, the distribution of masers is consistent with a disk, but the faint high-velocity masers are only marginally detected, and we constrain the mass of the SMBH to be in the range (1.5–2.0) × 107 M ⊙. The origin of the masers in Mrk 1210 is less clear, as the systemic and high-velocity masers are misaligned and show a disorganized velocity structure. We present one possible model in which the masers originate in a tilted, warped disk, but we do not rule out the possibility of other explanations including outflow masers. In NGC 6926, we detect a set of redshifted masers, clustered within a parsec of each other, and a single blueshifted maser about 4.4 pc away, an offset that would be unusually large for a maser disk system. Nevertheless, if it is a disk system, we estimate the enclosed mass to be M SMBH < 4.8 × 107 M ⊙. For NGC 5793, we detect redshifted masers spaced about 1.4 pc from a clustered set of blueshifted features. The orientation of the structure supports a disk scenario as suggested by Hagiwara et al. We estimate the enclosed mass to be M SMBH < 1.3 × 107 M ⊙. For NGC 2824 and J0350‑0127, the masers may be associated with parsec- or subparsec-scale jets or outflows.

  18. Measurement of few-electron uranium ions on a high-energy electron beam ion trap

    International Nuclear Information System (INIS)

    Beiersdorfer, P.

    1994-01-01

    The high-energy electron beam ion trap, dubbed Super-EBIT, was used to produce, trap, and excite uranium ions as highly charged as fully stripped U 92+ . The production of such highly charged ions was indicated by the x-ray emission observed with high-purity Ge detectors. Moreover, high-resolution Bragg crystal spectromters were used to analyze the x-ray emission, including a detailed measurement of both the 2s 1/2 -2p 3/2 electric dipole and 2p 1/2 -2p 3/2 magnetic dipole transitions. Unlike in ion accelerators, where the uranium ions move at relativistic speeds, the ions in this trap are stationary. Thus very precise measurements of the transition energies could be made, and the QED contribution to the transition energies could be measured within less than 1 %. Details of the production of these highly charged ions and their measurement is given

  19. Time-of-flight secondary ion mass spectrometry of polymer surfaces

    International Nuclear Information System (INIS)

    Leeson, A.M.

    1997-09-01

    The effects of polymer variables (molecular weight, polydispersity, and tacticity) and sample preparation parameters (film thickness and casting solvent) on ToF SIMS spectra were studied using a series of polymethyl methacrylate (PMMA) and polybutyl methacrylate (PBMA) standards. The polymers were extensively characterized by a variety of spectroscopic and chromatographic techniques. Films were prepared by solution casting and spin casting methods onto aluminium substrates, which were evaluated by x-ray photoelectron spectroscopy (XPS). These films were characterized by high- and unit-mass resolution ToF SIMS. To determine the level of spectral repeatability standard errors were calculated using three methods of data analysis (absolute intensity (counts), normalised peak intensities (NPIs), and ion intensity ratios). Molecular weight and film thickness had the greatest influence on the SIMS spectra of PMMA, with the differences being most marked at low molecular weight. This was observed in both total negative ion counts and negative ion intensity ratios. An explanation based on the surface concentration of polymer end groups is presented. From these results an extension to the existing mechanisms of ion formation is postulated, which includes end group cleavage. An ion beam damage study of PMMA showed that molecular weight and film thickness affect negative ion spectra. Extended 'surface lifetime' was seen in thin (spun cast) films when compared to thick (solution cast) films. This effect, which was only observed with 'Low' PMMA, was explained in terms of surface chain mobility. The effect of molecular weight was dramatic and an explanation in terms of different origins of diagnostic ions is presented. Molecular weight affected the SIMS spectra of PBMA. However, it was not possible to draw definitive conclusions, because the end groups in three of the samples were not known. (author)

  20. Focusing procedures in time-of-flight mass spectrometry

    International Nuclear Information System (INIS)

    Ioanoviciu, D.

    2002-01-01

    Time-of-flight mass spectrometry is a fast growing field due to its ability to handle very fast processes and due to its theoretically unlimited mass range. The performances of the time-of-flight mass analysers are heavily dependent on the progress in ion optics, a periodically reviewed field. In this presentation the various focusing procedures in time-of-flight mass spectrometry are reviewed. For ions of the same charge and mass flight time differences result from different potentials at the location of formation and from the initial velocity spread. There is no simultaneous space and velocity focusing in time-of-flight mass spectrometry. Space focusing of first and second order can be reached in time-of-flight mass analysers having two homogeneous electric field ion sources followed by a field free space in front of the detector. Single and double stage homogeneous electric field mirrors can focus in time ions of different energies. These different energies result when ions leaving different initial sites and arriving simultaneously to an intermediate space focus. Convenient mass dispersion can be obtained by including a mirror. Initial velocity focusing is obtained by the delayed extraction procedure in drift space and mirror time-of-flight mass analysers. Post source pulse focusing aims at the same purpose. Ion source electrodes of hyperbolic shape, operated by high voltage pulses can bring major improvements of the resolution, especially at high masses. For each focusing procedure the geometric and/or electric conditions are given as well as the aberrations allowing the mass resolution determination. The various focusing procedures are compared and a prediction of their future performances was tempted. (author)

  1. Generation of high brightness ion beam from insulated anode PED

    International Nuclear Information System (INIS)

    Matsukawa, Yoshinobu

    1988-01-01

    Generation and focusing of a high density ion beam with high brightness from a organic center part of anode of a PED was reported previously. Mass, charge and energy distribution of this beam were analyzed. Three kind of anode were tried. Many highly ionized medium mass ions (up to C 4+ , O 6+ ) accelarated to several times of voltage difference between anode and cathode were observed. In the case of all insulator anode the current carried by the medium mass ions is about half of that carried by protons. (author)

  2. High-Resolution, Long-Slit Spectroscopy of VY Canis Majoris: The Evidence for Localized High Mass Loss Events

    Science.gov (United States)

    Humphreys, Roberta M.; Davidson, Kris; Ruch, Gerald; Wallerstein, George

    2005-01-01

    High spatial and spectral resolution spectroscopy of the OH/IR supergiant VY CMa and its circumstellar ejecta reveals evidence for high mass loss events from localized regions on the star occurring over the past 1000 yr. The reflected absorption lines and the extremely strong K I emission lines show a complex pattern of velocities in the ejecta. We show that the large, dusty northwest arc, expanding at ~50 km s-1 with respect to the embedded star, is kinematically distinct from the surrounding nebulosity and was ejected about 400 yr ago. Other large, more filamentary loops were probably expelled as much as 800-1000 yr ago, whereas knots and small arcs close to the star resulted from more recent events 100-200 yr ago. The more diffuse, uniformly distributed gas and dust is surprisingly stationary, with little or no velocity relative to the star. This is not what we would expect for the circumstellar material from an evolved red supergiant with a long history of mass loss. We therefore suggest that the high mass loss rate for VY CMa is a measure of the mass carried out by these specific ejections accompanied by streams or flows of gas through low-density regions in the dust envelope. VY CMa may thus be our most extreme example of stellar activity, but our results also bring into question the evolutionary state of this famous star. In a separate appendix, we discuss the origin of the very strong K I and other rare emission lines in its spectrum.

  3. Next generation offline approaches to trace organic compound speciation: Approaching comprehensive speciation with soft ionization and very high resolution tandem mass spectrometry

    Science.gov (United States)

    Khare, P.; Marcotte, A.; Sheu, R.; Ditto, J.; Gentner, D. R.

    2017-12-01

    Intermediate- and semi-volatile organic compounds (IVOCs and SVOCs) have high secondary organic aerosol (SOA) yields, as well as significant ozone formation potentials. Yet, their emission sources and oxidation pathways remain largely understudied due to limitations in current analytical capabilities. Online mass spectrometers are able to collect real time data but their limited mass resolving power renders molecular level characterization of IVOCs and SVOCs from the unresolved complex mixture unfeasible. With proper sampling techniques and powerful analytical instrumentation, our offline tandem mass spectrometry (i.e. MS×MS) techniques provide molecular-level and structural identification over wide polarity and volatility ranges. We have designed a novel analytical system for offline analysis of gas-phase SOA precursors collected on custom-made multi-bed adsorbent tubes. Samples are desorbed into helium via a gradual temperature ramp and sample flow is split equally for direct-MS×MS analysis and separation via gas chromatography (GC). The effluent from GC separation is split again for analysis via atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-Q×TOF) and traditional electron ionization mass spectrometry (EI-MS). The compounds for direct-MS×MS analysis are delivered via a transfer line maintained at 70ºC directly to APCI-Q×TOF, thus preserving the molecular integrity of thermally-labile, or other highly-reactive, organic compounds. Both our GC-MS×MS and direct-MS×MS analyses report high accuracy parent ion masses as well as information on molecular structure via MS×MS, which together increase the resolution of unidentified complex mixtures. We demonstrate instrument performance and present preliminary results from urban atmospheric samples collected from New York City with a wide range of compounds including highly-functionalized organic compounds previously understudied in outdoor air. Our work offers new

  4. Structural and compositional characterization of X-cut LiNbO3 crystals implanted with high energy oxygen and carbon ions

    International Nuclear Information System (INIS)

    Bentini, G.G.; Bianconi, M.; Cerutti, A.; Chiarini, M.; Pennestri, G.; Sada, C.; Argiolas, N.; Bazzan, M.; Mazzoldi, P.; Guzzi, R.

    2005-01-01

    High energy implantation of medium-light elements such as oxygen and carbon was performed in X-cut LiNbO 3 single crystals in order to prepare high quality optical waveguides. The compositional and damage profiles, obtained by exploiting the secondary ion mass spectrometry and Rutherford back-scattering techniques respectively, were correlated to the structural properties measured by the high resolution X-ray diffraction. This study evidences the development of tensile strain induced by the ion implantation that can contribute to the decrease of the ordinary refractive index variation through the photo-elastic effect

  5. Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry.

    Science.gov (United States)

    Sun, Jianghao; Baker, Andrew; Chen, Pei

    2011-09-30

    An ultra-performance liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry (UPLC/IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine or ajmalicine core structure, plus methylated, oxidized and reduced species, were characterized. Common fragments and mass differences are described. It was shown that the use of IMS could provide another molecular descriptor, i.e. molecular shape by rotationally averaged collision cross-section; this is of great value for identification of constituents when reference materials are usually not available. Using the combination of high resolution (~40000) accurate mass measurement with time-aligned parallel (TAP) fragmentation, MS(E) (where E represents collision energy), ion mobility mass spectrometry (IMS) and UPLC chromatography, a total 55 indole alkaloids were characterized and a few new indole alkaloids are reported for the first time. Published in 2011 by John Wiley & Sons, Ltd.

  6. A very high yield electron impact ion source for analytical mass spectrometry

    International Nuclear Information System (INIS)

    Koontz, S.L.; Bonner Denton, M.

    1981-01-01

    A novel ion source designed for use in mass spectrometric determination of organic compounds is described. The source is designed around a low pressure, large volume, hot cathode Penning discharge. The source operates in the 10 -4 - 10 -7 torr pressure domain and is capable of producing focusable current densities several orders of magnitude greater than those produced by conventional Nier -type sources. Mass spectra of n-butane and octafluoro-2-butene are presented. An improved signal-to-noise ratio is demonstrated with a General Electric Monopole 300 mass spectrometer. (orig.)

  7. The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

    CERN Document Server

    Oganessian, Yu T; Dmitriev, S N; Itkis, M G; Gulbekyan, G G; Khabarov, M V; Bekhterev, V V; Bogomolov, S L; Efremov, A A; Pashenko, S V; Stepantsov, S V; Yeremin, A V; Yavor, M I; Kalimov, A G

    2003-01-01

    A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 sup - sup 3. The set up can work in the wide mass range from A approx 20 to A approx 500, its mass acceptance is as large as +-2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90 deg. electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considere...

  8. Analysis of High Resolution Satellite imagery to acsees Glacier Mass Balance and Lake Hazards in Sikkim Himalayas

    Science.gov (United States)

    Bhushan, S.; Shean, D. E.; Haritashya, U. K.; Arendt, A. A.; Syed, T. H.; Setiawan, L.

    2017-12-01

    Glacial lake outburst floods can impact downstream communities due to the sudden outflux of huge quantities of stored water. In this study, we develop a hazard assessment of the moraine dammed glacial lakes in Sikkim Himalayas by analyzing the morphometry of proglacial features, and the surface velocity and mass balance of glaciers. We generated high-resolution digital elevation models (DEMs) using the open-source NASA Ames Stereo Pipeline (ASP) and use other open-source tools to calculate surface velocity and patterns of glacier downwasting over time. Geodetic glacier mass balance is obtained for three periods using high-resolution WorldView/GeoEye stereo DEMs (8 m posting, 2014-2016), Cartosat-1 stereo DEMs (10 m, 2006-2008) and SRTM (30 m, 2000). Initial results reveal a region-wide mass balance of -0.31±0.13 m w.eq.a-1 for the 2007-2015 period, with some debris covered glaciers showing a very low mass loss rate. Additionally, 12 annual glacier velocity fields spanning from 1991 to 2017.derived from Landsat imagery are used to explore the relationship between glacier dynamics and changes in proglacial lakes. Multi-temporal glacial lake mapping is conducted using Landsat and Cartosat imagery. Avalanche and rockfall modeling are combined with morphometric analysis of the proglacial lake area to assess the likelihood of glacial lake dam failure. The above parameters are integrated into a decision tree approach enabling categorization of moraine-dammed lakes according to their potential for outburst events.

  9. Quantitative Multiclass Pesticide Residue Analysis in Apple, Pear, and Grape by Modified QuEChERS and Liquid Chromatography Coupled to High-Resolution Mass Spectrometry.

    Science.gov (United States)

    Munaretto, Juliana S; Viera, Mariela de S; Martins, Manoel L; Adaime, Martha B; Zanella, Renato

    2016-11-01

    Most of the analytical methods currently applied in food control laboratories are focused on the determination of target compounds using LC coupled to tandem MS, which is an effective technique, but low-resolution MS is limited. Thus, a method for determination of pesticide multiresidues in fruits (pear, apple, and grape) using a modified quick, easy, cheap, effective, rugged, and safe method and LC coupled to quadrupole time-of-flight (Q-TOF) MS was developed and validated. The proposed method showed good linearity (r2 > 0.99) from 1 to 100 μg/L. Recoveries for blank samples spiked at 0.01, 0.04, and 0.10 mg/kg were between 66 and 122%, with RSDs apple, pear, and grape matrixes were 0.01 mg/kg for 112, 120, and 118 compounds, and 0.04 mg/kg for 22, 12, and 17 compounds, and average mass accuracy error was 3.2 ppm. LC with Q-TOF MS detection using protonated molecular ion and/or adducts and mass accuracy provided reliability for the method. The proposed method is effective for pesticide residue determination in apple, pear, and grape samples, proving that high-resolution MS using full scan mode can be a powerful and reliable technique for quantification purposes, being adequate for application in the surveillance of maximum residue limits set by different legislations.

  10. Metabolic profile of Kudiezi injection in rats by UHPLC coupled with Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Zhang, Jingdan; Zhang, Xiaoxue; Zhao, Yangyang; Song, Aihua; Sun, Wei; Yin, Ran

    2018-02-01

    In this study, a reliable and sensitive ultra-high performance liquid chromatography coupled with fourier transform ion cyclotron resonance mass spectrometry method was developed for the systematic study of the metabolic profile of Kudiezi injection in rat plasma, bile, urine, and feces after intravenous administration of a single dose. The chromatographic separation was performed on an Agilent Eclipse Plus C 18 column (4.6 mm × 50 mm, 1.8 μm) and the identification of prototype components and metabolites was achieved on a Bruker Solarix 7.0 T ultra-high resolution spectrometer in negative ion mode. Results indicated that a total of 76 constituents including 29 prototype compounds and 47 metabolites (10 phase I metabolites and 37 phase II metabolites) were tentatively identified. And the metabolic pathways of these prototype compounds including hydroxylation, dehydrogenation, glucuronidation, and sulfate conjugation. In conclusion, the developed method with high resolution and sensitivity was effective for screening and identification of prototypes and metabolites of Kudiezi injection in vivo. Moreover, these results would provide significant information for further pharmacokinetic and pharmacological research of Kudiezi injection in vivo. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Binding energies of cluster ions

    International Nuclear Information System (INIS)

    Parajuli, R.; Matt, S.; Scheier, P.; Echt, O.; Stamatovic, A.; Maerk, T.D.

    2002-01-01

    The binding energy of charged clusters may be measured by analyzing the kinetic energy released in the metastable decay of mass selected parent ions. Using finite heat bath theory to determine the binding energies of argon, neon, krypton, oxygen and nitrogen from their respective average kinetic energy released were carried out. A high-resolution double focussing two-sector mass spectrometer of reversed Nier-Johnson type geometry was used. MIKE ( mass-analysed ion kinetic energy) were measured to investigate decay reactions of mass-selected ions. For the inert gases neon (Ne n + ), argon (Ar n + ) and krypton (Kr n + ), it is found that the binding energies initially decrease with increasing size n and then level off at a value above the enthalpy of vaporization of the condensed phase. Oxygen cluster ions shown a characteristic dependence on cluster size (U-shape) indicating a change in the metastable fragmentation mechanism when going from the dimer to the decamer ion. (nevyjel)

  12. Individual analysis of nonmetallic Inclusions in Steel by using the gallium focused ion beam secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Tomiyasu, Bunbunoshin; Inami, Akihiro; Abe, Masakazu; Nihei, Yoshimasa.

    1995-01-01

    Nonmetallic inclusions frequently exert a lot of unfavorable influences on the quality of steel. The size of nonmetallic inclusions in current steel products is less than a few μm in diameter. It is desirable to make clear the origin and generation process of such small particles of nonmetallic inclusion. In order to measure the shape, size, composition and inner elemental distribution, development of characterization methods for each inclusion particle is required. By employing a gallium focused ion beam (FIB) as a primary ion beam of secondary ion mass spectrometry (SIMS), the particle analysis with high spatial resolution is easily achieved. In this paper, we present the novel individual analysis of nonmetallic inclusions in steel by gallium FIB SIMS. We analyzed in two ways the nonmetallic inclusion particles segregated by electron beam melting. (1) By cross-sectioning of the particle using a gallium FIB, elemental maps of cross-section were obtained. The elements were distributed inhomogeneously on the cross-section. (2) We carried out the compositional analysis for several particles individually. Ten particles were analyzed by the shave-off analysis and the multivariate cluster analysis. Based on the composition of each particle, the inclusions were classified into six types. (author)

  13. Mass spectrum of secondary ions knocked-out from copper surface by argon ion beam

    International Nuclear Information System (INIS)

    Koval', A.G.; Bobkov, V.V.; Klimovskij, Yu.A.; Fogel', Ya.M.

    1976-01-01

    The mass-spectrum of secondary ions was studied within a mass range of 1-400. The ions were knocked-out by the beam of ions Ar + from the copper surface with different content of oxygen and sulphur solved in the volume. The studies were conducted at three temperatures of the target. The atomic and molecular ions of the metal matrix, volumetric impurities of metal and ions of chemical compounds molecules of the metal under study with gas particles adsorbed on its surface and atoms of the metal volumetric admixtures may be observed in the mass spectrum. Detection of secondary ions of the copper multi-atomic complexes and ions of these complexes compounds with the adsorbed molecules is of interest

  14. Mass measurements with the CIME cyclotron at GANIL

    International Nuclear Information System (INIS)

    Hornillos, M B Gomez; Chartier, M; Mittig, W; Blank, B; Chautard, F; Demonchy, C E; Gillibert, A; Jacquot, B; Jurado, B; Lecesne, N; Lepine-Szily, A; Orr, N A; Roussel-Chomaz, P; Savajols, H; Villari, A C C

    2005-01-01

    A new direct technique using the CIME cyclotron as a high-resolution mass spectrometer is being developed in order to measure the masses of exotic nuclei. Tests have been performed to check the feasibility of the method with a mixed beam of stable ions extracted from the SPIRAL ion source and injected into the CIME cyclotron. Preliminary results obtained with this new technique are presented and discussed

  15. Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

    Science.gov (United States)

    Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2013-03-01

    This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

  16. Phonon-assisted field emission in silicon nanomembranes for time-of-flight mass spectrometry of proteins.

    Science.gov (United States)

    Park, Jonghoo; Aksamija, Zlatan; Shin, Hyun-Cheol; Kim, Hyunseok; Blick, Robert H

    2013-06-12

    Time-of-flight (TOF) mass spectrometry has been considered as the method of choice for mass analysis of large intact biomolecules, which are ionized in low charge states by matrix-assisted-laser-desorption/ionization (MALDI). However, it remains predominantly restricted to the mass analysis of biomolecules with a mass below about 50,000 Da. This limitation mainly stems from the fact that the sensitivity of the standard detectors decreases with increasing ion mass. We describe here a new principle for ion detection in TOF mass spectrometry, which is based upon suspended silicon nanomembranes. Impinging ion packets on one side of the suspended silicon nanomembrane generate nonequilibrium phonons, which propagate quasi-diffusively and deliver thermal energy to electrons within the silicon nanomembrane. This enhances electron emission from the nanomembrane surface with an electric field applied to it. The nonequilibrium phonon-assisted field emission in the suspended nanomembrane connected to an effective cooling of the nanomembrane via field emission allows mass analysis of megadalton ions with high mass resolution at room temperature. The high resolution of the detector will give better insight into high mass proteins and their functions.

  17. The EPA iCSS Chemistry Dashboard to Support Compound Identification Using High Resolution Mass Spectrometry Data (ACS Fall meeting)

    Science.gov (United States)

    Abstract: There is a growing need for rapid chemical screening and prioritization to inform regulatory decision-making on thousands of chemicals in the environment. We have previously used high-resolution mass spectrometry to examine household vacuum dust samples using liquid chr...

  18. Application of High-Performance Liquid Chromatography Coupled with Linear Ion Trap Quadrupole Orbitrap Mass Spectrometry for Qualitative and Quantitative Assessment of Shejin-Liyan Granule Supplements

    Directory of Open Access Journals (Sweden)

    Jifeng Gu

    2018-04-01

    Full Text Available A method for high-performance liquid chromatography coupled with linear ion trap quadrupole Orbitrap high-resolution mass spectrometry (HPLC-LTQ-Orbitrap MS was developed and validated for the qualitative and quantitative assessment of Shejin-liyan Granule. According to the fragmentation mechanism and high-resolution MS data, 54 compounds, including fourteen isoflavones, eleven ligands, eight flavonoids, six physalins, six organic acids, four triterpenoid saponins, two xanthones, two alkaloids, and one licorice coumarin, were identified or tentatively characterized. In addition, ten of the representative compounds (matrine, galuteolin, tectoridin, iridin, arctiin, tectorigenin, glycyrrhizic acid, irigenin, arctigenin, and irisflorentin were quantified using the validated HPLC-LTQ-Orbitrap MS method. The method validation showed a good linearity with coefficients of determination (r2 above 0.9914 for all analytes. The accuracy of the intra- and inter-day variation of the investigated compounds was 95.0–105.0%, and the precision values were less than 4.89%. The mean recoveries and reproducibilities of each analyte were 95.1–104.8%, with relative standard deviations below 4.91%. The method successfully quantified the ten compounds in Shejin-liyan Granule, and the results show that the method is accurate, sensitive, and reliable.

  19. Application of High-Performance Liquid Chromatography Coupled with Linear Ion Trap Quadrupole Orbitrap Mass Spectrometry for Qualitative and Quantitative Assessment of Shejin-Liyan Granule Supplements.

    Science.gov (United States)

    Gu, Jifeng; Wu, Weijun; Huang, Mengwei; Long, Fen; Liu, Xinhua; Zhu, Yizhun

    2018-04-11

    A method for high-performance liquid chromatography coupled with linear ion trap quadrupole Orbitrap high-resolution mass spectrometry (HPLC-LTQ-Orbitrap MS) was developed and validated for the qualitative and quantitative assessment of Shejin-liyan Granule. According to the fragmentation mechanism and high-resolution MS data, 54 compounds, including fourteen isoflavones, eleven ligands, eight flavonoids, six physalins, six organic acids, four triterpenoid saponins, two xanthones, two alkaloids, and one licorice coumarin, were identified or tentatively characterized. In addition, ten of the representative compounds (matrine, galuteolin, tectoridin, iridin, arctiin, tectorigenin, glycyrrhizic acid, irigenin, arctigenin, and irisflorentin) were quantified using the validated HPLC-LTQ-Orbitrap MS method. The method validation showed a good linearity with coefficients of determination (r²) above 0.9914 for all analytes. The accuracy of the intra- and inter-day variation of the investigated compounds was 95.0-105.0%, and the precision values were less than 4.89%. The mean recoveries and reproducibilities of each analyte were 95.1-104.8%, with relative standard deviations below 4.91%. The method successfully quantified the ten compounds in Shejin-liyan Granule, and the results show that the method is accurate, sensitive, and reliable.

  20. Improved analytical sensitivity for uranium and plutonium in environmental samples: Cavity ion source thermal ionization mass spectrometry

    International Nuclear Information System (INIS)

    Ingeneri, Kristofer; Riciputi, L.

    2001-01-01

    Following successful field trials, environmental sampling has played a central role as a routine part of safeguards inspections since early 1996 to verify declared and to detect undeclared activity. The environmental sampling program has brought a new series of analytical challenges, and driven a need for advances in verification technology. Environmental swipe samples are often extremely low in concentration of analyte (ng level or lower), yet the need to analyze these samples accurately and precisely is vital, particularly for the detection of undeclared nuclear activities. Thermal ionization mass spectrometry (TIMS) is the standard method of determining isotope ratios of uranium and plutonium in the environmental sampling program. TIMS analysis typically employs 1-3 filaments to vaporize and ionize the sample, and the ions are mass separated and analyzed using magnetic sector instruments due to their high mass resolution and high ion transmission. However, the ionization efficiency (the ratio of material present to material actually detected) of uranium using a standard TIMS instrument is low (0.2%), even under the best conditions. Increasing ionization efficiency by even a small amount would have a dramatic impact for safeguards applications, allowing both improvements in analytical precision and a significant decrease in the amount of uranium and plutonium required for analysis, increasing the sensitivity of environmental sampling

  1. reSpect: Software for Identification of High and Low Abundance Ion Species in Chimeric Tandem Mass Spectra

    Science.gov (United States)

    Shteynberg, David; Mendoza, Luis; Hoopmann, Michael R.; Sun, Zhi; Schmidt, Frank; Deutsch, Eric W.; Moritz, Robert L.

    2015-11-01

    Most shotgun proteomics data analysis workflows are based on the assumption that each fragment ion spectrum is explained by a single species of peptide ion isolated by the mass spectrometer; however, in reality mass spectrometers often isolate more than one peptide ion within the window of isolation that contribute to additional peptide fragment peaks in many spectra. We present a new tool called reSpect, implemented in the Trans-Proteomic Pipeline (TPP), which enables an iterative workflow whereby fragment ion peaks explained by a peptide ion identified in one round of sequence searching or spectral library search are attenuated based on the confidence of the identification, and then the altered spectrum is subjected to further rounds of searching. The reSpect tool is not implemented as a search engine, but rather as a post-search engine processing step where only fragment ion intensities are altered. This enables the application of any search engine combination in the iterations that follow. Thus, reSpect is compatible with all other protein sequence database search engines as well as peptide spectral library search engines that are supported by the TPP. We show that while some datasets are highly amenable to chimeric spectrum identification and lead to additional peptide identification boosts of over 30% with as many as four different peptide ions identified per spectrum, datasets with narrow precursor ion selection only benefit from such processing at the level of a few percent. We demonstrate a technique that facilitates the determination of the degree to which a dataset would benefit from chimeric spectrum analysis. The reSpect tool is free and open source, provided within the TPP and available at the TPP website.

  2. Quantitation of stable isotopic tracers of calcium by fast atom bombardment mass spectrometry

    International Nuclear Information System (INIS)

    Jiang, X.; Smith, D.L.

    1987-01-01

    Instrumentation and methodology developed for quantitation of stable isotopic traces in urine are described. Calcium is isolated from urine as the insoluble oxalate salt which is subsequently dissolved in hydrochloric acid. The isotopic content of the acid solution is determined by use of a conventional mass spectrometer equipped with a fast atom bombardment ion source. Calcium ions are desorbed from the sample surface by a beam of high-energy xenon atoms and detected with a high-resolution mass spectrometer. A data acquisition system has been developed to control the mass spectrometer and record the ion signals. Detailed analysis of potential sources of error indicates that the precision of the method is presently limited primarily by an isotope effect that occurs during ion desorption. Results presented here demonstrate that the relative abundances of calcium isotopes in urine can be determined with high precision (coefficient of variation < 0.2%) and that the method is a viable alternative to conventional thermal ionization mass spectrometry. The method is especially attractive because it uses a conventional high-resolution mass spectrometer which is routinely used for analysis of organic substances

  3. DOTS: A High Resolution Orbitrap Mass Spectrometer for In Situ Analysis of the surface samples of Airless Planetary Bodies

    Science.gov (United States)

    Briois, Christelle; Thissen, Roland; Engrand, Cécile; Altwegg, Kathrin; Bouabdellah, Abdel; Boukrara, Amirouche; Carrasco, Nathalie; Chapuis, Claude; Cottin, Hervé; Grün, Eberhard; Grand, Noel; Henkel, Hartmut; Kempf, Sascha; Lebreton, Jean-Pierre; Makarov, Alexander A.; Postber, Frank; Srama, Ralf; Schmidt, Jürgen; Szopa, Cyril; Thirkell, Laurent; Tobie, Gabriel; Wurz, Peter; Zolotov, Mikhail Yu

    2013-04-01

    , Europa and Callisto. The high mass resolution capability of DOTS is especially beneficial for heavy species, as the mass resolving power (M/ΔM) of DOTS remains above 10 000 up to m/z=1 000 Da. Isotopic ratios can also be measured with DOTS, which would give insights into the origin and the processing of the parent molecules inside the grains. DOTS is designed with a dual polarity that allows for the detection of both negative and positive ions, best suited for both the detection of major rock forming elements (minerals, mostly cations) and organic compounds (preferentially anions in oxidizing medium). The recently discovered outer rings of Uranus [8] present striking similarity with Saturn's E ring, which is now considered as the result of ice volcanic activity of Enceladus. If a similar process is at work, this outer blue ring of Uranus could result from meteoroid impacts continually blasting dust off the surface of Mab (small embedded moon on the outermost blue ring) [9]. A DOTS-like instrument would be of great value to study the nature of this ring, in the context of a future mission to Uranus. References [1] Krüger, H. et al. (1999). Nature, 399, 558-560. [2] Krivov, A.V. et al. (2003) PSS 51, 251-269. [3] Postberg, F. et al. (2009) Nature, 459, 1098-1101. [4] Postberg, F. et al. (2011) Nature, 474, 620-622. [5] Makarov, A. (2000) Anal. Chem., 72, 1156-1162, [6] Makarov, A. et al. (2005) Anal. Chem., 78, 2113. [7] Dust OrbiTrap Sensor - DOTS proposal, PI Thissen R. (October 2012). [8] dePater I. et al. (2006) Science, 392, 92-94, [9] Showalter M.R. and Lissauer J.J. (2006) Science, 311, 973-977. Acknowledgements We thank the CNES (R&T SU-0003-039) for financial support.

  4. The European FAZIA initiative: a high-performance digital telescope array for heavy-ion studies

    International Nuclear Information System (INIS)

    Casini, G.; Barlini, S.; Pasquali, G.; Pastore, G.; Bini, M.; Carboni, S.; Olmi, A.; Piantelli, S.; Poggi, G.; Stefanini, A.; Valdre, S.; Bonnet, E.; Chbihi, A.; Frankland, J.D.; Gruyer, D.; Marini, P.; Borderie, B.; Edelbruck, P.; Rivet, M.F.; Salomon, F.; Bougault, R.; Le Neindre, N.; Lopez, O.; Parlog, M.; Vient, E.; Bruno, M.; Guerzoni, M.; Morelli, L.; Cinausero, M.; Gramegna, F.; Degerlier, M.; Kordjasz, A.; Twarog, T.; Kozik, T.; Marchi, T.; Ordine, A.; Rosato, E.; Spadaccini, G.; Vigilante, M.

    2014-01-01

    A modular array of 192 Si-Si-CsI(Tl) telescopes is under construction by the european FAZIA collaboration for charged product identification in heavy-ion studies. Thanks to an intense development phase, the ion identification capability of such modules has been improved both adopting specific solutions for the detectors and using fast digital electronics channels featuring high resolution. The silicons have been cut to present almost random orientation and have uniform doping homogeneity. To improve pulse shape analysis (PSA), they are reverse mounted in the telescopes. Full charge separation has been obtained up to over Z=54 also for ions stopping in the first silicon layer via PSA, with a threshold of 2.5 MeV/u for Carbon (Tin) ions. Isotopes are separated up to the iron region by the ΔE - E method for ions stopped in second silicon or in the CsI crystal. For slower particles, the PSA allows for isotopic resolution up to Z ∼ 14 with thresholds corresponding to ∼ 50 μm of (fully depleted) silicon detector. Preliminary results for partially depleted detectors indicate a strong improvement of mass separation with respect to the full depletion case at the cost of somewhat higher thresholds

  5. A cylindrical Penning trap for capture, mass selective cooling, and bunching of radioactive ion beams

    International Nuclear Information System (INIS)

    Raimbault-Hartmann, H.; Bollen, G.; Beck, D.; Koenig, M.; Kluge, H.-J.; Schwarz, S.; Schark, E.; Stein, J.; Szerypo, J.

    1997-01-01

    A Penning trap ion accumulator, cooler, and buncher for low-energy ion beams has been developed for the ISOLTRAP mass spectrometer at ISOLDE/CERN. A cylindrical electrode configuration is used for the creation of a nested trapping potential. This is required for efficient accumulation of externally produced ions and for high-mass selectivity by buffer gas cooling. The design goal of a mass resolving power of about 1 x 10 5 has been achieved. Isobar separation has been demonstrated for radioactive rare-earth ion beams delivered by the ISOLDE on-line mass separator. (orig.)

  6. A cylindrical Penning trap for capture, mass selective cooling, and bunching of radioactive ion beams

    CERN Document Server

    Raimbault-Hartmann, H; Bollen, G; König, M; Kluge, H J; Schark, E; Stein, J; Schwarz, S; Szerypo, J

    1997-01-01

    A Penning trap ion accumulator, cooler, and buncher for low energy ion beams has been developed for the ISOLTRAP mass spectrometer at ISOLDE/CERN. A cylindrical electrode configuration is used for the creation of a nested trapping potential. This is required for efficient accumulation of externally produced ions and for high mass selectivity by buffer gas cooling. The design goal of a mass resolving power of about $1\\cdot 10^{5}$ has been achieved. Isobar separation has been demonstrated for radioactive rare earth ion beams delivered by the ISOLDE on-line mass separator.

  7. Bayesian approach to peak deconvolution and library search for high resolution gas chromatography - Mass spectrometry.

    Science.gov (United States)

    Barcaru, A; Mol, H G J; Tienstra, M; Vivó-Truyols, G

    2017-08-29

    A novel probabilistic Bayesian strategy is proposed to resolve highly coeluting peaks in high-resolution GC-MS (Orbitrap) data. Opposed to a deterministic approach, we propose to solve the problem probabilistically, using a complete pipeline. First, the retention time(s) for a (probabilistic) number of compounds for each mass channel are estimated. The statistical dependency between m/z channels was implied by including penalties in the model objective function. Second, Bayesian Information Criterion (BIC) is used as Occam's razor for the probabilistic assessment of the number of components. Third, a probabilistic set of resolved spectra, and their associated retention times are estimated. Finally, a probabilistic library search is proposed, computing the spectral match with a high resolution library. More specifically, a correlative measure was used that included the uncertainties in the least square fitting, as well as the probability for different proposals for the number of compounds in the mixture. The method was tested on simulated high resolution data, as well as on a set of pesticides injected in a GC-Orbitrap with high coelution. The proposed pipeline was able to detect accurately the retention times and the spectra of the peaks. For our case, with extremely high coelution situation, 5 out of the 7 existing compounds under the selected region of interest, were correctly assessed. Finally, the comparison with the classical methods of deconvolution (i.e., MCR and AMDIS) indicates a better performance of the proposed algorithm in terms of the number of correctly resolved compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. System for studying a sample of material using a heavy ion induced mass spectrometer source

    Science.gov (United States)

    Fries, D.P.; Browning, J.F.

    1998-07-21

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high (n,f) reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu. 3 figs.

  9. Method for studying a sample of material using a heavy ion induced mass spectrometer source

    Science.gov (United States)

    Fries, D.P.; Browning, J.F.

    1999-02-16

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high n,f reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu. 3 figs.

  10. High resolution magnetic force microscopy using focused ion beam modified tips

    NARCIS (Netherlands)

    Phillips, G.N.; Siekman, Martin Herman; Abelmann, Leon; Lodder, J.C.

    2002-01-01

    Atomic force microscope tips coated by the thermal evaporation of a magnetic 30 nm thick Co film have been modified by focused ion beam milling with Ga+ ions to produce tips suitable for magnetic force microscopy. Such tips possess a planar magnetic element with high magnetic shape anisotropy, an

  11. Gas chromatographic quadrupole time-of-flight full scan high resolution mass spectrometric screening of human urine in antidoping analysis

    NARCIS (Netherlands)

    Abushareeda, Wadha; Lyris, Emmanouil; Kraiem, Suhail; Wahaibi, Aisha Al; Alyazidi, Sameera; Dbes, Najib; Lommen, Arjen; Nielen, Michel; Horvatovich, Peter L.; Alsayrafi, Mohammed; Georgakopoulos, Costas

    2017-01-01

    This paper presents the development and validation of a high-resolution full scan (FS) electron impact ionization (EI) gas chromatography coupled to quadrupole Time-of-Flight mass spectrometry (GC/QTOF) platform for screening anabolic androgenic steroids (AAS) in human urine samples. The World

  12. Theory of peak coalescence in Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Boldin, Ivan A; Nikolaev, Eugene N

    2009-10-01

    Peak coalescence, i.e. the merging of two close peaks in a Fourier transform ion cyclotron resonance (FTICR) mass spectrum at a high number of ions, plays an important role in various FTICR experiments. In order to describe the coalescence phenomenon we would like to propose a new theory of motion for ion clouds with close mass-to-charge ratios, driven by a uniform magnetic field and Coulomb interactions between the clouds. We describe the motion of the ion clouds in terms of their averaged drift motion in crossed magnetic and electric fields. The ion clouds are considered to be of constant size and their motion is studied in two dimensions. The theory deals with the first-order approximation of the equations of motion in relation to dm/m, where dm is the mass difference and m is the mass of a single ion. The analysis was done for an arbitrary inter-cloud interaction potential, which makes it possible to analyze finite-size ion clouds of any shape. The final analytical expression for the condition of the onset of coalescence is found for the case of uniformly charged spheres. An algorithm for finding this condition for an arbitrary interaction potential is proposed. The critical number of ions for the peak coalescence to take place is shown to depend quadratically on the magnetic field strength and to be proportional to the cyclotron radius and inversely proportional to the ion masses. Copyright (c) 2009 John Wiley & Sons, Ltd.

  13. Tissue imaging with a stigmatic mass microscope using laser desorption/ionization

    Science.gov (United States)

    Awazu, Kunio; Hazama, Hisanao; Hamanaka, Tomonori; Aoki, Jun; Toyoda, Michisato; Naito, Yasuhide

    2012-03-01

    A novel stigmatic mass microscope using laser desorption/ionization and a multi-turn time-of-flight mass spectrometer, MULTUM-IMG, has been developed. Stigmatic ion images of crystal violet masked by a fine square mesh grid with a 12.7 μm pitch were clearly observed, and the estimated spatial resolution was about 3 μm in the linear mode with a 20-fold ion optical magnification. Tissue sections of a brain and eyes of a mouse stained with crystal violet and methylene blue were observed in the linear mode, and the stigmatic total ion images of crystal violet and methylene blue agreed well with the optical photomicrograph of the same sections. Especially, the fine structure in the cornea tissue was clearly observed with a spatial resolution in the range of micrometers. Although the total measurement time of the stigmatic ion image for the whole-eye section was about 59 minutes using a laser with a 10 Hz repetition rate, the measurement time could be reduced to about 35 s using a laser with a 1 kHz repetition rate and automation of measurements. The stigmatic mass microscope developed in this research should be suitable for high-spatial resolution and high-throughput imaging mass spectrometry for pathology, pharmacokinetics, and so on.

  14. Identification of chemical components in Baidianling Capsule based on gas chromatography-mass spectrometry and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Wu, Wenying; Chen, Yu; Wang, Binjie; Sun, Xiaoyang; Guo, Ping; Chen, Xiaohui

    2017-08-01

    Baidianling Capsule, which is made from 16 Chinese herbs, has been widely used for treating vitiligo clinically. In this study, the sensitive and rapid method has been developed for the analysis of chemical components in Baidianling Capsule by gas chromatography-mass spectrometry in combination with retention indices and high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Firstly, a total of 110 potential volatile compounds obtained from different extraction procedures including alkanes, alkenes, alkynes, ketones, ethers, aldehydes, alcohols, phenols, organic acids, esters, furans, pyrrole, acid amides, heterocycles, and oxides were detected from Baidianling Capsule by gas chromatography-mass spectrometry, of which 75 were identified by mass spectrometry in combination with the retention index. Then, a total of 124 components were tentatively identified by high-performance liquid chromatography combined with Fourier transform ion cyclotron resonance mass spectrometry. Fifteen constituents from Baidianling Capsule were accurately identified by comparing the retention times with those of reference compounds, others were identified by comparing the retention times and mass spectrometry data, as well as retrieving the reference literature. This study provides a practical strategy for rapidly screening and identifying the multiple constituents of a complex traditional Chinese medicine. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Screening of Carotenoids in Tomato Fruits by Using Liquid Chromatography with Diode Array-Linear Ion Trap Mass Spectrometry Detection.

    Science.gov (United States)

    Gentili, Alessandra; Caretti, Fulvia; Ventura, Salvatore; Pérez-Fernández, Virginia; Venditti, Alessandro; Curini, Roberta

    2015-08-26

    This paper presents an analytical strategy for a large-scale screening of carotenoids in tomato fruits by exploiting the potentialities of the triple quadrupole-linear ion trap hybrid mass spectrometer (QqQLIT). The method involves separation on C30 reversed-phase column and identification by means of diode array detection (DAD) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). The authentic standards of six model compounds were used to optimize the separative conditions and to predict the chromatographic behavior of untargeted carotenoids. An information dependent acquisition (IDA) was performed with (i) enhanced-mass scan (EMS) as the survey scan, (ii) enhanced-resolution (ER) scan to obtain the exact mass of the precursor ions (16-35 ppm), and (iii) enhanced product ion (EPI) scan as dependent scan to obtain structural information. LC-DAD-multiple reaction monitoring (MRM) chromatograms were also acquired for the identification of targeted carotenoids occurring at low concentrations; for the first time, the relative abundance between the MRM transitions (ion ratio) was used as an extra tool for the MS distinction of structural isomers and the related families of geometrical isomers. The whole analytical strategy was high-throughput, because a great number of experimental data could be acquired with few analytical steps, and cost-effective, because only few standards were used; when applied to characterize some tomato varieties ('Tangerine', 'Pachino', 'Datterino', and 'Camone') and passata of 'San Marzano' tomatoes, our method succeeded in identifying up to 44 carotenoids in the 'Tangerine'" variety.

  16. High voltage and high specific capacity dual intercalating electrode Li-ion batteries

    Science.gov (United States)

    West, William C. (Inventor); Blanco, Mario (Inventor)

    2010-01-01

    The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

  17. Mass spectrometer and method with improved ion transmission

    International Nuclear Information System (INIS)

    Douglas, D.J.; French, J.B.

    1992-01-01

    This invention relates to a mass analyzer, and to a method of operating a mass analyzer, of the kind in which ions are transmitted through a first rod set for focussing and separation from an accompanying gas, before passing through a mass filter rod set which which permits transmission only of ions of a selected mass to charge ratio. (author). 19 figs

  18. Ambient mass spectrometry employing direct analysis in real time (DART) ion source for olive oil quality and authenticity assessment

    International Nuclear Information System (INIS)

    Vaclavik, Lukas; Cajka, Tomas; Hrbek, Vojtech; Hajslova, Jana

    2009-01-01

    A novel approach for the authentication of olive oil samples representing different quality grades has been developed. A new type of ion source, direct analysis in real time (DART), coupled to a high-resolution time-of-flight mass spectrometer (TOFMS) was employed for the comprehensive profiling of triacylglycerols (TAGs) and/or polar compounds extracted with a methanol-water mixture. The main parameters influencing the ionization efficiency of TAGs were the type of sample solvent, degree of sample dilution, ion beam temperature, and presence of a dopant (ammonia vapors). The ionization yield of polar compounds depended mainly on a content of water in the extract and ion beam temperature. Using DART-TOFMS, not only differentiation among extra virgin olive oil (EVOO), olive pomace oil (OPO) and olive oil (OO) could be easily achieved, but also EVOO adulteration with commonly used adulterant, hazelnut oil (HO), was feasible. Based on the linear discriminant analysis (LDA), the introduced method allowed detection of HO addition of 6 and 15% (v/v) when assessing DART-TOFMS mass profiles of polar compounds and TAGs, respectively.

  19. Ambient mass spectrometry employing direct analysis in real time (DART) ion source for olive oil quality and authenticity assessment

    Energy Technology Data Exchange (ETDEWEB)

    Vaclavik, Lukas; Cajka, Tomas; Hrbek, Vojtech [Institute of Chemical Technology Prague, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 5, 166 28 Prague 6 (Czech Republic); Hajslova, Jana, E-mail: jana.hajslova@vscht.cz [Institute of Chemical Technology Prague, Faculty of Food and Biochemical Technology, Department of Food Chemistry and Analysis, Technicka 5, 166 28 Prague 6 (Czech Republic)

    2009-07-10

    A novel approach for the authentication of olive oil samples representing different quality grades has been developed. A new type of ion source, direct analysis in real time (DART), coupled to a high-resolution time-of-flight mass spectrometer (TOFMS) was employed for the comprehensive profiling of triacylglycerols (TAGs) and/or polar compounds extracted with a methanol-water mixture. The main parameters influencing the ionization efficiency of TAGs were the type of sample solvent, degree of sample dilution, ion beam temperature, and presence of a dopant (ammonia vapors). The ionization yield of polar compounds depended mainly on a content of water in the extract and ion beam temperature. Using DART-TOFMS, not only differentiation among extra virgin olive oil (EVOO), olive pomace oil (OPO) and olive oil (OO) could be easily achieved, but also EVOO adulteration with commonly used adulterant, hazelnut oil (HO), was feasible. Based on the linear discriminant analysis (LDA), the introduced method allowed detection of HO addition of 6 and 15% (v/v) when assessing DART-TOFMS mass profiles of polar compounds and TAGs, respectively.

  20. Isotopomer analysis of lipid biosynthesis by high resolution mass spectrometry and NMR

    Energy Technology Data Exchange (ETDEWEB)

    Lane, Andrew N., E-mail: anlane01@louisville.edu [JG Brown Cancer Center, 529 S. Jackson Street, Louisville, KY 40202 (United States); Center for Regulatory and Environmental Analytical Metabolomics (CREAM), University of Louisville, Louisville, KY (United States); Fan, Teresa W.-M. [JG Brown Cancer Center, 529 S. Jackson Street, Louisville, KY 40202 (United States); Center for Regulatory and Environmental Analytical Metabolomics (CREAM), University of Louisville, Louisville, KY (United States); Department of Chemistry, University of Louisville, Louisville, KY 40292 (United States); Xie, Zhengzhi; Moseley, Hunter N.B.; Higashi, Richard M. [Center for Regulatory and Environmental Analytical Metabolomics (CREAM), University of Louisville, Louisville, KY (United States); Department of Chemistry, University of Louisville, Louisville, KY 40292 (United States)

    2009-10-05

    We have coupled 2D-NMR and infusion FT-ICR-MS with computer-assisted assignment to profile {sup 13}C-isotopologues of glycerophospholipids (GPL) directly in crude cell extracts, resulting in very high information throughput of >3000 isobaric molecules in a few minutes. A mass accuracy of better than 1 ppm combined with a resolution of 100,000 at the measured m/z was required to distinguish isotopomers from other GPL structures. Isotopologue analysis of GPLs extracted from LCC2 breast cancer cells grown on [U-{sup 13}C]-glucose provided a rich trove of information about the biosynthesis and turnover of the GPLs. The isotopologue intensity ratios from the FT-ICR-MS were accurate to {approx}1% or better based on natural abundance background, and depended on the signal-to-nose ratio. The time course of incorporation of {sup 13}C from [U-{sup 13}C]-glucose into a particular phosphatidylcholine was analyzed in detail, to provide a quantitative measure of the sizes of glycerol, acetyl CoA and total GPL pools in growing LCC2 cells. Independent and complementary analysis of the positional {sup 13}C enrichment in the glycerol and fatty acyl chains obtained from high resolution 2D NMR was used to verify key aspects of the model. This technology enables simple and rapid sample preparation, has rapid analysis, and is generally applicable to unfractionated GPLs of almost any head group, and to mixtures of other classes of metabolites.

  1. Isotopomer analysis of lipid biosynthesis by high resolution mass spectrometry and NMR

    International Nuclear Information System (INIS)

    Lane, Andrew N.; Fan, Teresa W.-M.; Xie, Zhengzhi; Moseley, Hunter N.B.; Higashi, Richard M.

    2009-01-01

    We have coupled 2D-NMR and infusion FT-ICR-MS with computer-assisted assignment to profile 13 C-isotopologues of glycerophospholipids (GPL) directly in crude cell extracts, resulting in very high information throughput of >3000 isobaric molecules in a few minutes. A mass accuracy of better than 1 ppm combined with a resolution of 100,000 at the measured m/z was required to distinguish isotopomers from other GPL structures. Isotopologue analysis of GPLs extracted from LCC2 breast cancer cells grown on [U- 13 C]-glucose provided a rich trove of information about the biosynthesis and turnover of the GPLs. The isotopologue intensity ratios from the FT-ICR-MS were accurate to ∼1% or better based on natural abundance background, and depended on the signal-to-nose ratio. The time course of incorporation of 13 C from [U- 13 C]-glucose into a particular phosphatidylcholine was analyzed in detail, to provide a quantitative measure of the sizes of glycerol, acetyl CoA and total GPL pools in growing LCC2 cells. Independent and complementary analysis of the positional 13 C enrichment in the glycerol and fatty acyl chains obtained from high resolution 2D NMR was used to verify key aspects of the model. This technology enables simple and rapid sample preparation, has rapid analysis, and is generally applicable to unfractionated GPLs of almost any head group, and to mixtures of other classes of metabolites.

  2. Desorption atmospheric pressure photoionization high-resolution mass spectrometry: a complementary approach for the chemical analysis of atmospheric aerosols.

    Science.gov (United States)

    Parshintsev, Jevgeni; Vaikkinen, Anu; Lipponen, Katriina; Vrkoslav, Vladimir; Cvačka, Josef; Kostiainen, Risto; Kotiaho, Tapio; Hartonen, Kari; Riekkola, Marja-Liisa; Kauppila, Tiina J

    2015-07-15

    On-line chemical characterization methods of atmospheric aerosols are essential to increase our understanding of physicochemical processes in the atmosphere, and to study biosphere-atmosphere interactions. Several techniques, including aerosol mass spectrometry, are nowadays available, but they all suffer from some disadvantages. In this research, desorption atmospheric pressure photoionization high-resolution (Orbitrap) mass spectrometry (DAPPI-HRMS) is introduced as a complementary technique for the fast analysis of aerosol chemical composition without the need for sample preparation. Atmospheric aerosols from city air were collected on a filter, desorbed in a DAPPI source with a hot stream of toluene and nitrogen, and ionized using a vacuum ultraviolet lamp at atmospheric pressure. To study the applicability of the technique for ambient aerosol analysis, several samples were collected onto filters and analyzed, with the focus being on selected organic acids. To compare the DAPPI-HRMS data with results obtained by an established method, each filter sample was divided into two equal parts, and the second half of the filter was extracted and analyzed by liquid chromatography/mass spectrometry (LC/MS). The DAPPI results agreed with the measured aerosol particle number. In addition to the targeted acids, the LC/MS and DAPPI-HRMS methods were found to detect different compounds, thus providing complementary information about the aerosol samples. DAPPI-HRMS showed several important oxidation products of terpenes, and numerous compounds were tentatively identified. Thanks to the soft ionization, high mass resolution, fast analysis, simplicity and on-line applicability, the proposed methodology has high potential in the field of atmospheric research. Copyright © 2015 John Wiley & Sons, Ltd.

  3. Gas chromatographic quadrupole time-of-flight full scan high resolution mass spectrometric screening of human urine in antidoping analysis

    NARCIS (Netherlands)

    Abushareeda, Wadha; Lyris, Emmanouil; Kraiem, Suhail; Wahaibi, Aisha Al; Alyazidi, Sameera; Dbes, Najib; Lommen, Arjen; Nielen, Michel; Horvatovich, Peter L.; Alsayrafi, Mohammed; Georgakopoulos, Costas

    2017-01-01

    This paper presents the development and validation of a high-resolution full scan (FS) electron impact ionization (EI) gas chromatography coupled to quadrupole Time-of-Flight mass spectrometry (GC/QTOF) platform for screening anabolic androgenic steroids (AAS) in human urine samples. The World

  4. Structuring of material parameters in lithium niobate crystals with low-mass, high-energy ion radiation

    Science.gov (United States)

    Peithmann, K.; Eversheim, P.-D.; Goetze, J.; Haaks, M.; Hattermann, H.; Haubrich, S.; Hinterberger, F.; Jentjens, L.; Mader, W.; Raeth, N. L.; Schmid, H.; Zamani-Meymian, M.-R.; Maier, K.

    2011-10-01

    Ferroelectric lithium niobate crystals offer a great potential for applications in modern optics. To provide powerful optical components, tailoring of key material parameters, especially of the refractive index n and the ferroelectric domain landscape, is required. Irradiation of lithium niobate crystals with accelerated ions causes strong structured modifications in the material. The effects induced by low-mass, high-energy ions (such as 3He with 41 MeV, which are not implanted, but transmit through the entire crystal volume) are reviewed. Irradiation yields large changes of the refractive index Δn, improved domain engineering capability within the material along the ion track, and waveguiding structures. The periodic modification of Δn as well as the formation of periodically poled lithium niobate (PPLN) (supported by radiation damage) is described. Two-step knock-on displacement processes, 3He→Nb and 3He→O causing thermal spikes, are identified as origin for the material modifications.

  5. Multiple-ion-beam time-of-flight mass spectrometer

    International Nuclear Information System (INIS)

    Rohrbacher, Andreas; Continetti, Robert E.

    2001-01-01

    An innovative approach to increase the throughput of mass spectrometric analyses using a multiple-ion-beam mass spectrometer is described. Two sample spots were applied onto a laser desorption/ionization target and each spot was simultaneously irradiated by a beam of quadrupled Nd:YLF laser radiation (261.75 nm) to produce ions by laser-desorption ionization. Acceleration of the ions in an electric field created parallel ion beams that were focused by two parallel einzel lens systems. After a flight path of 2.34 m, the ions were detected with a microchannel plate-phosphor screen assembly coupled with a charge coupled device camera that showed two resolved ion beams. Time-of-flight mass spectra were also obtained with this detector. Experiments were performed using both metal atom cations (Ti + and Cr + ) produced by laser desorption/ionization and the molecular ions of two different proteins (myoglobin and lysozyme), created by matrix assisted laser desorption/ionization using an excess of nicotinic acid as matrix

  6. reSpect: software for identification of high and low abundance ion species in chimeric tandem mass spectra.

    Science.gov (United States)

    Shteynberg, David; Mendoza, Luis; Hoopmann, Michael R; Sun, Zhi; Schmidt, Frank; Deutsch, Eric W; Moritz, Robert L

    2015-11-01

    Most shotgun proteomics data analysis workflows are based on the assumption that each fragment ion spectrum is explained by a single species of peptide ion isolated by the mass spectrometer; however, in reality mass spectrometers often isolate more than one peptide ion within the window of isolation that contribute to additional peptide fragment peaks in many spectra. We present a new tool called reSpect, implemented in the Trans-Proteomic Pipeline (TPP), which enables an iterative workflow whereby fragment ion peaks explained by a peptide ion identified in one round of sequence searching or spectral library search are attenuated based on the confidence of the identification, and then the altered spectrum is subjected to further rounds of searching. The reSpect tool is not implemented as a search engine, but rather as a post-search engine processing step where only fragment ion intensities are altered. This enables the application of any search engine combination in the iterations that follow. Thus, reSpect is compatible with all other protein sequence database search engines as well as peptide spectral library search engines that are supported by the TPP. We show that while some datasets are highly amenable to chimeric spectrum identification and lead to additional peptide identification boosts of over 30% with as many as four different peptide ions identified per spectrum, datasets with narrow precursor ion selection only benefit from such processing at the level of a few percent. We demonstrate a technique that facilitates the determination of the degree to which a dataset would benefit from chimeric spectrum analysis. The reSpect tool is free and open source, provided within the TPP and available at the TPP website. Graphical Abstract ᅟ.

  7. High-Resolution Experimental Investigation of mass transfer enhancement by chemical oxidation from DNAPL entrapped in variable-aperture fractures

    Science.gov (United States)

    Arshadi, M.; Rajaram, H.; Detwiler, R. L.; Jones, T.

    2012-12-01

    Permanganate oxidation of DNAPL- contaminated fractured rock is an effective remediation technology. Permanganate ion reacts with dissolved DNAPL in a bi-molecular oxidation-reduction reaction. The consumption of dissolved DNAPL in this reaction results in increased concentration gradients away from the free-phase DNAPL, resulting in reaction-enhanced mass transfer, which accelerates contaminant removal. The specific objective of our research was to perform high-resolution non-intrusive experimental studies of permanganate oxidation in a 15.24 × 15.24 cm, transparent, analog, variable-aperture fracture with complex initial TCE entrapped phase geometry. Our experimental system uses light-transmission techniques to accurately measure both fracture aperture and the evolution of individual entrapped DNAPL blobs during the remediation experiments at high resolution (pixel size : 6.2×10-3 cm). Three experiments were performed with different flow rates and permanganate inflow concentrations to observe DNAPL-permanganate interactions across a broader range of conditions. Prior to initiating each experiment, the aperture field within the fracture was measured. The oxidation experiment was initiated by TCE injection into the water saturated fracture till the TCE reached the outflow end, followed by water re-injection through the fracture. The flowing water mobilized some TCE. We continued injection of water till TCE mobilization ceased, leaving behind the residual TCE entrapped within the variable-aperture fracture. Subsequently, permanganate injection through the fracture resulted in propagation of a fingered reaction front into the fracture. We developed image processing algorithms to analyze the evolution of DNAPL phase geometry over the duration of the experiment. The permanganate consumption rate varied significantly within the fracture due to the complex flow and DNAPL concentration fields. Precipitated MnO2 was clearly evident on the downstream side of DNAPL blobs

  8. Gamma Radiation from Fission Fragments Experimental Apparatus-Mass Spectrum Resolution

    Energy Technology Data Exchange (ETDEWEB)

    Higbie, Jack

    1969-08-15

    The gamma-radiation from fission fragments was studied as a function of the fragment mass. The mass was determined from the fragment energies using solid state detectors. The mass resolution which can be achieved by this method is treated in detail. The average initial fragment mass and the initial mass resolution is calculated as a function of the measured (apparent) mass yield for three different thicknesses of the fissile material deposit. This treatment gives a clear indication of those factors most important for good mass resolution work. A detailed description of the experimental apparatus is given in the appendices.

  9. Effect of energy selection on quantitative analysis in secondary ion microanalysis

    International Nuclear Information System (INIS)

    Steele, I.M.; Solberg, T.N.; Smith, J.V.; Clayton, R.N.; Hutcheon, I.D.

    1977-01-01

    Systematic change of voltage on the components of the secondary ion (SI) extraction system of our AEI-IM20 ion microprobe produced major changes of relative intensities of secondary ions passing through the mass spectrometer. The repeller, which bends the SI beam through about 60 0 , has the greatest effect, and can be used to plot the energy distribution. The extractor and the deflecting and focusing components have smaller but significant effects. Because low-energy secondary ions have a near-symmetrical distribution, whereas high-energy ones have an assymetric distribution favoring high energies, tuning of the acceptance band to higher energy reduces interference from low-energy ions, which tend to be unwanted molecular ions, at the expense of reduced transmission. Tuning to lower energy increases interference but gives higher transmission. The former condition is desirable for instruments restricted to low mass resolution, whereas both conditions are valuable for instruments adjustable for both high and low mass resolution. Other important factors are (a) sensitivity to surface irregularities which perturb SI energy collection, and (b) change in derived 'temperatures' from thermodynamic sputtering models merely from tuning the energy acceptance band. Careful attention to the above factors yielded reproducible SI ratios for the binary series of plagioclase feldspars. (Auth.)

  10. Biomarker Discovery Using New Metabolomics Software for Automated Processing of High Resolution LC-MS Data

    Science.gov (United States)

    Hnatyshyn, S.; Reily, M.; Shipkova, P.; McClure, T.; Sanders, M.; Peake, D.

    2011-01-01

    Robust biomarkers of target engagement and efficacy are required in different stages of drug discovery. Liquid chromatography coupled to high resolution mass spectrometry provides sensitivity, accuracy and wide dynamic range required for identification of endogenous metabolites in biological matrices. LCMS is widely-used tool for biomarker identification and validation. Typical high resolution LCMS profiles from biological samples may contain greater than a million mass spectral peaks corresponding to several thousand endogenous metabolites. Reduction of the total number of peaks, component identification and statistical comparison across sample groups remains to be a difficult and time consuming challenge. Blood samples from four groups of rats (male vs. female, fully satiated and food deprived) were analyzed using high resolution accurate mass (HRAM) LCMS. All samples were separated using a 15 minute reversed-phase C18 LC gradient and analyzed in both positive and negative ion modes. Data was acquired using 15K resolution and 5ppm mass measurement accuracy. The entire data set was analyzed using software developed in collaboration between Bristol Meyers Squibb and Thermo Fisher Scientific to determine the metabolic effects of food deprivation on rats. Metabolomic LC-MS data files are extraordinarily complex and appropriate reduction of the number of spectral peaks via identification of related peaks and background removal is essential. A single component such as hippuric acid generates more than 20 related peaks including isotopic clusters, adducts and dimers. Plasma and urine may contain 500-1500 unique quantifiable metabolites. Noise filtering approaches including blank subtraction were used to reduce the number of irrelevant peaks. By grouping related signals such as isotopic peaks and alkali adducts, data processing was greatly simplified by reducing the total number of components by 10-fold. The software processes 48 samples in under 60minutes. Principle

  11. The kick-out mass selection technique for ions stored in an Electrostatic Ion Beam Trap

    International Nuclear Information System (INIS)

    Toker, Y; Altstein, N; Aviv, O; Rappaport, M L; Heber, O; Schwalm, D; Strasser, D; Zajfman, D

    2009-01-01

    A simple mass selection technique which allows one to clean a keV ion beam of undesirable masses while stored in an Electrostatic Ion Beam Trap (EIBT) is described. The technique is based on the time-of-flight principle and takes advantage of the long storage times and self-bunching that are possible in this type of traps (self bunching being the effect that keeps ions of the same mass bunched in spite of their finite distributions of velocities and trajectories). As the oscillation period is proportional to the square root of the ion mass, bunches containing ions of different masses will separate in space with increasing storage time and can be kicked out by a pulsed deflector mounted inside the trap. A mass selector of this type has been implemented successfully in an EIBT connected to an Even-Lavie supersonic expansion source and is routinely used in ongoing cluster experiments.

  12. Mass and Charge Measurements on Heavy Ions

    Science.gov (United States)

    Sugai, Toshiki

    2017-01-01

    The relationship between mass and charge has been a crucial topic in mass spectrometry (MS) because the mass itself is typically evaluated based on the m/z ratio. Despite the fact that this measurement is indirect, a precise mass can be obtained from the m/z value with a high m/z resolution up to 105 for samples in the low mass and low charge region under 10,000 Da and 20 e, respectively. However, the target of MS has recently been expanded to the very heavy region of Mega or Giga Da, which includes large particles and biocomplexes, with very large and widely distributed charge from kilo to Mega range. In this region, it is necessary to evaluate charge and mass simultaneously. Recent studies for simultaneous mass and charge observation and related phenomena are discussed in this review. PMID:29302406

  13. The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

    Science.gov (United States)

    Oganessian, Yu. Ts.; Shchepunov, V. A.; Dmitriev, S. N.; Itkis, M. G.; Gulbekyan, G. G.; Khabarov, M. V.; Bekhterev, V. V.; Bogomolov, S. L.; Efremov, A. A.; Pashenko, S. V.; Stepantsov, S. V.; Yeremin, A. V.; Yavor, M. I.; Kalimov, A. G.

    2003-05-01

    A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 -3. The set up can work in the wide mass range from A≈20 to A≈500, its mass acceptance is as large as ±2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90° electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considered. Description of its elements and subsystems is given.

  14. The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

    International Nuclear Information System (INIS)

    Oganessian, Yu.Ts.; Shchepunov, V.A.; Dmitriev, S.N.; Itkis, M.G.; Gulbekyan, G.G.; Khabarov, M.V.; Bekhterev, V.V.; Bogomolov, S.L.; Efremov, A.A.; Pashenko, S.V.; Stepantsov, S.V.; Yeremin, A.V.; Yavor, M.I.; Kalimov, A.G.

    2003-01-01

    A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 -3 . The set up can work in the wide mass range from A∼20 to A∼500, its mass acceptance is as large as ±2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90 deg. electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considered. Description of its elements and subsystems is given

  15. The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

    Energy Technology Data Exchange (ETDEWEB)

    Oganessian, Yu.Ts.; Shchepunov, V.A. E-mail: shchepun@sunhe.jinr.rushchepun@cv.jinr.ru; Dmitriev, S.N.; Itkis, M.G.; Gulbekyan, G.G.; Khabarov, M.V.; Bekhterev, V.V.; Bogomolov, S.L.; Efremov, A.A.; Pashenko, S.V.; Stepantsov, S.V.; Yeremin, A.V.; Yavor, M.I.; Kalimov, A.G

    2003-05-01

    A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10{sup -3}. The set up can work in the wide mass range from A{approx}20 to A{approx}500, its mass acceptance is as large as {+-}2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90 deg. electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considered. Description of its elements and subsystems is given.

  16. Study of SiO{sub 2} surface sputtering by a 250-550 keV He{sup +} ion beam during high-resolution Rutherford backscattering measurements

    Energy Technology Data Exchange (ETDEWEB)

    Kusanagi, Susumu [Materials Analysis Laboratory, Advanced Design Technology Center, Sony Corporation, 4-16-1 Okata Atsugi-shi, Kanagawa 243-0021 (Japan)]. E-mail: susumu.kusanagi@jp.sony.com; Kobayashi, Hajime [Materials Analysis Laboratory, Advanced Design Technology Center, Sony Corporation, 4-16-1 Okata Atsugi-shi, Kanagawa 243-0021 (Japan)

    2006-08-15

    Decreases in oxygen signal intensities in spectra of high-resolution Rutherford backscattering spectrometry (HRBS) were observed during measurements on a 5-nm thick SiO{sub 2} layer on a Si substrate when irradiated by 250-550 keV He{sup +} ions. Shifts in an implanted arsenic profile in a 5-nm thick SiO{sub 2}/Si substrate were also observed as a result of He{sup +} ion irradiation. These results lead to the conclusion that the SiO{sub 2} surface was sputtered by He{sup +} ions in this energy range.

  17. Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  18. 'Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry'

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  19. [Uncertainty evaluation of the determination of toxic equivalent quantity of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil by isotope dilution high resolution gas chromatography and high resolution mass spectrometry].

    Science.gov (United States)

    Du, Bing; Liu Aimin; Huang, Yeru

    2014-09-01

    Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in soil samples were analyzed by isotope dilution method with high resolution gas chromatography and high resolution mass spectrometry (ID-HRGC/HRMS), and the toxic equivalent quantity (TEQ) were calculated. The impacts of major source of measurement uncertainty are discussed, and the combined relative standard uncertainties were calculated for each 2, 3, 7, 8 substituted con- gener. Furthermore, the concentration, combined uncertainty and expanded uncertainty for TEQ of PCDD/Fs in a soil sample in I-TEF, WHO-1998-TEF and WHO-2005-TEF schemes are provided as an example. I-TEF, WHO-1998-TEF and WHO-2005-TEF are the evaluation schemes of toxic equivalent factor (TEF), and are all currently used to describe 2,3,7,8 sub- stituted relative potencies.

  20. An Improvement on Space Focusing Resolution in Two-Field Time-of-Flight Mass Spectrometers

    International Nuclear Information System (INIS)

    Yildirim, M.; Aydin, R.; Akin, U.; Kilic, H. S.; Sise, O.; Ulu, M.; Dogan, M.

    2007-01-01

    Time-of-Flight Mass Spectrometer (TOFMS) is a sophisticated device for the mass selective analysis of a variety of samples. The main limitation on TOFMS technique is the obtainable resolution where the two main limiting factors are the initial space and energy spread of particles created in ionization region. Similar charged particles starting at different points will reach the detector at different times. So, this problem makes space focusing is very important subject. We have presented principles of two-fields TOFMS with second-order space focusing both using analytical methods and ray-tracing simulation. This work aims understanding of ion optical system clearly and gives hint of expectation for future developments

  1. Relativistic, QED and nuclear effects in highly charged ions revealed by resonant electron-ion recombination in storage rings

    OpenAIRE

    Schippers, Stefan

    2008-01-01

    Dielectronic recombination (DR) of few-electron ions has evolved into a sensitive spectroscopic tool for highly charged ions. This is due to technological advances in electron-beam preparation and ion-beam cooling techniques at heavy-ion storage rings. Recent experiments prove unambiguously that DR collision spectroscopy has become sensitive to 2nd order QED and to nuclear effects. This review discusses the most recent developments in high-resolution spectroscopy of low-energy DR resonances, ...

  2. High-resolution spectroscopy for Doppler-broadening ion temperature measurements of implosions at the National Ignition Facility

    Energy Technology Data Exchange (ETDEWEB)

    Koch, J. A.; Stewart, R. E.; Beiersdorfer, P.; Shepherd, R.; Schneider, M. B.; Miles, A. R.; Scott, H. A.; Smalyuk, V. A.; Hsing, W. W. [Lawrence Livermore National Laboratory, P.O. Box 808, L-493, Livermore, California 94550 (United States)

    2012-10-15

    Future implosion experiments at the national ignition facility (NIF) will endeavor to simultaneously measure electron and ion temperatures with temporal and spatial resolution in order to explore non-equilibrium temperature distributions and their relaxation toward equilibrium. In anticipation of these experiments, and with understanding of the constraints of the NIF facility environment, we have explored the use of Doppler broadening of mid-Z dopant emission lines, such as krypton He-{alpha} at 13 keV, as a diagnostic of time- and potentially space-resolved ion temperature. We have investigated a number of options analytically and with numerical raytracing, and we have identified several promising candidate spectrometer designs that meet the expected requirements of spectral and temporal resolution and data signal-to-noise ratio for gas-filled exploding pusher implosions, while providing maximum flexibility for use on a variety of experiments that potentially include burning plasma.

  3. High-resolution spectroscopy diagnostics for measuring impurity ion temperature and velocity on the COMPASS tokamak

    Energy Technology Data Exchange (ETDEWEB)

    Weinzettl, Vladimir, E-mail: vwei@ipp.cas.cz [Institute of Plasma Physics ASCR, Prague (Czech Republic); Shukla, Gaurav [Institute of Plasma Physics ASCR, Prague (Czech Republic); Department of Applied Physics, Ghent University, Ghent (Belgium); Faculty of Mathematics and Physics, Charles University in Prague, Prague (Czech Republic); Ghosh, Joydeep [Institute for Plasma Research, Bhat, Gandhinagar (India); Melich, Radek; Panek, Radomir [Institute of Plasma Physics ASCR, Prague (Czech Republic); Tomes, Matej; Imrisek, Martin; Naydenkova, Diana [Institute of Plasma Physics ASCR, Prague (Czech Republic); Faculty of Mathematics and Physics, Charles University in Prague, Prague (Czech Republic); Varju, Josef [Institute of Plasma Physics ASCR, Prague (Czech Republic); Pereira, Tiago [Instituto de Plasmas e Fusão Nuclear, Lisboa (Portugal); Instituto Superior Técnico, Universidade de Lisboa, Lisboa (Portugal); Gomes, Rui [Instituto de Plasmas e Fusão Nuclear, Lisboa (Portugal); Abramovic, Ivana; Jaspers, Roger [Eindhoven University of Technology, Eindhoven (Netherlands); Pisarik, Michael [SQS Vlaknova optika a.s., Nova Paka (Czech Republic); Department of Electromagnetic Field, Faculty of Electrical Engineering, Czech Technical University in Prague (Czech Republic); Odstrcil, Tomas [Max-Planck-Institut fur Plasmaphysik, Garching (Germany); Van Oost, Guido [Department of Applied Physics, Ghent University, Ghent (Belgium)

    2015-10-15

    Highlights: • We built a new diagnostic of poloidal plasma rotation on the COMPASS tokamak. • Improvements in throughput via toroidal integration and fiber optimizations shown. • Poloidal rotation and ion temperature measured in L- and H-mode and during RMP. • Design and parameters of a new CXRS diagnostic for COMPASS are introduced. - Abstract: High-resolution spectroscopy is a powerful tool for the measurement of plasma rotation as well as ion temperature using the Doppler shift of the emitted spectral lines and their Doppler broadening, respectively. Both passive and active diagnostic variants for the COMPASS tokamak are introduced. The passive diagnostic focused on the C III lines at about 465 nm is utilized for the observation of the poloidal plasma rotation. The current set-up of the measuring system is described, including the intended high-throughput optics upgrade. Different options to increase the fiber collection area are mentioned, including a flower-like fiber bundle, and the use of micro-lenses or tapered fibers. Recent measurements of poloidal plasma rotation of the order of 0–6 km/s are shown. The design of the new active diagnostic using a deuterium heating beam and based on charge exchange recombination spectroscopy (C VI line at 529 nm) is introduced. The tool will provide both space (0.5–5 cm) and time (10 ms) resolved toroidal plasma rotation and ion temperature profiles. The results of the Simulation of Spectra code used to examine the feasibility of charge exchange measurements on COMPASS are shown and connected with a selection of the spectrometer coupled with the CCD camera.

  4. High-resolution spectroscopy diagnostics for measuring impurity ion temperature and velocity on the COMPASS tokamak

    International Nuclear Information System (INIS)

    Weinzettl, Vladimir; Shukla, Gaurav; Ghosh, Joydeep; Melich, Radek; Panek, Radomir; Tomes, Matej; Imrisek, Martin; Naydenkova, Diana; Varju, Josef; Pereira, Tiago; Gomes, Rui; Abramovic, Ivana; Jaspers, Roger; Pisarik, Michael; Odstrcil, Tomas; Van Oost, Guido

    2015-01-01

    Highlights: • We built a new diagnostic of poloidal plasma rotation on the COMPASS tokamak. • Improvements in throughput via toroidal integration and fiber optimizations shown. • Poloidal rotation and ion temperature measured in L- and H-mode and during RMP. • Design and parameters of a new CXRS diagnostic for COMPASS are introduced. - Abstract: High-resolution spectroscopy is a powerful tool for the measurement of plasma rotation as well as ion temperature using the Doppler shift of the emitted spectral lines and their Doppler broadening, respectively. Both passive and active diagnostic variants for the COMPASS tokamak are introduced. The passive diagnostic focused on the C III lines at about 465 nm is utilized for the observation of the poloidal plasma rotation. The current set-up of the measuring system is described, including the intended high-throughput optics upgrade. Different options to increase the fiber collection area are mentioned, including a flower-like fiber bundle, and the use of micro-lenses or tapered fibers. Recent measurements of poloidal plasma rotation of the order of 0–6 km/s are shown. The design of the new active diagnostic using a deuterium heating beam and based on charge exchange recombination spectroscopy (C VI line at 529 nm) is introduced. The tool will provide both space (0.5–5 cm) and time (10 ms) resolved toroidal plasma rotation and ion temperature profiles. The results of the Simulation of Spectra code used to examine the feasibility of charge exchange measurements on COMPASS are shown and connected with a selection of the spectrometer coupled with the CCD camera.

  5. Receptor-based high-throughput screening and identification of estrogens in dietary supplements using bioaffinity liquid-chromatography ion mobility mass spectrometry.

    Science.gov (United States)

    Aqai, Payam; Blesa, Natalia Gómez; Major, Hilary; Pedotti, Mattia; Varani, Luca; Ferrero, Valentina E V; Haasnoot, Willem; Nielen, Michel W F

    2013-11-01

    A high-throughput bioaffinity liquid chromatography-mass spectrometry (BioMS) approach was developed and applied for the screening and identification of recombinant human estrogen receptor α (ERα) ligands in dietary supplements. For screening, a semi-automated mass spectrometric ligand binding assay was developed applying (13)C2, (15) N-tamoxifen as non-radioactive label and fast ultra-high-performance-liquid chromatography-electrospray ionisation-triple-quadrupole-MS (UPLC-QqQ-MS), operated in the single reaction monitoring mode, as a readout system. Binding of the label to ERα-coated paramagnetic microbeads was inhibited by competing estrogens in the sample extract yielding decreased levels of the label in UPLC-QqQ-MS. The label showed high ionisation efficiency in positive electrospray ionisation (ESI) mode, so the developed BioMS approach is able to screen for estrogens in dietary supplements despite their poor ionisation efficiency in both positive and negative ESI modes. The assay was performed in a 96-well plate, and all these wells could be measured within 3 h. Estrogens in suspect extracts were identified by full-scan accurate mass and collision-cross section (CCS) values from a UPLC-ion mobility-Q-time-of-flight-MS (UPLC-IM-Q-ToF-MS) equipped with a novel atmospheric pressure ionisation source. Thanks to the novel ion source, this instrument provided picogram sensitivity for estrogens in the negative ion mode and an additional identification point (experimental CCS values) next to retention time, accurate mass and tandem mass spectrometry data. The developed combination of bioaffinity screening with UPLC-QqQ-MS and identification with UPLC-IM-Q-ToF-MS provides an extremely powerful analytical tool for early warning of ERα bioactive compounds in dietary supplements as demonstrated by analysis of selected dietary supplements in which different estrogens were identified.

  6. Improved single ion cyclotron resonance mass spectroscopy

    International Nuclear Information System (INIS)

    Boyce, K.R.

    1993-01-01

    The author has improved the state of the art for precision mass spectroscopy of a mass doublet to below one part in 10 10 . By alternately loading single ions into a Penning trap, the author has determined the mass ratio M(CO + )/M(N + 2 ) = 0.999 598 887 74(11), an accuracy of 1 x 10 -10 . This is a factor of 4 improvement over previous measurements, and a factor of 10 better than the 1985 atomic mass table adjustment [WAA85a]. Much of the author's apparatus has been rebuilt, increasing the signal-to-noise ratio and improving the reliability of the machine. The typical time needed to make and cool a single ion has been reduced from about half an hour to under 5 minutes. This was done by a combination of faster ion-making and a much faster procedure for driving out ions of the wrong species. The improved S/N, in combination with a much better signal processing algorithm to extract the ion phase and frequency from the author's data, has substantially reduced the time required for the actual measurements. This is important now that the measurement time is a substantial fraction of the cycle time (the time to make a new ion and measure it). The improvements allow over 30 comparisons in one night, compared to 2 per night previously. This not only improves the statistics, but eliminates the possibility of large non-Gaussian errors due to sudden magnetic field shifts

  7. MATS and LaSpec: High-precision experiments using ion traps and lasers at FAIR

    Science.gov (United States)

    Rodríguez, D.; Blaum, K.; Nörtershäuser, W.; Ahammed, M.; Algora, A.; Audi, G.; Äystö, J.; Beck, D.; Bender, M.; Billowes, J.; Block, M.; Böhm, C.; Bollen, G.; Brodeur, M.; Brunner, T.; Bushaw, B. A.; Cakirli, R. B.; Campbell, P.; Cano-Ott, D.; Cortés, G.; Crespo López-Urrutia, J. R.; Das, P.; Dax, A.; de, A.; Delheij, P.; Dickel, T.; Dilling, J.; Eberhardt, K.; Eliseev, S.; Ettenauer, S.; Flanagan, K. T.; Ferrer, R.; García-Ramos, J.-E.; Gartzke, E.; Geissel, H.; George, S.; Geppert, C.; Gómez-Hornillos, M. B.; Gusev, Y.; Habs, D.; Heenen, P.-H.; Heinz, S.; Herfurth, F.; Herlert, A.; Hobein, M.; Huber, G.; Huyse, M.; Jesch, C.; Jokinen, A.; Kester, O.; Ketelaer, J.; Kolhinen, V.; Koudriavtsev, I.; Kowalska, M.; Krämer, J.; Kreim, S.; Krieger, A.; Kühl, T.; Lallena, A. M.; Lapierre, A.; Le Blanc, F.; Litvinov, Y. A.; Lunney, D.; Martínez, T.; Marx, G.; Matos, M.; Minaya-Ramirez, E.; Moore, I.; Nagy, S.; Naimi, S.; Neidherr, D.; Nesterenko, D.; Neyens, G.; Novikov, Y. N.; Petrick, M.; Plaß, W. R.; Popov, A.; Quint, W.; Ray, A.; Reinhard, P.-G.; Repp, J.; Roux, C.; Rubio, B.; Sánchez, R.; Schabinger, B.; Scheidenberger, C.; Schneider, D.; Schuch, R.; Schwarz, S.; Schweikhard, L.; Seliverstov, M.; Solders, A.; Suhonen, M.; Szerypo, J.; Taín, J. L.; Thirolf, P. G.; Ullrich, J.; van Duppen, P.; Vasiliev, A.; Vorobjev, G.; Weber, C.; Wendt, K.; Winkler, M.; Yordanov, D.; Ziegler, F.

    2010-05-01

    -destructive Fourier-Transform Ion-Cyclotron-Resonance (FT-ICR) detection technique on single stored ions. This accuracy limit is important for fundamental interaction tests, but also allows for the study of the fine structure of the nuclear mass surface with unprecedented accuracy, whenever required. The use of the FT-ICR technique provides true single ion sensitivity. This is essential to access isotopes that are produced with minimum rates which are very often the most interesting ones. Instead of pushing for highest accuracy, the high charge state of the ions can also be used to reduce the storage time of the ions, hence making measurements on even shorter-lived isotopes possible. Decay studies in ion traps will become possible with MATS. Novel spectroscopic tools for in-trap high-resolution conversion-electron and charged-particle spectroscopy from carrier-free sources will be developed, aiming e.g. at the measurements of quadrupole moments and E0 strengths. With the possibility of both high-accuracy mass measurements of the shortest-lived isotopes and decay studies, the high sensitivity and accuracy potential of MATS is ideally suited for the study of very exotic nuclides that will only be produced at the FAIR facility.Laser spectroscopy of radioactive isotopes and isomers is an efficient and model-independent approach for the determination of nuclear ground and isomeric state properties. Hyperfine structures and isotope shifts in electronic transitions exhibit readily accessible information on the nuclear spin, magnetic dipole and electric quadrupole moments as well as root-mean-square charge radii. The dependencies of the hyperfine splitting and isotope shift on the nuclear moments and mean square nuclear charge radii are well known and the theoretical framework for the extraction of nuclear parameters is well established. These extracted parameters provide fundamental information on the structure of nuclei at the limits of stability. Vital information on both bulk and valence

  8. Evaluation of gas chromatography – electron ionization – full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

    International Nuclear Information System (INIS)

    Mol, Hans G.J.; Tienstra, Marc; Zomer, Paul

    2016-01-01

    Gas chromatography with electron ionization and full scan high resolution mass spectrometry with an Orbitrap mass analyzer (GC-EI-full scan Orbitrap HRMS) was evaluated for residue analysis. Pesticides in fruit and vegetables were taken as an example application. The relevant aspects for GC-MS based residue analysis, including the resolving power (15,000 to 120,000 FWHM at m/z 200), scan rate, dynamic range, selectivity, sensitivity, analyte identification, and utility of existing EI-libraries, are assessed and discussed in detail. The optimum acquisition conditions in full scan mode (m/z 50–500) were a resolving power of 60,000 and an automatic-gain-control target value of 3E6. These conditions provided (i) an optimum mass accuracy: within 2 ppm over a wide concentration range, with/without matrix, enabling the use of ±5 ppm mass extraction windows (ii) adequate scan speed: minimum 12 scans/peak, (iii) an intra-scan dynamic range sufficient to achieve LOD/LOQs ≤0.5 pg in fruit/vegetable matrices (corresponding to ≤0.5 μg kg"−"1) for most pesticides. EI-Orbitrap spectra were consistent over a very wide concentration range (5 orders) with good match values against NIST (EI-quadrupole) spectra. The applicability for quantitative residue analysis was verified by validation of 54 pesticides in three matrices (tomato, leek, orange) at 10 and 50 μg/kg. The method involved a QuEChERS-based extraction with a solvent switch into iso-octane, and 1 μL hot splitless injection into the GC-HRMS system. A recovery between 70 and 120% and a repeatability RSD <10% was obtained in most cases. Linearity was demonstrated for the range ≤5–250 μg kg"−"1. The pesticides could be identified according to the applicable EU criteria for GC-HRMS (SANTE/11945/2015). GC-EI-full scan Orbitrap HRMS was found to be highly suited for quantitative pesticide residue analysis. The potential of qualitative screening to extend the scope makes it an attractive alternative to

  9. Evaluation of gas chromatography – electron ionization – full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

    Energy Technology Data Exchange (ETDEWEB)

    Mol, Hans G.J., E-mail: hans.mol@wur.nl; Tienstra, Marc; Zomer, Paul

    2016-09-07

    Gas chromatography with electron ionization and full scan high resolution mass spectrometry with an Orbitrap mass analyzer (GC-EI-full scan Orbitrap HRMS) was evaluated for residue analysis. Pesticides in fruit and vegetables were taken as an example application. The relevant aspects for GC-MS based residue analysis, including the resolving power (15,000 to 120,000 FWHM at m/z 200), scan rate, dynamic range, selectivity, sensitivity, analyte identification, and utility of existing EI-libraries, are assessed and discussed in detail. The optimum acquisition conditions in full scan mode (m/z 50–500) were a resolving power of 60,000 and an automatic-gain-control target value of 3E6. These conditions provided (i) an optimum mass accuracy: within 2 ppm over a wide concentration range, with/without matrix, enabling the use of ±5 ppm mass extraction windows (ii) adequate scan speed: minimum 12 scans/peak, (iii) an intra-scan dynamic range sufficient to achieve LOD/LOQs ≤0.5 pg in fruit/vegetable matrices (corresponding to ≤0.5 μg kg{sup −1}) for most pesticides. EI-Orbitrap spectra were consistent over a very wide concentration range (5 orders) with good match values against NIST (EI-quadrupole) spectra. The applicability for quantitative residue analysis was verified by validation of 54 pesticides in three matrices (tomato, leek, orange) at 10 and 50 μg/kg. The method involved a QuEChERS-based extraction with a solvent switch into iso-octane, and 1 μL hot splitless injection into the GC-HRMS system. A recovery between 70 and 120% and a repeatability RSD <10% was obtained in most cases. Linearity was demonstrated for the range ≤5–250 μg kg{sup −1}. The pesticides could be identified according to the applicable EU criteria for GC-HRMS (SANTE/11945/2015). GC-EI-full scan Orbitrap HRMS was found to be highly suited for quantitative pesticide residue analysis. The potential of qualitative screening to extend the scope makes it an attractive

  10. High Time-Resolved Kinetic Temperatures of Solar Wind Minor Ions Measured with SOHO/CELIAS/CTOF

    Science.gov (United States)

    Janitzek, N. P.; Berger, L.; Drews, C.; Wimmer-Schweingruber, R. F.

    2017-12-01

    Solar wind heavy ions with an atomic number Z > 2 are referred to as minor ions since they represent a fraction of less than one percent of all solar wind ions. They can be therefore regarded as test particles, only reacting to but not driving the dynamics of the solar wind plasma, which makes them a unique diagnostic tool for plasma wave phenomena both in the solar atmosphere and the extended heliosphere. In the past, several studies have investigated the kinetic temperatures of minor ions, but due to low counting statistics these studies are based on ion velocity distribution functions (VDFs) recorded over time periods of several hours. The Charge Time-Of-Flight (CTOF) mass spectrometer as part of the Charge, ELement and Isotope Analysis System (CELIAS) onboard the SOlar and Heliospheric Observatory (SOHO) provides solar wind heavy ion 1D radial VDFs with excellent charge state separation, an unprecedented cadence of 5 minutes and very high counting statistics, exceeding similar state-of-the-art instruments by a factor of ten. In our study, based on CTOF measurements at Langrangian point L1 between DOY 150 and DOY 220 in 1996, we investigate systematically the influence of the VDF time resolution on the derived kinetic temperatures for solar wind silicon and iron ions. The selected ion set spans a wide range of mass-per-charge from 3 amu/e heavy ions with ion-cyclotron waves.

  11. The performance of atmospheric pressure gas chromatography-tandem mass spectrometry compared to gas chromatography-high resolution mass spectrometry for the analysis of polychlorinated dioxins and polychlorinated biphenyls in food and feed samples.

    Science.gov (United States)

    Ten Dam, Guillaume; Pussente, Igor Cabreira; Scholl, Georges; Eppe, Gauthier; Schaechtele, Alexander; van Leeuwen, Stefan

    2016-12-16

    Recently, gas chromatography tandem mass spectrometry (GC-MS/MS) has been added in European Union (EU) legislation as an alternative to magnetic sector high resolution mass spectrometry (HRMS) for the analysis of dioxins and dioxin like polychlorinated biphenyls (dl-PCB) in food and feed. In this study the performance of APGC-MS/MS compared to GC-HRMS is investigated and compared with EU legislation. The study includes the legislative parameters, relative intermediate precision standard deviation (S Rw ,rel), trueness, sensitivity, linear range and ion ratio tolerance. In addition, over 200 real samples of large variety and spanning several orders of magnitude in concentration were analyzed by both techniques and the selectivity was evaluated by comparing chromatograms. The S Rw ,rel and trueness were evaluated using (in-house) reference samples and fulfill to EU legislation, though the S Rw ,rel was better with GC-HRMS. The sensitivity was considerably better than of GC-HRMS while the linear range was similar. Ion ratios were mostly within the tolerable range of ±15%. A (temporary unresolved) systematic deviation in ion ratio was observed for several congeners, yet this did not lead to exceeding of the maximum ion ratio limits. The APGC-MS/MS results for the non-dioxin-like-PCBs (ndl-PCBs) were negatively biased, particularly for PCB138 and 153 in contaminated samples. The selectivity of APGC-MS/MS was lower for several matrices. Particularly for contaminated samples, interfering peaks were observed in the APGC chromatograms of the native compounds (dioxins) and labeled internal standards (PCBs). These can lead to biased results and ultimately to false positive samples. It was concluded that the determination of dioxins and PCBs using APGC-MS/MS meets the requirements set by the European Commission. However, due to generally better selectivity and S Rw ,rel, GC-HRMS is the preferred method for monitoring purposes. Copyright © 2016 Elsevier B.V. All rights

  12. Mass loss of evolved massive stars: the circumstellar environment at high angular resolution

    International Nuclear Information System (INIS)

    Montarges, Miguel

    2014-01-01

    Mass loss of evolved stars is still largely mysterious, despite its importance as the main evolution engine for the chemical composition of the interstellar medium. For red supergiants (RSG), the triggering of the outflow and the mechanism of dust condensation remain unknown. Concerning red giant stars, we still do not know how their mass loss is able to form a bipolar planetary nebula. During my PhD thesis, I observed evolved stars with high angular resolution techniques. They allowed us to study the surface and the close environment of these stars, from where mass loss originates. With near-infrared interferometric observations, I characterized the water vapor and carbon monoxide envelope of the nearby RSG Betelgeuse. I also monitored a hot spot on its surface and analyzed the structure of its convection, as well as that of Antares (another very nearby supergiant) thanks to radiative hydrodynamical simulations. Diffraction-limited imaging techniques (near-infrared adaptive optics, ultraviolet space telescope) allowed me to observe the evolution of inhomogeneities in the circumstellar envelope of Betelgeuse and to discover a circumstellar disk around L2 Puppis, an asymptotic giant branch star. These multi-scale and multi-wavelength observations obtained at several epochs allowed us to monitor the evolution of the structures and to derive information on the dynamics of the stellar environment. With a wider stellar sample expected in the next few years, this observing program will allow a better understanding of the mass loss of evolved stars. (author)

  13. Multicomponent mixed dopant optimization for rapid screening of polycyclic aromatic hydrocarbons using ultra high performance liquid chromatography coupled to atmospheric pressure photoionization high-resolution mass spectrometry

    KAUST Repository

    Sioud, Salim

    2012-05-04

    RATIONALE To enhance the ionization efficiencies in atmospheric pressure photoionization mass spectrometry a dopant with favorable ionization energy such as chlorobenzene is typically used. These dopants are typically toxic and difficult to mix with water-soluble organic solvents. In order to achieve a more efficient and less toxic dopant, a multicomponent mixed dopant was explored. METHODS A multicomponent mixed dopant for non-targeted rapid screening of polycyclic aromatic hydrocarbons (PAHs) was developed and optimized using ultra high performance liquid chromatography (UPLC) coupled to atmospheric pressure photoionization high-resolution mass spectrometry. Various single and multicomponent mixed dopants consisting of ethanol, chlorobenzene, bromobenzene, anisole and toluene were evaluated. RESULTS Fourteen out of eighteen PAHs were successfully separated and detected at low pg/μL levels within 5 min with high mass accuracy ≤4 ppm. The optimal mixed multicomponent dopant consisted of ethanol/chlorobenzene/bromobenzene/anisole (98.975:0.1:0.9:0.025, v/v %) and it improved the limit of detection (LOD) by 2- to 10-fold for the tested PAHs compared to those obtained with pure chlorobenzene. CONCLUSIONS A novel multicomponent dopant that contains 99% ethanol and 1% mixture of chlorobenzene, bromobenzene and anisole was found to be an effective dopant mixture to ionize PAHs. The developed UPLC multicomponent dopant assisted atmospheric pressure photoionization high-resolution mass spectrometry offered a rapid non targeted screening method for detecting the PAHs at low pg/;μL levels within a 5 min run time with high mass accuracy a;circ4 ppm. Copyright © 2012 John Wiley & Sons, Ltd.

  14. Chemical characterization of long-range transport biomass burning emissions to the Himalayas: insights from high-resolution aerosol mass spectrometry

    Science.gov (United States)

    Zhang, Xinghua; Xu, Jianzhong; Kang, Shichang; Liu, Yanmei; Zhang, Qi

    2018-04-01

    An intensive field measurement was conducted at a remote, background, high-altitude site (Qomolangma Station, QOMS, 4276 m a.s.l.) in the northern Himalayas, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) along with other collocated instruments. The field measurement was performed from 12 April to 12 May 2016 to chemically characterize the high time-resolved submicron particulate matter (PM1) and obtain the dynamic processes (emissions, transport, and chemical evolution) of biomass burning (BB), frequently transported from South Asia to the Himalayas during pre-monsoon season. Overall, the average (±1σ) PM1 mass concentration was 4.44 (±4.54) µg m-3 for the entire study, which is comparable with those observed at other remote sites worldwide. Organic aerosol (OA) was the dominant PM1 species (accounting for 54.3 % of total PM1 on average) followed by black carbon (BC) (25.0 %), sulfate (9.3 %), ammonium (5.8 %), nitrate (5.1 %), and chloride (0.4 %). The average size distributions of PM1 species all peaked at an overlapping accumulation mode (˜ 500 nm), suggesting that aerosol particles were internally well-mixed and aged during long-range transport. Positive matrix factorization (PMF) analysis on the high-resolution organic mass spectra identified three distinct OA factors, including a BB-related OA (BBOA, 43.7 %), a nitrogen-containing OA (NOA, 13.9 %) and a more-oxidized oxygenated OA (MO-OOA, 42.4 %). Two polluted episodes with enhanced PM1 mass loadings and elevated BBOA contributions from the west and southwest of QOMS during the study were observed. A typical BB plume was investigated in detail to illustrate the chemical evolution of aerosol characteristics under distinct air mass origins, meteorological conditions, and atmospheric oxidation processes.

  15. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, R.; Jilbert, T.; de Lange, G.J.; Reichart, G.J.

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (µm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

  16. Ion microprobe Sr isotope analysis of carbonates with about 5 μm spatial resolution: An example from an ayu otolith

    International Nuclear Information System (INIS)

    Sano, Yuji; Shirai, Kotaro; Takahata, Naoto; Amakawa, Hiroshi; Otake, Tsuguo

    2008-01-01

    A high lateral resolution secondary ion mass spectrometer (NanoSIMS NS50 ion microprobe) has been used to measure 87 Sr/ 86 Sr ratios in natural CaCO 3 samples. A ∼2 nA O - primary beam was used to sputter a 5-7-μm diameter crater on the sample surface and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. The multi-collector system was adjusted to detect 43 Ca + (by a detector EM2), 80 Ca 2 + (EM3), 86 Sr + (EM4), and 87 Sr + (EM4b) ions at the same time. Then the magnetic field was scanned for the EM4 to detect 85 Rb + , 86 Sr + and 87 Sr + , while the EM4b can measure 86 Sr + , 87 Sr + and 88 Sr + , respectively. A mass resolution of 3600 at 10% peak height was attained with a flat peak top, while the sensitivity of Sr was about 10 cps/nA/ppm. An aragonite sample (coral skeleton standard; JCp-1) was used as a reference for Sr isotope ratio calibration. Repeated analyses of the JCp-1 show that the 87 Sr/ 86 Sr ratio agrees well with the seawater signature within a precision of 0.3 per mille at 2σ, after the series of corrections such as the Ca dimer, 87 Rb, and a mass bias estimated by the 88 Sr/ 86 Sr ratio. The method was applied to an otolith (ear-stone) from ayu (Plecoglossus altivelis altivelis) collected from the Yodo river, Japan. Although experimental errors are relatively large, up to 3 per mille at 2σ, the ratios of the core region are higher than the seawater signature while more distal values agree well with seawater. The very outermost part again shows the relatively higher 87 Sr/ 86 Sr ratios. The spatial variation of 87 Sr/ 86 Sr ratios was consistent with amphidromous migration of the fish, namely, born in the lake and grown in the coastal sea and finally collected in a river

  17. Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.; Wolff, Jeremy J.; Somogyi, Árpád; Pedder, Randall E.; Quintyn, Royston S.; Morrison, Lindsay J.; Easterling, Michael L.; Paša-Tolić, Ljiljana; Wysocki, Vicki H.

    2017-01-03

    Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on non-covalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 kDa to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.

  18. Advances in high-resolution mass spectrometry based on metabolomics studies for food--a review.

    Science.gov (United States)

    Rubert, Josep; Zachariasova, Milena; Hajslova, Jana

    2015-01-01

    Food authenticity becomes a necessity for global food policies, since food placed in the market without fail has to be authentic. It has always been a challenge, since in the past minor components, called also markers, have been mainly monitored by chromatographic methods in order to authenticate the food. Nevertheless, nowadays, advanced analytical methods have allowed food fingerprints to be achieved. At the same time they have been also combined with chemometrics, which uses statistical methods in order to verify food and to provide maximum information by analysing chemical data. These sophisticated methods based on different separation techniques or stand alone have been recently coupled to high-resolution mass spectrometry (HRMS) in order to verify the authenticity of food. The new generation of HRMS detectors have experienced significant advances in resolving power, sensitivity, robustness, extended dynamic range, easier mass calibration and tandem mass capabilities, making HRMS more attractive and useful to the food metabolomics community, therefore becoming a reliable tool for food authenticity. The purpose of this review is to summarise and describe the most recent metabolomics approaches in the area of food metabolomics, and to discuss the strengths and drawbacks of the HRMS analytical platforms combined with chemometrics.

  19. Single photon imaging at ultra-high resolution

    Energy Technology Data Exchange (ETDEWEB)

    Bellazzini, R. [INFN sez. Pisa, Pisa (Italy); Spandre, G. [INFN sez. Pisa, Pisa (Italy)], E-mail: Gloria.Spandre@pi.infn.it; Minuti, M.; Brez, A.; Baldini, L.; Latronico, L.; Omodei, N.; Sgro, C.; Bregeon, J.; Razzano, M.; Pinchera, M. [INFN sez. Pisa, Pisa (Italy); Tremsin, A.; McPhate, J.; Vallerga, J.V.; Siegmund, O. [SSL, Berkeley (United States)

    2008-06-11

    We present a detection system capable of imaging both single photon/positive ion and multiple coincidence photons/positive ions with extremely high spatial resolution. In this detector the photoelectrons excited by the incoming photons are multiplied by microchannel plate(s) (MCP). The process of multiplication is spatially constrained within an MCP pore, which can be as small as 4 {mu}m for commercially available MCPs. An electron cloud originated by a single photoelectron is then encoded by a pixellated custom analog ASIC consisting of 105 K charge sensitive pixels of 50 {mu}m in size arranged on a hexagonal grid. Each pixel registers the charge with an accuracy of <100 electrons rms. Computation of the event centroid from the readout charges results in an accurate event position. A large number of simultaneous photons spatially separated by {approx}0.4 mm can be detected simultaneously allowing multiple coincidence operation for the experiments where a large number of incoming photons/positive ions have to be detected simultaneously. The experimental results prove that the spatial resolution of the readout system itself is {approx}3 {mu}m FWHM enabling detection resolution better than 6 {mu}m for the small pore MCPs. An attractive feature of the detection system is its capability to register the timing of each incoming photon/positive ion (in single photon detection mode) or of the first incoming particle (for the multiple coincidence detection) with an accuracy of {approx}130 ps FWHM. There is also virtually no dark count noise in the detection system making it suitable for low count rate applications.

  20. Investigation of bio-oil produced by hydrothermal liquefaction of food waste using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Kostyukevich, Yury; Vlaskin, Mikhail; Borisova, Ludmila; Zherebker, Alexander; Perminova, Irina; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

    2018-02-01

    Recent research has revealed that more than 1.3 billion tons of food is wasted globally every year. The disposal of such huge biomass has become a challenge. In the present paper, we report the production of the bio-oil by hydrothermal liquefaction of three classes of food waste: meat, cheese and fruits. The highest yield of the bio-oil was observed for meat (∼60%) and cheese (∼75%), while for fruits, it was considerably low (∼10%). The molecular composition of the obtained bio-oil was investigated using ultrahigh resolution Fourier Transform Ion Cyclotron Resonance mass spectrometry and was found to be similar to that obtained from algae. Several thousand heteroatom compounds (N, N 2 , ON 2 , etc. classes) were reliably identified from each sample. It was found that bio-oils produced from meat and cheese have many compounds (∼90%) with common molecular formulas, while bio-oil produced from fruits differs considerably (∼30% of compounds are unique).

  1. Current position of high-resolution MS for drug quantification in clinical & forensic toxicology.

    Science.gov (United States)

    Meyer, Markus R; Helfer, Andreas G; Maurer, Hans H

    2014-08-01

    This paper reviews high-resolution MS approaches published from January 2011 until March 2014 for the quantification of drugs (of abuse) and/or their metabolites in biosamples using LC-MS with time-of-flight or Orbitrap™ mass analyzers. Corresponding approaches are discussed including sample preparation and mass spectral settings. The advantages and limitations of high-resolution MS for drug quantification, as well as the demand for a certain resolution or a specific mass accuracy are also explored.

  2. Concept for high-charge-state ion induction accelerators

    International Nuclear Information System (INIS)

    Logan, B.G.; Perry, M.D.; Caporaso, G.J.

    1996-01-01

    This work describes a particular concept for ion induction linac accelerators using high-charge-state ions produced by an intense, short pulse laser, and compares the costs of a modular driver system producing 6.5 MJ for a variety of ion masses and charge states using a simple but consistent cost model

  3. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, Rick; Jilbert, Tom; Mason, Paul R D; de Lange, Gert J.; Reichart, Gert Jan

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (μm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

  4. Application of selected ion monitoring to the analysis of triacylglycerols in olive oil by high temperature-gas chromatography/mass spectrometry.

    Science.gov (United States)

    Ruiz-Samblás, C; González-Casado, A; Cuadros-Rodríguez, L; García, F P Rodríguez

    2010-06-30

    The analysis of the triacylglycerol (TAG) composition of oils is a very challenging task, since the TAGs have very similar physico-chemical properties. In this work, a high temperature-gas chromatographic method coupled to electron ionization-mass spectrometry (HT-GC/EI-MS), in the Selected Ion Monitoring (SIM) mode, method was developed for the analysis of TAGs in the olive oil; this is a method suitable for routine analysis. This method was developed using commercially available standard TAGs. The TAGs studied were separated according to their equivalent carbon number and degree of unsaturation. The peak assignment was carried out by locating the characteristic fragment ions having the same retention time on the SIM profile such as [RCO+74](+) and [RCO+128](+) ions, due to the fatty acyl residues on sn-1, sn-2 and sn-3 positions of the TAG molecule and the [M-OCOR](+) ions corresponding to the acyl ions. The developed method was very useful to eliminate the interferences that appeared in the mass spectrum since electron ionization can prevent satisfactory interpretation of spectra. Copyright 2010 Elsevier B.V. All rights reserved.

  5. Calibration of the OHREX high-resolution imaging crystal spectrometer at the Livermore electron beam ion traps

    Energy Technology Data Exchange (ETDEWEB)

    Hell, N. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Dr. Remeis-Sternwarte and ECAP, Universität Erlangen-Nürnberg, Bamberg 96049 (Germany); Beiersdorfer, P.; Magee, E. W.; Brown, G. V. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States)

    2016-11-15

    We report the calibration of the Orion High-Resolution X-ray (OHREX) imaging crystal spectrometer at the EBIT-I electron beam ion trap at Livermore. Two such instruments, dubbed OHREX-1 and OHREX-2, are fielded for plasma diagnostics at the Orion laser facility in the United Kingdom. The OHREX spectrometer can simultaneously house two spherically bent crystals with a radius of curvature of r = 67.2 cm. The focusing properties of the spectrometer allow both for larger distance to the source due to the increase in collected light and for observation of extended sources. OHREX is designed to cover a 2.5°–3° spectral range at Bragg angles around 51.3°. The typically high resolving powers at these large Bragg angles are ideally suited for line shape diagnostics. For instance, the nominal resolving power of the instrument (>10 000) is much higher than the effective resolving power associated with the Doppler broadening due to the temperature of the trapped ions in EBIT-I. The effective resolving power is only around 3000 at typical EBIT-I conditions, which nevertheless is sufficient to set up and test the instrument’s spectral characteristics. We have calibrated the spectral range for a number of crystals using well known reference lines in the first and second order and derived the ion temperatures from these lines. We have also made use of the 50 μm size of the EBIT-I source width to characterize the spatial focusing of the spectrometer.

  6. Organic environments on Saturn's moon, Titan: simulating chemical reactions and analyzing products by FT-ICR and ion-trap mass spectrometry.

    Science.gov (United States)

    Somogyi, Arpad; Oh, Chu-Ha; Smith, Mark A; Lunine, Jonathan I

    2005-06-01

    Laboratory simulations have been carried out to model chemical reactions that possibly take place in the stratosphere of Saturn's moon, Titan. The aerosol products of these reactions (tholin samples) have been systematically analyzed by mass spectrometry using electrospray ionization (ESI) and laser desorption (LD). A wide variety of ions with a general formula C(x)H(y)N(z) detected by ultrahigh resolution and accurate mass measurements in a Fourier transform/ion cyclotron resonance (FT-ICR) cell reflect the complexity of these polymeric products, both in chemical compositions and isomeric distributions. As a common feature, however, tandem mass spectral (MS/MS) data and H/D exchange products in the solution phase support the presence of amino and nitrile functionalities in these (highly unsaturated) "tholin" compounds. The present work demonstrates that ESI-MS coupled with FT-ICR is a suitable and "intact" method to analyze tholin components formed under anaerobic conditions; only species with C(x)H(y)N(z) are detected for freshly prepared and harvested samples. However, when intentionally exposed to water, oxygen-containing compounds are unambiguously detected.

  7. High-mass twins & resolution of the reconfinement, masquerade and hyperon puzzles of compact star interiors

    International Nuclear Information System (INIS)

    Blaschke, David; Alvarez-Castillo, David E.

    2016-01-01

    We aim at contributing to the resolution of three of the fundamental puzzles related to the still unsolved problem of the structure of the dense core of compact stars (CS): (i) the hyperon puzzle: how to reconcile pulsar masses of 2 M ⊙ with the hyperon softening of the equation of state (EoS); (ii) the masquerade problem: modern EoS for cold, high density hadronic and quark matter are almost identical; and (iii) the reconfinement puzzle: what to do when after a deconfinement transition the hadronic EoS becomes favorable again? We show that taking into account the compositeness of baryons (by excluded volume and/or quark Pauli blocking) on the hadronic side and confining and stiffening effects on the quark matter side results in an early phase transition to quark matter with sufficient stiffening at high densities which removes all three present-day puzzles of CS interiors. Moreover, in this new class of EoS for hybrid CS falls the interesting case of a strong first order phase transition which results in the observable high mass twin star phenomenon, an astrophysical observation of a critical endpoint in the QCD phase diagram

  8. Identification of ortho-Substituted Benzoic Acid/Ester Derivatives via the Gas-Phase Neighboring Group Participation Effect in (+)-ESI High Resolution Mass Spectrometry.

    Science.gov (United States)

    Blincoe, William D; Rodriguez-Granillo, Agustina; Saurí, Josep; Pierson, Nicholas A; Joyce, Leo A; Mangion, Ian; Sheng, Huaming

    2018-04-01

    Benzoic acid/ester/amide derivatives are common moieties in pharmaceutical compounds and present a challenge in positional isomer identification by traditional tandem mass spectrometric analysis. A method is presented for exploiting the gas-phase neighboring group participation (NGP) effect to differentiate ortho-substituted benzoic acid/ester derivatives with high resolution mass spectrometry (HRMS 1 ). Significant water/alcohol loss (>30% abundance in MS 1 spectra) was observed for ortho-substituted nucleophilic groups; these fragment peaks are not observable for the corresponding para and meta-substituted analogs. Experiments were also extended to the analysis of two intermediates in the synthesis of suvorexant (Belsomra) with additional analysis conducted with nuclear magnetic resonance (NMR), density functional theory (DFT), and ion mobility spectrometry-mass spectrometry (IMS-MS) studies. Significant water/alcohol loss was also observed for 1-substituted 1, 2, 3-triazoles but not for the isomeric 2-substituted 1, 2, 3-triazole analogs. IMS-MS, NMR, and DFT studies were conducted to show that the preferred orientation of the 2-substituted triazole rotamer was away from the electrophilic center of the reaction, whereas the 1-subtituted triazole was oriented in close proximity to the center. Abundance of NGP product was determined to be a product of three factors: (1) proton affinity of the nucleophilic group; (2) steric impact of the nucleophile; and (3) proximity of the nucleophile to carboxylic acid/ester functional groups. Graphical Abstract ᅟ.

  9. An algorithm to correct saturated mass spectrometry ion abundances for enhanced quantitation and mass accuracy in omic studies

    Energy Technology Data Exchange (ETDEWEB)

    Bilbao, Aivett; Gibbons, Bryson C.; Slysz, Gordon W.; Crowell, Kevin L.; Monroe, Matthew E.; Ibrahim, Yehia M.; Smith, Richard D.; Payne, Samuel H.; Baker, Erin S.

    2018-04-01

    The mass accuracy and peak intensity of ions detected by mass spectrometry (MS) measurements are essential to facilitate compound identification and quantitation. However, high concentration species can easily cause problems if their ion intensities reach beyond the limits of the detection system, leading to distorted and non-ideal detector response (e.g. saturation), and largely precluding the calculation of accurate m/z and intensity values. Here we present an open source computational method to correct peaks above a defined intensity (saturated) threshold determined by the MS instrumentation such as the analog-to-digital converters or time-to-digital converters used in conjunction with time-of-flight MS. In this method, the isotopic envelope for each observed ion above the saturation threshold is compared to its expected theoretical isotopic distribution. The most intense isotopic peak for which saturation does not occur is then utilized to re-calculate the precursor m/z and correct the intensity, resulting in both higher mass accuracy and greater dynamic range. The benefits of this approach were evaluated with proteomic and lipidomic datasets of varying complexities. After correcting the high concentration species, reduced mass errors and enhanced dynamic range were observed for both simple and complex omic samples. Specifically, the mass error dropped by more than 50% in most cases with highly saturated species and dynamic range increased by 1-2 orders of magnitude for peptides in a blood serum sample.

  10. Ion mobility spectrometer / mass spectrometer (IMS-MS).

    Energy Technology Data Exchange (ETDEWEB)

    Hunka Deborah Elaine; Austin, Daniel E.

    2005-07-01

    The use of Ion Mobility Spectrometry (IMS) in the Detection of Contraband Sandia researchers use ion mobility spectrometers for trace chemical detection and analysis in a variety of projects and applications. Products developed in recent years based on IMS-technology include explosives detection personnel portals, the Material Area Access (MAA) checkpoint of the future, an explosives detection vehicle portal, hand-held detection systems such as the Hound and Hound II (all 6400), micro-IMS sensors (1700), ordnance detection (2500), and Fourier Transform IMS technology (8700). The emphasis to date has been on explosives detection, but the detection of chemical agents has also been pursued (8100 and 6400). Combining Ion Mobility Spectrometry (IMS) with Mass Spectrometry (MS) is described. The IMS-MS combination overcomes several limitations present in simple IMS systems. Ion mobility alone is insufficient to identify an unknown chemical agent. Collision cross section, upon which mobility is based, is not sufficiently unique or predictable a priori to be able to make a confident peak assignment unless the compounds present are already identified. Molecular mass, on the other hand, is much more readily interpreted and related to compounds. For a given compound, the molecular mass can be determined using a pocket calculator (or in one's head) while a reasonable value of the cross-section might require hours of computation time. Thus a mass spectrum provides chemical specificity and identity not accessible in the mobility spectrum alone. In addition, several advanced mass spectrometric methods, such as tandem MS, have been extensively developed for the purpose of molecular identification. With an appropriate mass spectrometer connected to an ion mobility spectrometer, these advanced identification methods become available, providing greater characterization capability.

  11. Image resolution influence on determination of resin injection rock mass

    Science.gov (United States)

    Wang, Weixing; Hakami, Eva

    2006-01-01

    In the context of nuclear waste repositories, an important approach to understanding brittle rock mass behavior to integrate new and powerful observational and numerical methods with multi-functional 3-D imaging and visualization techniques. Since 1994, Swedish Nuclear Fuel and Waste Management Company (SKB) have identified the need for a better understanding of radionuclide transport and retention processes in fractured rock. As a cooperation project between Sweden and China, we sampled a number of rock specimens for analyze rock fracture network by optical image technique. The samples are resin injected, in which way; opened fractures can be seen clearly by means of UV (Ultraviolet) light illumination. In the study period, we used different optical focuses to obtain the images from the same samples; we found that Image resolution influences on porosity determination of resin injected rock mass. This paper presents and discusses the six issues based on our research results: (1) Fracture porosity increases as camera focus distance decreases; (2) Porosity increases as illumination increases in resin injected fracture images; (3) To roughly estimate the porosity, the low resolution image can be used; (4) To collect more details of fracture information, the high resolution image is needed; (5) The resolution of image should be determined based on the aim of fracture analysis; (6) To acquire high resolution image, constructing a special illumination (standard) box maybe helpful to avoid light reflection and diffusion.

  12. An improved experimental scheme for simultaneous measurement of high-resolution zero electron kinetic energy (ZEKE) photoelectron and threshold photoion (MATI) spectra

    Science.gov (United States)

    Michels, François; Mazzoni, Federico; Becucci, Maurizio; Müller-Dethlefs, Klaus

    2017-10-01

    An improved detection scheme is presented for threshold ionization spectroscopy with simultaneous recording of the Zero Electron Kinetic Energy (ZEKE) and Mass Analysed Threshold Ionisation (MATI) signals. The objective is to obtain accurate dissociation energies for larger molecular clusters by simultaneously detecting the fragment and parent ion MATI signals with identical transmission. The scheme preserves an optimal ZEKE spectral resolution together with excellent separation of the spontaneous ion and MATI signals in the time-of-flight mass spectrum. The resulting improvement in sensitivity will allow for the determination of dissociation energies in clusters with substantial mass difference between parent and daughter ions.

  13. Characterization of chemical constituents in Rhodiola Crenulate by high-performance liquid chromatography coupled with Fourier-transform ion cyclotron resonance mass spectrometer (HPLC-FT-ICR MS).

    Science.gov (United States)

    Han, Fei; Li, Yanting; Mao, Xinjuan; Xu, Rui; Yin, Ran

    2016-05-01

    In this work, an approach using high-performance liquid chromatography coupled with diode-array detection and Fourier-transform ion cyclotron resonance mass spectrometer (HPLC-FT-ICR MS) for the identification and profiling of chemical constituents in Rhodiola crenulata was developed for the first time. The chromatographic separation was achieved on an Inertsil ODS-3 column (150 mm × 4.6 mm,3 µm) using a gradient elution program, and the detection was performed on a Bruker Solarix 7.0 T mass spectrometer equipped with electrospray ionization source in both positive and negative modes. Under the optimized conditions, a total of 48 chemical compounds, including 26 alcohols and their glycosides, 12 flavonoids and their glycosides, 5 flavanols and gallic acid derivatives, 4 organic acids and 1 cyanogenic glycoside were identified or tentatively characterized. The results indicated that the developed HPLC-FT-ICR MS method with ultra-high sensitivity and resolution is suitable for identifying and characterizing the chemical constituents in R. crenulata. And it provides a helpful chemical basis for further research on R. crenulata. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  14. Multifactorial Understanding of Ion Abundance in Tandem Mass Spectrometry Experiments.

    Science.gov (United States)

    Fazal, Zeeshan; Southey, Bruce R; Sweedler, Jonathan V; Rodriguez-Zas, Sandra L

    2013-01-29

    In a bottom-up shotgun approach, the proteins of a mixture are enzymatically digested, separated, and analyzed via tandem mass spectrometry. The mass spectra relating fragment ion intensities (abundance) to the mass-to-charge are used to deduce the amino acid sequence and identify the peptides and proteins. The variables that influence intensity were characterized using a multi-factorial mixed-effects model, a ten-fold cross-validation, and stepwise feature selection on 6,352,528 fragment ions from 61,543 peptide ions. Intensity was higher in fragment ions that did not have neutral mass loss relative to any mass loss or that had a +1 charge state. Peptide ions classified for proton mobility as non-mobile had lowest intensity of all mobility levels. Higher basic residue (arginine, lysine or histidine) counts in the peptide ion and low counts in the fragment ion were associated with lower fragment ion intensities. Higher counts of proline in peptide and fragment ions were associated with lower intensities. These results are consistent with the mobile proton theory. Opposite trends between peptide and fragment ion counts and intensity may be due to the different impact of factor under consideration at different stages of the MS/MS experiment or to the different distribution of observations across peptide and fragment ion levels. Presence of basic residues at all three positions next to the fragmentation site was associated with lower fragment ion intensity. The presence of proline proximal to the fragmentation site enhanced fragmentation and had the opposite trend when located distant from the site. A positive association between fragment ion intensity and presence of sulfur residues (cysteine and methionine) on the vicinity of the fragmentation site was identified. These results highlight the multi-factorial nature of fragment ion intensity and could improve the algorithms for peptide identification and the simulation in tandem mass spectrometry experiments.

  15. High-throughput screening and confirmation of 22 banned veterinary drugs in feedstuffs using LC-MS/MS and high-resolution Orbitrap mass spectrometry.

    Science.gov (United States)

    Wang, Xufeng; Liu, Yanghong; Su, Yijuan; Yang, Jianwen; Bian, Kui; Wang, Zongnan; He, Li-Min

    2014-01-15

    A new analytical strategy based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) combined with accurate mass high-resolution Orbitrap mass spectrometry (HR-Orbitrap MS) was performed for high-throughput screening, confirmation, and quantification of 22 banned or unauthorized veterinary drugs in feedstuffs according to Bulletin 235 of the Ministry of Agriculture, China. Feed samples were extracted with acidified acetonitrile, followed by cleanup using solid-phase extraction cartridge. The extracts were first screened by LC-MS/MS in a single selected reaction monitoring mode. The suspected positive samples were subjected to a specific pretreatment for confirmation and quantification of analyte of interest with LC-MS/MS and HR-Orbitrap MS. Mean recoveries for all target analytes (except for carbofuran and chlordimeform, which were about 35 and 45%, respectively) ranged from 52.2 to 90.4%, and the relative standard deviations were screening of real samples obtained from local feed markets and confirmation of the suspected target analytes. It provides a high-throughput, sensitive, and reliable screening, identification, and quantification of banned veterinary drugs in routine monitoring programs of feedstuffs.

  16. Metabolite localization by atmospheric pressure high-resolution scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging in whole-body sections and individual organs of the rove beetle Paederus riparius.

    Science.gov (United States)

    Bhandari, Dhaka Ram; Schott, Matthias; Römpp, Andreas; Vilcinskas, Andreas; Spengler, Bernhard

    2015-03-01

    Mass spectrometry imaging provides for non-targeted, label-free chemical imaging. In this study, atmospheric pressure high-resolution scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) was used for the first time to describe the chemical distribution of the defensive compounds pederin, pseudopederin, and pederon in tissue sections (16 μm thick) of the rove beetle Paederus riparius. The whole-insect tissue section was scanned with a 20-μm step size. Mass resolution of the orbital trapping mass spectrometer was set to 100,000 at m/z 200. Additionally, organ-specific compounds were identified for brain, nerve cord, eggs, gut, ovaries, and malpighian tubules. To confirm the distribution of the specific compounds, individual organs from the insect were dissected, and MSI experiments were performed on the dissected organs. Three ganglia of the nerve cord, with a dimension of 250-500 μm, were measured with 10-μm spatial resolution. High-quality m/z images, based on high spatial resolution and high mass accuracy were generated. These features helped to assign mass spectral peaks with high confidence. Mass accuracy of the imaging experiments was section. Without any labeling, we assigned key lipids for specific organs to describe their location in the body and to identify morphological structures with a specificity higher than with staining or immunohistology methods.

  17. Ion-neutral transport through quadrupole interfaces of mass-spectrometer systems

    International Nuclear Information System (INIS)

    Jugroot, M.; Groth, C.P.T.; Thomson, B.A.; Baranov, V.; Collings, B.A.; French, J.B.

    2004-01-01

    The transport of free ions through highly under-expanded jet flows of neutral gases and in the presence of applied electric fields is investigated by continuum-based numerical simulations. In particular, numerical results are described which are relevant to ion flows occurring in quadrupole interfaces of mass spectrometer systems. A five-moment mathematical model and parallel multi-block numerical solution procedure is developed for predicting the ion transport. The model incorporates the effects of ion-neutral collision processes and is used in conjunction with a Navier-Stokes model and flow solver for the neutral gas to examine the key influences controlling the ion motion. The effects of the neutral gas flow, electric fields (both dc and rf), and flow field geometry on ion mobility are carefully assessed. The capability of controlling the charged particle motions through a combination of directed neutral flow and applied electric field is demonstrated for these high-speed, hypersonic, jet flows. (author)

  18. Coupling of gas chromatography and electrospray ionization high resolution mass spectrometry for the analysis of anabolic steroids as trimethylsilyl derivatives in human urine.

    Science.gov (United States)

    Cha, Eunju; Jeong, Eun Sook; Cha, Sangwon; Lee, Jaeick

    2017-04-29

    In this study, gas chromatography (GC) was interfaced with high resolution mass spectrometry (HRMS) with electrospray ionization source (ESI) and the relevant parameters were investigated to enhance the ionization efficiency. In GC-ESI, the distances (x-, y- and z) and angle between the ESI needle, GC capillary column and MS orifice were set to 7 (x-distance), 4 (y-distance), and 1 mm (z-distance). The ESI spray solvent, acid modifier and nebulizer gas flow were methanol, 0.1% formic acid and 5 arbitrary units, respectively. Based on these results, analytical conditions for GC-ESI/HRMS were established. In particular, the results of spray solvent flow indicated a concentration-dependent mechanism (peak dilution effect), and other parameters also greatly influenced the ionization performance. The developed GC-ESI/HRMS was then applied to the analysis of anabolic steroids as trimethylsilyl (TMS) derivatives in human urine to demonstrate its application. The ionization profiles of TMS-derivatized steroids were investigated and compared with those of underivatized steroids obtained from gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS). The steroids exhibited ionization profiles based on their structural characteristics, regardless of the analyte phase or derivatization. Groups I and II with conjugated or unconjugated keto functional groups at C3 generated the [M+H] + and [M+H-TMS] + ions, respectively. On the other hand, Groups III and IV gave rise to the characteristic fragment ions [M+H-TMS-H 2 O] + and [M+H-2TMS-H 2 O] + , corresponding to loss of a neutral TMS·H 2 O moiety from the protonated molecular ion by in-source dissociation. To the best of our knowledge, this is the first study to successfully ionize and analyze steroids as TMS derivatives using ESI coupled with GC. The present system has enabled the ionization of TMS derivatives under ESI conditions

  19. High-definition velocity-space tomography of fast-ion dynamics

    DEFF Research Database (Denmark)

    Salewski, Mirko; Geiger, B.; Jacobsen, A.S.

    2016-01-01

    Velocity-space tomography of the fast-ion distribution function in a fusion plasma is usually a photon-starved tomography method due to limited optical access and signal-to-noise ratio of fast-ion Dα (FIDA) spectroscopy as well as the strive for high-resolution images. In high-definition tomography...... information to reconstruct where in velocity space the measurements and the simulation disagree. This alternative approach is demonstrated for four-view as well as for two-view FIDA measurements. The high-definition tomography tools allow us to study fast ions in sawtoothing plasmas and the formation of NBI...

  20. TEM Imaging of Mass-selected Polymer Molecules

    International Nuclear Information System (INIS)

    Nasibulin, Albert G.; Kauppinen, Esko I.; Thomson, Bruce A.; Fernandez de la Mora, J.

    2002-01-01

    Polyethylene glycol (PEG) molecules with masses below 1300 amu are electrosprayed (ES) from solution, mobility-selected at high resolution in a differential mobility analyzer (DMA), collected on a grid and imaged by transmission electron microscopy (ES-DMA-TEM). The DMA resolves individual n-mers, and selects only one out of the many present in the original sample. Ion identity is established from parallel mass spectra (ES-MS). The images reveal spherical particles 1.46 nm in diameter, in good agreement with the known ion mass and bulk density. The DMA-selection technique opens new paths for the study of very small particles

  1. In-depth glycoproteomic characterization of γ-conglutin by high-resolution accurate mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Silvia Schiarea

    Full Text Available The molecular characterization of bioactive food components is necessary for understanding the mechanisms of their beneficial or detrimental effects on human health. This study focused on γ-conglutin, a well-known lupin seed N-glycoprotein with health-promoting properties and controversial allergenic potential. Given the importance of N-glycosylation for the functional and structural characteristics of proteins, we studied the purified protein by a mass spectrometry-based glycoproteomic approach able to identify the structure, micro-heterogeneity and attachment site of the bound N-glycan(s, and to provide extensive coverage of the protein sequence. The peptide/N-glycopeptide mixtures generated by enzymatic digestion (with or without N-deglycosylation were analyzed by high-resolution accurate mass liquid chromatography-multi-stage mass spectrometry. The four main micro-heterogeneous variants of the single N-glycan bound to γ-conglutin were identified as Man2(Xyl (Fuc GlcNAc2, Man3(Xyl (Fuc GlcNAc2, GlcNAcMan3(Xyl (Fuc GlcNAc2 and GlcNAc 2Man3(Xyl (Fuc GlcNAc2. These carry both core β1,2-xylose and core α1-3-fucose (well known Cross-Reactive Carbohydrate Determinants, but corresponding fucose-free variants were also identified as minor components. The N-glycan was proven to reside on Asn131, one of the two potential N-glycosylation sites. The extensive coverage of the γ-conglutin amino acid sequence suggested three alternative N-termini of the small subunit, that were later confirmed by direct-infusion Orbitrap mass spectrometry analysis of the intact subunit.

  2. In situ investigation of ion-induced dewetting of a thin iron-oxide film on silicon by high resolution scanning electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Amirthapandian, S. [Institut fuer Halbleiteroptik und Funktionelle Grenzflaechen, Universitaet Stuttgart, 70569 Stuttgart (Germany); Material Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Schuchart, F.; Garmatter, D.; Bolse, W. [Institut fuer Halbleiteroptik und Funktionelle Grenzflaechen, Universitaet Stuttgart, 70569 Stuttgart (Germany)

    2012-11-15

    Using our new in situ high resolution scanning electron microscope, which is integrated into the UNILAC ion beamline at the Helmholtzzentrum fuer Schwerionenforschung (GSI) in Darmstadt, Germany, we investigated the swift heavy ion induced dewetting of a thin iron oxide layer on Si. Besides heterogeneous hole nucleation at defects and spontaneous (homogeneous) hole nucleation, we could clearly identify a dewetting mechanism, which is similar to the spinodal dewetting observed for liquid films. Instead of being due to capillary waves, it is based on a stress induced surface instability. The latter results in the formation of a wavy surface with constant dominant wave-length and increasing amplitude during ion irradiation. Dewetting sets in as soon as the wave-troughs reach the film-substrate interface. Inspection of the hole radii and rim shapes indicates that removal of the material from the hole area occurs mainly by plastic deformation at the inner boundary and ion induced viscous flow in the peripheral zone due to surface tension.

  3. The mass of $^{22}$Mg and a concept for a novel laser ion source trap

    CERN Document Server

    Mukherjee, Manas

    Clean and high-quality radioactive ion beams can be prepared by combining ion trap and resonance laser ionization techniques. A feasibility study for such a laser ion source trap has been carried out which shows enormous improvement in the beam emittance, purity, and in addition allows for a variation of the ion beam time structure. Direct high-precision mass measurements around mass number A=22 are of utmost importance. First, the masses of the superallowed $\\beta$-emitter $^{22}$Mg and its daughter $^{22}$Na are needed to test the conserved-vector-current(CVC) hypothesis and the Cabibbo-Kobayashi-Maskawa(CKM) matrix unitarity, both being predictions of the Standard Model. Second, to calculate the reaction rate of $^{21}$Na($p,\\gamma$)$^{22}$Mg the involved masses are required very accurately. This rate is needed in order to extract an upper limit on the amount of a characteristic $\\gamma$-radiation emitted from classical nova bursts which has been searched for but not yet detected. At the triple trap mass s...

  4. Characterizing filaments in regions of high-mass star formation: High-resolution submilimeter imaging of the massive star-forming complex NGC 6334 with ArTéMiS

    Science.gov (United States)

    André, Ph.; Revéret, V.; Könyves, V.; Arzoumanian, D.; Tigé, J.; Gallais, P.; Roussel, H.; Le Pennec, J.; Rodriguez, L.; Doumayrou, E.; Dubreuil, D.; Lortholary, M.; Martignac, J.; Talvard, M.; Delisle, C.; Visticot, F.; Dumaye, L.; De Breuck, C.; Shimajiri, Y.; Motte, F.; Bontemps, S.; Hennemann, M.; Zavagno, A.; Russeil, D.; Schneider, N.; Palmeirim, P.; Peretto, N.; Hill, T.; Minier, V.; Roy, A.; Rygl, K. L. J.

    2016-07-01

    Context. Herschel observations of nearby molecular clouds suggest that interstellar filaments and prestellar cores represent two fundamental steps in the star formation process. The observations support a picture of low-mass star formation according to which filaments of ~0.1 pc width form first in the cold interstellar medium, probably as a result of large-scale compression of interstellar matter by supersonic turbulent flows, and then prestellar cores arise from gravitational fragmentation of the densest filaments. Whether this scenario also applies to regions of high-mass star formation is an open question, in part because the resolution of Herschel is insufficient to resolve the inner width of filaments in the nearest regions of massive star formation. Aims: In an effort to characterize the inner width of filaments in high-mass star-forming regions, we imaged the central part of the NGC 6334 complex at a resolution higher by a factor of >3 than Herschel at 350 μm. Methods: We used the large-format bolometer camera ArTéMiS on the APEX telescope and combined the high-resolution ArTéMiS data at 350 μm with Herschel/HOBYS data at 70-500 μm to ensure good sensitivity to a broad range of spatial scales. This allowed us to study the structure of the main narrow filament of the complex with a resolution of 8″ or Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory.The final ArTéMiS+SPIRE 350 μm map (Fig. 1b) is available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/592/A54

  5. Development of a new screening method for the detection of antibiotic residues in muscle tissues using liquid chromatography and high resolution mass spectrometry with a LC-LTQ-Orbitrap instrument.

    OpenAIRE

    2011-01-01

    Abstract In the present work, a liquid chromatography- high resolution mass spectrometry method was developed for the screening in meat of a wide range of antibiotics used in veterinary medicine. Full scan mode under high resolution mass spectral conditions using LTQ-Orbitrap mass spectrometer with resolving power 60.000 FWHM was applied for analysis of the samples. Samples were prepared using two extractions protocols prior to LC-MS analysis. The scope of the method focuses on the...

  6. Complementary scattered and recoiled ion data from TOF-E heavy ion elastic recoil detection analysis

    International Nuclear Information System (INIS)

    Johnston, P.N.; El Bouanani, M.; Stannard, W.B.; Bubb, I.F.; Cohen, D.D.; Dytlewski, N.; Siegele, R.

    1998-01-01

    The advantage of Time of Flight and Energy (ToF-E) Heavy Ion Elastic Recoil Detection Analysis (HIERDA) over Rutherford Backscattering (RBS) analysis is its mass and energy dispersive capabilities. The mass resolution of ToF-E HIERDA deteriorates for very heavy elements. The limitation is related to the poor energy resolution of Si detectors for heavy ions. While the energy spectra from ToF-E HIERDA data are normally used to extract depth profiles, this work discusses the benefits of using the time spectra of both the recoiled and the scattered ions for depth profiling. The simulation of the complementary scattered and recoiled ion time spectra improves depth profiling and reduced current limitations when dealing with very heavy ions, such as Pt, Bi, Ta. (authors)

  7. An improved pseudotargeted metabolomics approach using multiple ion monitoring with time-staggered ion lists based on ultra-high performance liquid chromatography/quadrupole time-of-flight mass spectrometry.

    Science.gov (United States)

    Wang, Yang; Liu, Fang; Li, Peng; He, Chengwei; Wang, Ruibing; Su, Huanxing; Wan, Jian-Bo

    2016-07-13

    Pseudotargeted metabolomics is a novel strategy integrating the advantages of both untargeted and targeted methods. The conventional pseudotargeted metabolomics required two MS instruments, i.e., ultra-high performance liquid chromatography/quadrupole-time- of-flight mass spectrometry (UHPLC/Q-TOF MS) and UHPLC/triple quadrupole mass spectrometry (UHPLC/QQQ-MS), which makes method transformation inevitable. Furthermore, the picking of ion pairs from thousands of candidates and the swapping of the data between two instruments are the most labor-intensive steps, which greatly limit its application in metabolomic analysis. In the present study, we proposed an improved pseudotargeted metabolomics method that could be achieved on an UHPLC/Q-TOF/MS instrument operated in the multiple ion monitoring (MIM) mode with time-staggered ion lists (tsMIM). Full scan-based untargeted analysis was applied to extract the target ions. After peak alignment and ion fusion, a stepwise ion picking procedure was used to generate the ion lists for subsequent single MIM and tsMIM. The UHPLC/Q-TOF tsMIM MS-based pseudotargeted approach exhibited better repeatability and a wider linear range than the UHPLC/Q-TOF MS-based untargeted metabolomics method. Compared to the single MIM mode, the tsMIM significantly increased the coverage of the metabolites detected. The newly developed method was successfully applied to discover plasma biomarkers for alcohol-induced liver injury in mice, which indicated its practicability and great potential in future metabolomics studies. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Investigation of gas discharge ion sources for on-line mass separation

    International Nuclear Information System (INIS)

    Kirchner, R.

    1976-03-01

    The development of efficient gas discharge ion sources with axial beam extraction for on-line mass separation is described. The aim of the investigation was to increase the ion source temperature, the lifetime and the ionisation yield in comparison to present low-pressure are discharge ion sources and to reduce the ion current density from usually 1 to 100 mA/cm 3 . In all ion sources the pressure range below the minimal ignition pressure of the arc discharge was investigated. As a result an ion source was developed which works at small changes in geometry and in electric device of a Nielsen source with high ionization yield (up to 50% for xenon) stabil and without ignition difficulties up to 10 -5 Torr. At a typical pressure of 3 x 10 -5 Torr ion current and ion current density are about 1 μA and 0.1 mA/cm 3 respectively besides high yield and a great emission aperture (diameter 1.2 mm). (orig.) [de

  9. Improved environmental and forensics measurements using multiple ion counters in isotope ratio mass spectrometry

    International Nuclear Information System (INIS)

    Goldberg, S.A.; Richter, S.; Schwieters, H.

    2002-01-01

    Full text: A new detector system designed for isotope ratio mass spectrometers provides improved precision on measurements of samples with very low amounts ( -11 grams) of analyte. An array of continuous dynode electron multipliers has been installed on a new ThermoFinnigan MAT Triton thermal ionization mass spectrometer acquired by the New Brunswick Laboratory. These ion counters are modifications of miniaturized, commercially-available continuous dynode electron multipliers. They can be readily installed to replace individual Faraday cups in a multi-detector mass spectrometer or bundled together and located along the detector plane with a set of Faraday cups. On the New Brunswick Laboratory mass spectrometer, nine Faraday cups, one conventional discrete dynode electron multiplier, and seven miniaturized ion counters were installed. Six of the small ion counters were bundled together and positioned on the high mass side of the Low 4 Faraday cup. One additional ion counter was positioned on the low mass side of the Low 4 Faraday cup. This arrangement allows for the simultaneous measurement of all uranium (including 233 U) or plutonium (including 244 Pu) isotopes, and allows for the measurement of larger 238 U intensities on the Faraday cup if needed. Unit mass spacing of U, Pu, or other actinides is readily achieved by the use of a mass dispersion zoom lens. The advantage of multiple ion counting is the simultaneous collection of isotopes. It overcomes many of the problems such as transient signal variation in sample emission and ionization. For a given sample, multiple ion counting generates a greater number of counts for each isotope relative to single detector ion counting and provides improved counting statistics by a factor of two or more. Initial tests indicate that the multiple ion counters exhibit high counting efficiency, a dark noise of less than 10 counts per minute and typically less than 1 count per minute, and show linear response characteristics over

  10. Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer

    Directory of Open Access Journals (Sweden)

    P. S. Chhabra

    2010-05-01

    Full Text Available The elemental composition of laboratory chamber secondary organic aerosol (SOA from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NOx, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NOx SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

  11. Analysis of Nitro-aromatic and Nitramine Explosives by Atmospheric Pressure Chemical Ionization / High Performance Liquid Chromatography / Mass Spectrometry / Mass Spectrometry

    International Nuclear Information System (INIS)

    Hicks, B.J.; Han, W.; Robben, J.R.

    2009-01-01

    This procedure is capable of separating and quantifying twenty-nine high explosives and internal surrogates with a single injection. After the initial preparation step, the sample is introduced to the high performance liquid chromatograph for target separation, ionized by atmospheric pressure chemical ionization and the explosives of interest are isolated / quantified by mass spectrometry / mass spectrometry. Concentrations of the target explosives are measured relative to the response of both internal and external standard concentrations. A C-18 reverse phase high performance liquid chromatograph column is used for separation. Ionization is performed using both positive and negative atmospheric pressure chemical ionization resulting in a molecular ion with little fragmentation. These ions are isolated at the first quadrupole of the mass spectrometer, dissociated by collision with argon in the collision cell and the resulting daughter ions are isolated at the second quadrupole. These daughter ions then reach the detector where they are quantified. To date this procedure represents the most thorough high performance liquid chromatography / mass spectrometry / mass spectrometry explosives analysis available in the environmental chemistry market. (authors)

  12. Metabolism of nitazoxanide in rats, pigs, and chickens: Application of liquid chromatography coupled to hybrid linear ion trap/Orbitrap mass spectrometer.

    Science.gov (United States)

    Huang, Xianhui; Guo, Chunna; Chen, Zhangliu; Liu, Yahong; He, Limin; Zeng, Zhenling; Yan, Chaoqun; Pan, Guangfang; Li, Shuaipeng

    2015-09-01

    Nitazoxanide (NTZ) is a nitrothiazole benzamide compound with a broad activity spectrum against parasites, Gram-positive and Gram-negative anaerobic bacteria, and viruses. In this study, hybrid linear ion trap/Orbitrap mass spectrometer providing a high mass resolution and accuracy was used to investigate the metabolism of NTZ in rats, pigs, and chickens. The results revealed that acetylation and glucuronidation were the main metabolic pathways in rats and pigs, whereas acetylation and sulfation were the major metabolic pathways in chickens, which indicated interspecies variations in drug metabolism and elimination. With the accurate mass data and the characteristic MS(n) product ions, we identified six metabolites in which tizoxanide and hydroxylated tizoxanide were phase I metabolites and tizoxanide glucuronide, tizoxanide glucose, tizoxanide sulfate and hydroxyl tizoxanide sulfate were phase II metabolites. Hydroxylated tizoxanide and tizoxanide glucose were identified for the first time. All the comprehensive data were provided to make out the metabolism of NTZ in rats, pigs and chickens more clearly. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. High-resolution Mass Spectrometry of Skin Mucus for Monitoring Physiological Impacts in Fish Exposed to Wastewater Effluent at a Great Lakes AOC

    Science.gov (United States)

    High-resolution mass spectrometry is advantageous for monitoring physiological impacts and contaminant biotransformation products in fish exposed to complex wastewater effluent. We evaluated this technique using skin mucus from male and female fathead minnows (Pimephales promela...

  14. Imaging with Mass Spectrometry: A SIMS and VUV-Photoionization Study of Ion-Sputtered Atoms and Clusters from GaAs and Au

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Lynelle; Zhou, Jia; Wilson, Kevin R.; Leone, Stephen R.; Ahmed, Musahid

    2008-12-05

    A new mass spectrometry surface imaging method is presented in which ion-sputtered neutrals are postionized by wavelength-tunable vacuum ultraviolet (VUV) light from a synchrotron source. Mass spectra and signal counts of the photoionized neutrals from GaAs (100) and Au are compared to those of the secondary ions. While clusters larger than dimers are more efficiently detected as secondary ions, certain species, such as As2, Au and Au2, are more efficiently detected through the neutral channel. Continuously tuning the photon wavelength allows photoionization efficiency (PIE) curves to be obtained for sputtered Asm (m=1,2) and Aun (n=1-4). From the observed ionization thresholds, sputtered neutral As and Au show no clear evidence of electronic excitation, while neutral clusters have photoionization onsets shifted to lower energies by ~;;0.3 eV. These shifts are attributed to unresolved vibrational and rotational excitations. High-spatial resolution chemical imaging with synchrotron VUV postionization is demonstrated at two different photon energies using a copper TEM grid embedded in indium. The resulting images are used to illustrate the use of tunable VUV light for verifying mass peak assignments by exploiting the unique wavelength-dependent PIE of each sputtered neutral species. This capability is valuable for identifying compounds when imaging chemically complex systems with mass spectrometry-based techniques.

  15. Development of High Resolution Resonance Ionization Mass Spectrometry for Neutron Dosimetry Technique with93Nb(n,n'93mNb Reaction

    Directory of Open Access Journals (Sweden)

    Tomita Hideki

    2016-01-01

    Full Text Available We have proposed an advanced technique to measure the 93mNb yield precisely by Resonance Ionization Mass Spectrometry, instead of conventional characteristic X-ray spectroscopy. 93mNb-selective resonance ionization is achievable by distinguishing the hyperfine splitting of the atomic energy levels between 93Nb and 93mNb at high resolution. In advance of 93mNb detection, we could successfully demonstrate high resolution resonant ionization spectroscopy of stable 93Nb using an all solid-state, narrow-band and tunable Ti:Sapphire laser system operated at 1 kHz repetition rate.

  16. Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

    Science.gov (United States)

    Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

    2001-08-01

    Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry.

  17. Chemical characterization of long-range transport biomass burning emissions to the Himalayas: insights from high-resolution aerosol mass spectrometry

    Directory of Open Access Journals (Sweden)

    X. Zhang

    2018-04-01

    Full Text Available An intensive field measurement was conducted at a remote, background, high-altitude site (Qomolangma Station, QOMS, 4276 m a.s.l. in the northern Himalayas, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS along with other collocated instruments. The field measurement was performed from 12 April to 12 May 2016 to chemically characterize the high time-resolved submicron particulate matter (PM1 and obtain the dynamic processes (emissions, transport, and chemical evolution of biomass burning (BB, frequently transported from South Asia to the Himalayas during pre-monsoon season. Overall, the average (±1σ PM1 mass concentration was 4.44 (±4.54 µg m−3 for the entire study, which is comparable with those observed at other remote sites worldwide. Organic aerosol (OA was the dominant PM1 species (accounting for 54.3 % of total PM1 on average followed by black carbon (BC (25.0 %, sulfate (9.3 %, ammonium (5.8 %, nitrate (5.1 %, and chloride (0.4 %. The average size distributions of PM1 species all peaked at an overlapping accumulation mode (∼ 500 nm, suggesting that aerosol particles were internally well-mixed and aged during long-range transport. Positive matrix factorization (PMF analysis on the high-resolution organic mass spectra identified three distinct OA factors, including a BB-related OA (BBOA, 43.7 %, a nitrogen-containing OA (NOA, 13.9 % and a more-oxidized oxygenated OA (MO-OOA, 42.4 %. Two polluted episodes with enhanced PM1 mass loadings and elevated BBOA contributions from the west and southwest of QOMS during the study were observed. A typical BB plume was investigated in detail to illustrate the chemical evolution of aerosol characteristics under distinct air mass origins, meteorological conditions, and atmospheric oxidation processes.

  18. Mass spectrometer with two ion sources

    International Nuclear Information System (INIS)

    Glickman, L.G.; Mit', A.G.

    2002-01-01

    Static mass spectrometer with mid-plane near which ions are moving is considered in this article. Two ion sources are used, their exit slits are perpendicular to the mid-plane. The simple method of the replacement of source is offered. Two concave two-electrode transaxial mirrors with two-plate electrodes are used for this aim. The mid-plane of these mirrors coincides with the mid-plane of the device. The exit slit of each source is located in the principal plane of the object space. The principal planes of the image space of the both mirrors coincide. The images of the exit slits of the sources are in these planes and coincide too. We used the mirrors making stigmatic images with the magnification one to one, in which the dispersion on energy and spherical aberrations of the second order are equal to zero. These images are the objects on which the ion-optical system of the mass spectrometer is tuned. When you choose one from two ion sources it is enough to switch the corresponding mirror

  19. Molecular characterization of phytoplankton dissolved organic matter (DOM) and sulfur components using high resolution Orbitrap mass spectrometry.

    Science.gov (United States)

    Mangal, Vaughn; Stock, Naomi L; Guéguen, Celine

    2016-03-01

    Orbitrap high resolution mass spectrometry (HRMS) with electrospray ionization in both positive and negative polarity was conducted on Suwannee River fulvic acid (SRFA), Pony Lake fulvic acid (PLFA) standards, and dissolved organic matter (DOM) released by freshwater phytoplankton (Scenedesmus obliquus, Euglena mutabilis, and Euglena gracilis). Three-dimensional van Krevelen diagrams expressing various oxygenation states of sulfur molecules and abundance plots of sulfur-containing species were constructed. Orbitrap HRMS analysis of SRFA found a high density of peaks in the lignin region (77 %) and low density of protein material (6.53 %), whereas for PLFA, 25 % of the total peaks were lignin related compared to 56 % of peaks in protein regions, comparable with other HRMS studies. Phytoplankton-derived DOM of S. obliquus, E. mutabilis, and E. gracilis was dominated by protein molecules at respective percentages of 36, 46, and 49 %, and is consistent with previous experiments examining phytoplankton-derived DOM composition. The normalized percentage of SO-containing compounds was determined among the three phytoplankton to be 56 % for Scenedesmus, 54 % for E. mutabilis, and 47 % for E. gracilis, suggesting variation between sulfur content in phytoplankton-derived DOM and differences in metal binding capacities. These results suggest the level of resolution by Orbitrap mass spectrometry is sufficient for preliminary characterization of phytoplankton DOM at an affordable cost relative to other HRMS techniques.

  20. High resolution Thomson Parabola Spectrometer for full spectral capture of multi-species ion beams

    International Nuclear Information System (INIS)

    Alejo, A.; Kar, S.; Ahmed, H.; Doria, D.; Borghesi, M.; Tebartz, A.; Ding, J.; Neumann, N.; Astbury, S.; Carroll, D. C.; Scott, G. G.; Higginson, A.; McKenna, P.; Wagner, F.; Roth, M.

    2016-01-01

    We report on the experimental characterisation of laser-driven ion beams using a Thomson Parabola Spectrometer (TPS) equipped with trapezoidally shaped electric plates, proposed by Gwynne et al. [Rev. Sci. Instrum. 85, 033304 (2014)]. While a pair of extended (30 cm long) electric plates was able to produce a significant increase in the separation between neighbouring ion species at high energies, deploying a trapezoidal design circumvented the spectral clipping at the low energy end of the ion spectra. The shape of the electric plate was chosen carefully considering, for the given spectrometer configuration, the range of detectable ion energies and species. Analytical tracing of the ion parabolas matches closely with the experimental data, which suggests a minimal effect of fringe fields on the escaping ions close to the wedged edge of the electrode. The analytical formulae were derived considering the relativistic correction required for the high energy ions to be characterised using such spectrometer.

  1. High resolution Thomson Parabola Spectrometer for full spectral capture of multi-species ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Alejo, A.; Kar, S., E-mail: s.kar@qub.ac.uk; Ahmed, H.; Doria, D.; Borghesi, M. [Centre for Plasma Physics, School of Mathematics and Physics, Queen’s University Belfast, Belfast BT7 1NN (United Kingdom); Tebartz, A.; Ding, J.; Neumann, N. [Institut für Kernphysik, Technische Universität Darmstadt, Schloßgartenstrasse 9, D-64289 Darmstadt (Germany); Astbury, S.; Carroll, D. C.; Scott, G. G. [Central Laser Facility, Rutherford Appleton Laboratory, Didcot, Oxfordshire OX11 0QX (United Kingdom); Higginson, A.; McKenna, P. [Department of Physics, SUPA, University of Strathclyde, Glasgow G4 0NG (United Kingdom); Wagner, F. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, Planckstraße 1, 64291 Darmstadt (Germany); Roth, M. [Institut für Kernphysik, Technische Universität Darmstadt, Schloßgartenstraße 9, D-64289 Darmstadt (Germany)

    2016-08-15

    We report on the experimental characterisation of laser-driven ion beams using a Thomson Parabola Spectrometer (TPS) equipped with trapezoidally shaped electric plates, proposed by Gwynne et al. [Rev. Sci. Instrum. 85, 033304 (2014)]. While a pair of extended (30 cm long) electric plates was able to produce a significant increase in the separation between neighbouring ion species at high energies, deploying a trapezoidal design circumvented the spectral clipping at the low energy end of the ion spectra. The shape of the electric plate was chosen carefully considering, for the given spectrometer configuration, the range of detectable ion energies and species. Analytical tracing of the ion parabolas matches closely with the experimental data, which suggests a minimal effect of fringe fields on the escaping ions close to the wedged edge of the electrode. The analytical formulae were derived considering the relativistic correction required for the high energy ions to be characterised using such spectrometer.

  2. High resolution Thomson Parabola Spectrometer for full spectral capture of multi-species ion beams

    Science.gov (United States)

    Alejo, A.; Kar, S.; Tebartz, A.; Ahmed, H.; Astbury, S.; Carroll, D. C.; Ding, J.; Doria, D.; Higginson, A.; McKenna, P.; Neumann, N.; Scott, G. G.; Wagner, F.; Roth, M.; Borghesi, M.

    2016-08-01

    We report on the experimental characterisation of laser-driven ion beams using a Thomson Parabola Spectrometer (TPS) equipped with trapezoidally shaped electric plates, proposed by Gwynne et al. [Rev. Sci. Instrum. 85, 033304 (2014)]. While a pair of extended (30 cm long) electric plates was able to produce a significant increase in the separation between neighbouring ion species at high energies, deploying a trapezoidal design circumvented the spectral clipping at the low energy end of the ion spectra. The shape of the electric plate was chosen carefully considering, for the given spectrometer configuration, the range of detectable ion energies and species. Analytical tracing of the ion parabolas matches closely with the experimental data, which suggests a minimal effect of fringe fields on the escaping ions close to the wedged edge of the electrode. The analytical formulae were derived considering the relativistic correction required for the high energy ions to be characterised using such spectrometer.

  3. High-resolution bent-crystal spectrometer for the ultra-soft x-ray region

    International Nuclear Information System (INIS)

    Beiersdorfer, P.; von Goeler, S.; Bitter, M.; Hill, K.W.; Hulse, R.A.; Walling, R.S.

    1988-10-01

    A multichannel vacuum Brag-crystal spectrometer has been developed for high-resolution measurements of the line emission from tokamak plasmas in the wavelength region between 4 and 25 /angstrom/. The spectrometer employs a bent crystal in Johann geometry and a microchannel-plate intensified photodiode array. The instrument is capable of measuring high-resolution spectra (λ/Δλ ∼ 3000) with fast time resolution (4 msec per spectrum) and good spatial resolution (3 cm). The spectral bandwidth is Δλ/λ 0 = 8/angstrom/. A simple tilt mechanism allows access to different wavelength intervals. In order to illustrate the utility of the new spectrometer, time- and space-resolved measurements of the n = 3 to n = 2 spectrum of selenium from the Princeton Large Torus tokamak plasmas are presented. The data are used to determine the plasma transport parameters and to infer the radial distribution of fluorinelike, neonlike, and sodiumlike ions of selenium in the plasma. The new ultra-soft x-ray spectrometer has thus enabled us to demonstrate the utility of high-resolution L-shell spectroscopy of neonlike ions as a fusion diagnostic. 43 refs., 23 figs

  4. High throughput electrophysiology: new perspectives for ion channel drug discovery

    DEFF Research Database (Denmark)

    Willumsen, Niels J; Bech, Morten; Olesen, Søren-Peter

    2003-01-01

    Proper function of ion channels is crucial for all living cells. Ion channel dysfunction may lead to a number of diseases, so-called channelopathies, and a number of common diseases, including epilepsy, arrhythmia, and type II diabetes, are primarily treated by drugs that modulate ion channels....... A cornerstone in current drug discovery is high throughput screening assays which allow examination of the activity of specific ion channels though only to a limited extent. Conventional patch clamp remains the sole technique with sufficiently high time resolution and sensitivity required for precise and direct...... characterization of ion channel properties. However, patch clamp is a slow, labor-intensive, and thus expensive, technique. New techniques combining the reliability and high information content of patch clamping with the virtues of high throughput philosophy are emerging and predicted to make a number of ion...

  5. Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modeling of complete high time-resolution aerosol mass spectra

    Science.gov (United States)

    McGuire, M. L.; Chang, R. Y.-W.; Slowik, J. G.; Jeong, C.-H.; Healy, R. M.; Lu, G.; Mihele, C.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

    2014-08-01

    method would be even more useful for HR-ToF-AMS data, due to the ability to understand better the chemical nature of atypical factors from high-resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of the extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably resolved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

  6. Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

    Science.gov (United States)

    McGuire, M. L.; Chang, R. Y.-W.; Slowik, J. G.; Jeong, C.-H.; Healy, R. M.; Lu, G.; Mihele, C.; Abbatt, J. P. D.; Brook, J. R.; Evans, G. J.

    2014-02-01

    to better understand the chemical nature of atypical factors from high resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably resolved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

  7. Ion deposition by inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Hu, K.; Houk, R.S.

    1996-01-01

    An atmospheric pressure inductively coupled plasma (ICP) is used with a quadrupole mass spectrometer (MS) for ion deposition. The deposited element is introduced as a nebulized aqueous solution. Modifications to the ICP-MS device allow generation and deposition of a mass-resolved beam of 165 Ho + at 5x10 12 ions s -1 . The ICP is a universal, multielement ion source that can potentially be used for applications such as deposition of mixtures of widely varying stoichiometry or of alternating layers of different elements. copyright 1996 American Vacuum Society

  8. Atomic structure of highly-charged ions. Final report

    International Nuclear Information System (INIS)

    Livingston, A. Eugene

    2002-01-01

    Atomic properties of multiply charged ions have been investigated using excitation of energetic heavy ion beams. Spectroscopy of excited atomic transitions has been applied from the visible to the extreme ultraviolet wavelength regions to provide accurate atomic structure and transition rate data in selected highly ionized atoms. High-resolution position-sensitive photon detection has been introduced for measurements in the ultraviolet region. The detailed structures of Rydberg states in highly charged beryllium-like ions have been measured as a test of long-range electron-ion interactions. The measurements are supported by multiconfiguration Dirac-Fock calculations and by many-body perturbation theory. The high-angular-momentum Rydberg transitions may be used to establish reference wavelengths and improve the accuracy of ionization energies in highly charged systems. Precision wavelength measurements in highly charged few-electron ions have been performed to test the most accurate relativistic atomic structure calculations for prominent low-lying excited states. Lifetime measurements for allowed and forbidden transitions in highly charged few-electron ions have been made to test theoretical transition matrix elements for simple atomic systems. Precision lifetime measurements in laser-excited alkali atoms have been initiated to establish the accuracy of relativistic atomic many-body theory in many-electron systems

  9. Rapid profiling of antimicrobial compounds characterising B. subtilis TR50 cell-free filtrate by high-performance liquid chromatography coupled to high-resolution Orbitrap™ mass spectrometry.

    Science.gov (United States)

    Monaci, Linda; Quintieri, Laura; Caputo, Leonardo; Visconti, Angelo; Baruzzi, Federico

    2016-01-15

    Several Bacillus strains, typically isolated from different food sources, represent renowned producers of a multitude of low and high molecular weight compounds, including lipopeptides and macrolactones, with an importance for their antimicrobial activity. The high homology shared by many of these compounds also occurring as closely related isoforms poses a challenge in their prompt detection. Identification and structural elucidation is generally achieved by matrix-assisted laser desorption/ionization (MALDI) or liquid chromatography (LC) coupled to mass spectrometry (MS) after a pre-fractionation and/or purification step of the extract. In this paper we report the application of a method based on LC separation and high-resolution Orbitrap™-based MS for the rapid screening of raw filtrate of the strain Bacillus subtilis TR50 endowed with antimicrobial activity, without requiring any sample pre-treatment. Upon direct analysis of the cell-free filtrate of Bacillus subtilis TR50 by high-resolution mass spectrometry (HRMS), different compounds families, that proved to exert a remarked antimicrobial activity against several foodborne pathogens, can be readily displayed along the chromatographic run. Among them, three different classes were identified and characterized belonging to the iturin, fengycin and surfactin groups. The high resolving power and accurate mass accuracy provided by the HRMS system in use ensured an enhanced selectivity compared to other mass spectrometers. In addition, after activation of the HCD cell, the HR-MS/MS spectra can provide insights in the structural elucidation of several compounds. The acquisition of HRMS spectra of raw filtrates of subtilis strains allows untargeted analysis of the major classes of compounds produced to be performed, thus facilitating identification of other unknown bioactive molecules after retrospective analysis. These features make this approach a fast tool applicable to the rapid screening and further

  10. High throughput electrophysiology: new perspectives for ion channel drug discovery

    DEFF Research Database (Denmark)

    Willumsen, Niels J; Bech, Morten; Olesen, Søren-Peter

    2003-01-01

    . A cornerstone in current drug discovery is high throughput screening assays which allow examination of the activity of specific ion channels though only to a limited extent. Conventional patch clamp remains the sole technique with sufficiently high time resolution and sensitivity required for precise and direct....... The introduction of new powerful HTS electrophysiological techniques is predicted to cause a revolution in ion channel drug discovery....

  11. Recent ion optics and mass spectrometers

    International Nuclear Information System (INIS)

    Matsuda, Hisashi

    1976-01-01

    The establishment of the third order approximation method for computing the orbit of the ion optical system for mass spectrometers and the completion of its computer program are reported. A feature of this orbit computation is in that the effect of the fringing field can be considered with the accuracy of third order approximation. Several new ion optical systems for mass spectrometers have been proposed by using such orbit computing programs. Brief explanation and the description on the future prospect and problems are made on the following items: the vertual image double focusing mass spectrometer, the second order double focusing mass spectrometer, the E x B superposed field mass spectrometer, and the apparatus with a cylindrical electric field and Q-lens. In the E x B superposed field with Matsuda plates, if the magnetic field is generated by an electromagnet instead of a permanent magnet, the dispersion of mass and energy can be changed at will. The Matsuda plates are known as the auxiliary electrodes positioned at the top and bottom of a cylindrical capacitor. Utilizing those characteristics, a zoom spectrometer can be made, with which only a necessary part of mass spectra can be investigated in detail, but the whole spectra are investigated roughly. In addition, the distribution of energy can be investigated simultaneously after the separation of ionic mass similarly to the parabola apparatus. (Iwakiri, K.)

  12. Sensitive helium leak detection in a deuterium atmosphere using a high-resolution quadrupole mass spectrometer

    International Nuclear Information System (INIS)

    Hiroki, S.; Abe, T.; Murakami, Y.

    1996-01-01

    In fusion machines, realizing a high-purity plasma is a key to improving the plasma parameters. Thus, leak detection is a necessary part of reducing the leak rate to a tolerable level. However, a conventional helium ( 4 He) leak detector is useless in fusion machines with a deuterium (D 2 ) plasma, because retained D particles on the first walls release D 2 for a long period and the released D 2 interferes with the signals from the leaked 4 He due to the near identical masses of 4.0026 u ( 4 He) and 4.0282 u (D 2 ). A high-resolution quadrupole mass spectrometer (HR-QMS) that we have recently developed, can detect a 4 He + population as small as 10 -4 peak in a D 2 atmosphere. Thus, the HR-QMS has been applied to detect 4 He leaks. To improve the minimum detectable limit of 4 He leak, a differentially pumped HR-QMS analyzer was attached to a chamber of the 4 He leak detector. In conclusion, the improved 4 He leak detector could detect 4 He leaks of the order of 10 -10 Pa · m 3 /s in a D 2 atmosphere. (Author)

  13. Calorimetric low temperature detectors for heavy ion physics

    Energy Technology Data Exchange (ETDEWEB)

    Egelhof, P.; Kraft-Bermuth, S. [Gesellschaft fuer Schwerionenforschung mbH, Darmstadt (Germany)]|[Mainz Univ. (Germany). Inst. fuer Physik

    2005-05-01

    Calorimetric low temperature detectors have the potential to become powerful tools for applications in many fields of heavy ion physics. A brief overview of heavy ion physics at present and at the next generation heavy ion facilities is given with a special emphasis on the conditions for heavy ion detection and the potential advantage of cryogenic detectors for applications in heavy ion physics. Two types of calorimetric low temperature detectors for the detection of energetic heavy ions have been developed and their response to the impact of heavy ions was investigated systematically for a wide range of energies (E=0.1-360 MeV/amu) and ion species ({sup 4}He.. {sup 238}U). Excellent results with respect to energy resolution, {delta}E/E ranging from 1 to 5 x 10{sup -3} even for the heaviest ions, and other basic detector properties such as energy linearity with no indication of a pulse height defect, energy threshold, detection efficiency and radiation hardness have been obtained, representing a considerable improvement as compared to conventional heavy ion detectors based on ionization. With the achieved performance, calorimetric low temperature detectors bear a large potential for applications in various fields of basic and applied heavy ion research. A brief overview of a few prominent examples, such as high resolution nuclear spectroscopy, high resolution nuclear mass determination, which may be favourably used for identification of superheavy elements or in direct reaction experiments with radioactive beams, as well as background discrimination in accelerator mass spectrometry, is given, and first results are presented. For instance, the use of cryogenic detectors allowed to improve the sensitivity in trace analysis of {sup 236}U by one order of magnitude and to determine the up to date smallest isotope ratio of {sup 236}U/{sup 238}U = 6.1 x 10{sup -12} in a sample of natural uranium. Besides the detection of heavy ions, the concept of cryogenic detectors also

  14. Calorimetric low temperature detectors for heavy ion physics

    International Nuclear Information System (INIS)

    Egelhof, P.; Kraft-Bermuth, S.; Mainz Univ.

    2005-07-01

    Calorimetric low temperature detectors have the potential to become powerful tools for applications in many fields of heavy ion physics. A brief overview of heavy ion physics at present and at the next generation heavy ion facilities is given with a special emphasis on the conditions for heavy ion detection and the potential advantage of cryogenic detectors for applications in heavy ion physics. Two types of calorimetric low temperature detectors for the detection of energetic heavy ions have been developed and their response to the impact of heavy ions was investigated systematically for a wide range of energies (E=0.1-360 MeV/amu) and ion species ( 4 He.. 238 U). Excellent results with respect to energy resolution, ΔE/E ranging from 1 to 5 x 10 -3 even for the heaviest ions, and other basic detector properties such as energy linearity with no indication of a pulse height defect, energy threshold, detection efficiency and radiation hardness have been obtained, representing a considerable improvement as compared to conventional heavy ion detectors based on ionization. With the achieved performance, calorimetric low temperature detectors bear a large potential for applications in various fields of basic and applied heavy ion research. A brief overview of a few prominent examples, such as high resolution nuclear spectroscopy, high resolution nuclear mass determination, which may be favourably used for identification of superheavy elements or in direct reaction experiments with radioactive beams, as well as background discrimination in accelerator mass spectrometry, is given, and first results are presented. For instance, the use of cryogenic detectors allowed to improve the sensitivity in trace analysis of 236 U by one order of magnitude and to determine the up to date smallest isotope ratio of 236 U/ 238 U = 6.1 x 10 -12 in a sample of natural uranium. Besides the detection of heavy ions, the concept of cryogenic detectors also provides considerable advantage for X

  15. Electron capture by highly charged low-velocity ions

    International Nuclear Information System (INIS)

    Cocke, C.L.; Dubois, R.; Justiniano, E.; Gray, T.J.; Can, C.

    1982-01-01

    This paper describes the use of a fast heavy ion beam to produce, by bombardment of gaseous targets, highly-charged low-velocity recoil ions, and the use of these secondary ions in turn as projectiles in studies of electron capture and ionization in low-energy collision systems. The interest in collisions involving low-energy highly-charged projectiles comes both from the somewhat simplifying aspects of the physics which attend the long-range capture and from applications to fusion plasmas, astrophysics and more speculative technology such as the production of X-ray lasers. The ions of interest in such applications should have both electronic excitation and center-of-mass energies in the keV range and cannot be produced by simply stripping fast heavy ion beams. Several novel types of ion source have been developed to produce low-energy highly-charged ions, of which the secondary ion recoil source discussed in this paper is one. (Auth.)

  16. Nontargeted SWATH acquisition for identifying 47 synthetic cannabinoid metabolites in human urine by liquid chromatography-high-resolution tandem mass spectrometry.

    Science.gov (United States)

    Scheidweiler, Karl B; Jarvis, Michael J Y; Huestis, Marilyn A

    2015-01-01

    Clandestine laboratories constantly produce new synthetic cannabinoids to circumvent legislative scheduling efforts, challenging and complicating toxicological analysis. Sundstrom et al. (Anal Bioanal Chem 405(26):8463-8474, [9]) and Kronstrand et al. (Anal Bioanal Chem 406(15):3599-3609, [10]) published nontargeted liquid chromatography, high-resolution, quadrupole/time-of-flight mass spectrometric (LC-QTOF) assays with validated detection of 18 and 38 urinary synthetic cannabinoid metabolites, respectively. We developed and validated a LC-QTOF urine method for simultaneously identifying the most current 47 synthetic cannabinoid metabolites from 21 synthetic cannabinoid families (5-fluoro AB-PINACA, 5-fluoro-AKB48, 5-fluoro PB-22, AB-PINACA, ADB-PINACA, AKB48, AM2201, JWH-018, JWH-019, JWH-073, JWH-081, JWH-122, JWH-200, JWH-210, JWH-250, JWH-398, MAM2201, PB-22, RCS-4, UR-144, and XLR11). β-Glucuronidase-hydrolyzed urine was extracted with 1-mL Biotage SLE+ columns. Specimens were reconstituted in 150-μL mobile phase consisting of 80% A (0.1% formic acid in water) and 20% B (0.1% formic acid in acetonitrile). Fifty microliters was injected, and SWATH™ MS data were acquired in positive electrospray mode. The LC-QTOF instrument consisted of a Shimadzu UFLCxr system and an ABSciex 5600+ TripleTOF® mass spectrometer. Gradient chromatographic separation was achieved with a Restek Ultra Biphenyl column with a 0.5-mL/min flow rate and an overall run time of 15 min. Identification criteria included molecular ion mass error, isotopic profiles, retention time, and library fit criteria. Limits of detection were 0.25-5 μg/L (N = 10 unique fortified urine samples), except for two PB-22 metabolites with limits of 10 and 20 μg/L. Extraction efficiencies and matrix effects (N = 10) were 55-104 and -65-107%, respectively. We present a highly useful novel LC-QTOF method for simultaneously confirming 47 synthetic cannabinoid metabolites in human urine.

  17. High resolution mass spectrometry method and system for analysis of whole proteins and other large molecules

    Science.gov (United States)

    Reilly, Peter T. A. [Knoxville, TN; Harris, William A [Naperville, IL

    2010-03-02

    A matrix assisted laser desorption/ionization (MALDI) method and related system for analyzing high molecular weight analytes includes the steps of providing at least one matrix-containing particle inside an ion trap, wherein at least one high molecular weight analyte molecule is provided within the matrix-containing particle, and MALDI on the high molecular weight particle while within the ion trap. A laser power used for ionization is sufficient to completely vaporize the particle and form at least one high molecular weight analyte ion, but is low enough to avoid fragmenting the high molecular weight analyte ion. The high molecular weight analyte ion is extracted out from the ion trap, and is then analyzed using a detector. The detector is preferably a pyrolyzing and ionizing detector.

  18. Ion microprobe Sr isotope analysis of carbonates with about 5 {mu}m spatial resolution: An example from an ayu otolith

    Energy Technology Data Exchange (ETDEWEB)

    Sano, Yuji [Center for Advanced Marine Research, Ocean Research Institute, University of Tokyo, Nakano-ku, Tokyo 164-8639 (Japan)], E-mail: ysano@ori.u-tokyo.ac.jp; Shirai, Kotaro [International Coastal Research Center, Ocean Research Institute, University of Tokyo, Otsuchi, Iwate 028-1102 (Japan); Takahata, Naoto; Amakawa, Hiroshi [Center for Advanced Marine Research, Ocean Research Institute, University of Tokyo, Nakano-ku, Tokyo 164-8639 (Japan); Otake, Tsuguo [International Coastal Research Center, Ocean Research Institute, University of Tokyo, Otsuchi, Iwate 028-1102 (Japan)

    2008-08-15

    A high lateral resolution secondary ion mass spectrometer (NanoSIMS NS50 ion microprobe) has been used to measure {sup 87}Sr/{sup 86}Sr ratios in natural CaCO{sub 3} samples. A {approx}2 nA O{sup -} primary beam was used to sputter a 5-7-{mu}m diameter crater on the sample surface and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. The multi-collector system was adjusted to detect {sup 43}Ca{sup +} (by a detector EM2), {sup 80}Ca{sub 2}{sup +} (EM3), {sup 86}Sr{sup +} (EM4), and {sup 87}Sr{sup +} (EM4b) ions at the same time. Then the magnetic field was scanned for the EM4 to detect {sup 85}Rb{sup +}, {sup 86}Sr{sup +} and {sup 87}Sr{sup +}, while the EM4b can measure {sup 86}Sr{sup +}, {sup 87}Sr{sup +} and {sup 88}Sr{sup +}, respectively. A mass resolution of 3600 at 10% peak height was attained with a flat peak top, while the sensitivity of Sr was about 10 cps/nA/ppm. An aragonite sample (coral skeleton standard; JCp-1) was used as a reference for Sr isotope ratio calibration. Repeated analyses of the JCp-1 show that the {sup 87}Sr/{sup 86}Sr ratio agrees well with the seawater signature within a precision of 0.3 per mille at 2{sigma}, after the series of corrections such as the Ca dimer, {sup 87}Rb, and a mass bias estimated by the {sup 88}Sr/{sup 86}Sr ratio. The method was applied to an otolith (ear-stone) from ayu (Plecoglossus altivelis altivelis) collected from the Yodo river, Japan. Although experimental errors are relatively large, up to 3 per mille at 2{sigma}, the ratios of the core region are higher than the seawater signature while more distal values agree well with seawater. The very outermost part again shows the relatively higher {sup 87}Sr/{sup 86}Sr ratios. The spatial variation of {sup 87}Sr/{sup 86}Sr ratios was consistent with amphidromous migration of the fish, namely, born in the lake and grown in the coastal sea and finally collected in a river.

  19. Development of an improved high resolution mass spectrometry based multi-residue method for veterinary drugs in various food matrices.

    Science.gov (United States)

    Kaufmann, A; Butcher, P; Maden, K; Walker, S; Widmer, M

    2011-08-26

    Multi-residue methods for veterinary drugs or pesticides in food are increasingly often based on ultra performance liquid chromatography (UPLC) coupled to high resolution mass spectrometry (HRMS). Previous available time of flight (TOF) technologies, showing resolutions up to 15,000 full width at half maximum (FWHM), were not sufficiently selective for monitoring low residue concentrations in difficult matrices (e.g. hormones in tissue or antibiotics in honey). The approach proposed in this paper is based on a single stage Orbitrap mass spectrometer operated at 50,000 FWHM. Extracts (liver and kidney) which were produced according to a validated multi-residue method (time of flight detection based) could not be analyzed by Orbitrap because of extensive signal suppression. This required the improvement of established extraction and clean-up procedures. The introduced, more extensive deproteinzation steps and dedicated instrumental settings successfully eliminated these detrimental suppression effects. The reported method, covering more than 100 different veterinary dugs, was validated according to the EU Commission Decision 2002/657/EEC. Validated matrices include muscle, kidney, liver, fish and honey. Significantly better performance parameters (e.g. linearity, reproducibility and detection limits) were obtained when comparing the new method with the older, TOF based method. These improvements are attributed to the higher resolution (50,000 versus 12,000 FWHM) and the superior mass stability of the of the Orbitrap over the previously utilized TOF instrument. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. X-ray radiography with highly charged ions

    Science.gov (United States)

    Marrs, Roscoe E.

    2000-01-01

    An extremely small (1-250 micron FWHM) beam of slow highly charged ions deexciting on an x-ray production target generates x-ray monochromatic radiation that is passed through a specimen and detected for imaging. The resolution of the x-ray radiograms is improved and such detection is achieved with relatively low dosages of radiation passing through the specimen. An apparatus containing an electron beam ion trap (and modifications thereof) equipped with a focusing column serves as a source of ions that generate radiation projected onto an image detector. Electronic and other detectors are able to detect an increased amount of radiation per pixel than achieved by previous methods and apparati.

  1. Identification of urinary biomarkers of exposure to di-(2-propylheptyl) phthalate using high-resolution mass spectrometry and two data-screening approaches.

    Science.gov (United States)

    Shih, Chia-Lung; Liao, Pao-Mei; Hsu, Jen-Yi; Chung, Yi-Ning; Zgoda, Victor G; Liao, Pao-Chi

    2018-02-01

    Di-(2-propylheptyl) phthalate (DPHP) is a plasticizer used in polyvinyl chloride and vinyl chloride copolymer that has been suggested to be a toxicant in rats and may affect human health. Because the use of DPHP is increasing, the general German population is being exposed to DPHP. Toxicant metabolism is important for human toxicant exposure assessments. To date, the knowledge regarding DPHP metabolism has been limited, and only four metabolites have been identified in human urine. Ultra-performance liquid chromatography was coupled with Orbitrap high-resolution mass spectrometry (MS) and two data-screening approaches-the signal mining algorithm with isotope tracing (SMAIT) and the mass defect filter (MDF)-for DPHP metabolite candidate discovery. In total, 13 and 104 metabolite candidates were identified by the two approaches, respectively, in in vitro DPHP incubation samples. Of these candidates, 17 were validated as tentative exposure biomarkers using a rat model, 13 of which have not been reported in the literature. The two approaches generated rather different tentative DPHP exposure biomarkers, indicating that these approaches are complementary for discovering exposure biomarkers. Compared with the four previously reported DPHP metabolites, the three tentative novel biomarkers had higher peak intensity ratios, and two were confirmed as DPHP hydroxyl metabolites based on their MS/MS product ion profiles. These three tentative novel biomarkers should be further investigated for potential application in human exposure assessment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. High Resolution Multiphoton Ionization/Dissociation of Molecular Beam of Acetone from 582.60 to 585.80 nm

    Science.gov (United States)

    Mejia-Ospino, Enrique; Garcia, Gladis; Guerrero, Alfonso; Alvarez, Ignacio; Cisneros, Carmen

    2003-05-01

    Multiphoton ionization and dissociation of a jet supersonic of acetone at wavelength from 582.60 to 585.80 nm is studied using a Nd:YAG-OPO (optical parametric oscillator) system coupled to time-of-flight mass spectrometer. We present high-resolution (1.5 cm-1) three-photon resonance multiphoton spectra of the acetone 3s CH3CO+), (CH3+) and (COH+), being CH3COCH3+ ---> CH3CO+ + CH3 the more likely channel. The molecular and acetyl ions are observed practically in overall wavelength range.

  3. Desalting Protein Ions in Native Mass Spectrometry Using Supercharging Reagents

    Science.gov (United States)

    Cassou, Catherine A.; Williams, Evan R.

    2014-01-01

    Effects of the supercharging reagents m-NBA and sulfolane on sodium ion adduction to protein ions formed using native mass spectrometry were investigated. There is extensive sodium adduction on protein ions formed by electrospray ionization from aqueous solutions containing millimolar concentrations of NaCl, which can lower sensitivity by distributing the signal of a given charge state over multiple adducted ions and can reduce mass measuring accuracy for large proteins and non-covalent complexes for which individual adducts cannot be resolved. The average number of sodium ions adducted to the most abundant ion formed from ten small (8.6–29 kDa) proteins for which adducts can be resolved is reduced by 58% or 80% on average, respectively, when 1.5% m-NBA or 2.5% sulfolane are added to aqueous solutions containing sodium compared to without the supercharging reagent. Sulfolane is more effective than m-NBA at reducing sodium ion adduction and at preserving non-covalent protein-ligand and protein-protein interactions. Desalting with 2.5% sulfolane enables detection of several glycosylated forms of 79.7 kDa holo-transferrin and NADH bound to the 146 kDa homotetramer LDH, which are otherwise unresolved due to peak broadening from extensive sodium adduction. Although sulfolane is more effective than m-NBA at protein ion desalting, m-NBA reduces salt clusters at high m/z and can increase the signal-to-noise ratios of protein ions by reducing chemical noise. Desalting is likely a result of these supercharging reagents binding sodium ions in solution, thereby reducing the sodium available to adduct to protein ions. PMID:25133273

  4. Proposal for a common nomenclature for fragment ions in mass spectra of lipids

    DEFF Research Database (Denmark)

    Pauling, Josch K; Hermansson, Martin; Hartler, Jürgen

    2017-01-01

    Advances in mass spectrometry-based lipidomics have in recent years prompted efforts to standardize the annotation of the vast number of lipid molecules that can be detected in biological systems. These efforts have focused on cataloguing, naming and drawing chemical structures of intact lipid...... molecules, but have provided no guidelines for annotation of lipid fragment ions detected using tandem and multi-stage mass spectrometry, albeit these fragment ions are mandatory for structural elucidation and high confidence lipid identification, especially in high throughput lipidomics workflows. Here we...... propose a nomenclature for the annotation of lipid fragment ions, describe its implementation and present a freely available web application, termed ALEX123 lipid calculator, that can be used to query a comprehensive database featuring curated lipid fragmentation information for more than 430...

  5. Laser Ablation Electrodynamic Ion Funnel for In Situ Mass Spectrometry on Mars

    Science.gov (United States)

    Johnson, Paul V.; Hodyss, Robert P.; Tang, Keqi; Smith, Richard D.

    2012-01-01

    A front-end instrument, the laser ablation ion funnel, was developed, which would ionize rock and soil samples in the ambient Martian atmosphere, and efficiently transport the product ions into a mass spectrometer for in situ analysis. Laser ablation creates elemental ions from a solid with a high-power pulse within ambient Mars atmospheric conditions. Ions are captured and focused with an ion funnel into a mass spectrometer for analysis. The electrodynamic ion funnel consists of a series of axially concentric ring-shaped electrodes whose inside diameters (IDs) decrease over the length of the funnel. DC potentials are applied to each electrode, producing a smooth potential slope along the axial direction. Two radio-frequency (RF) AC potentials, equal in amplitude and 180 out of phase, are applied alternately to the ring electrodes. This creates an effective potential barrier along the inner surface of the electrode stack. Ions entering the funnel drift axially under the influence of the DC potential while being restricted radially by the effective potential barrier created by the applied RF. The net result is to effectively focus the ions as they traverse the length of the funnel.

  6. High-resolution in-source laser spectroscopy in perpendicular geometry

    Energy Technology Data Exchange (ETDEWEB)

    Heinke, R., E-mail: reinhard.heinke@uni-mainz.de; Kron, T. [Universität Mainz, Institut für Physik (Germany); Raeder, S. [Helmholtz-Institut Mainz (Germany); Reich, T.; Schönberg, P. [Universität Mainz, Institut für Kernchemie (Germany); Trümper, M.; Weichhold, C.; Wendt, K. [Universität Mainz, Institut für Physik (Germany)

    2017-11-15

    Operation of the novel laser ion source unit LIST (Laser Ion Source and Trap), operating at the on-line radioactive ion beam facility ISOLDE at CERN allowed for the production of ultra-pure beams of exotic isotopes far-off stability as well as direct isobar-free laser spectroscopy, giving access to the study of atomic and nuclear properties of so far inaccessible nuclides. We present a specific upgrade and adaption of the LIST targeted for high resolution spectroscopy with a Doppler-reduced perpendicular atom - laser beam geometry. With this PI-LIST (Perpendicularly Illuminated Laser Ion Source and Trap) setup, experimental linewidths below 100 MHz could be demonstrated in optical laser spectroscopy off-line, applying a pulsed injection-locked high repetition rate Ti:sapphire laser. A dual repeller configuration ensured highest suppression of isobaric interferences and almost background-free measurements on small samples in the order of 10{sup 11} atoms.

  7. High-sensitivity mass spectrometry with a tandem accelerator

    International Nuclear Information System (INIS)

    Henning, W.

    1984-01-01

    The characteristic features of accelerator mass spectrometry are discussed. A short overview is given of the current status of mass spectrometry with high-energy (MeV/nucleon) heavy-ion accelerators. Emphasis is placed on studies with tandem accelerators and on future mass spectrometry of heavier isotopes with the new generation of higher-voltage tandems

  8. Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

    Directory of Open Access Journals (Sweden)

    X.-F. Huang

    2010-09-01

    Full Text Available As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008, an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008. The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m−3; the mean composition consisted of organics (37.9%, sulfate (26.7%, ammonium (15.9%, nitrate (15.8%, black carbon (3.1%, and chloride (0.87%. The average size distributions of the species (except BC were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA, cooking-related (COA, and two oxygenated organic aerosols (OOA-1 and OOA-2, which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses

  9. Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

    Science.gov (United States)

    Huang, X.-F.; He, L.-Y.; Hu, M.; Canagaratna, M. R.; Sun, Y.; Zhang, Q.; Zhu, T.; Xue, L.; Zeng, L.-W.; Liu, X.-G.; Zhang, Y.-H.; Jayne, J. T.; Ng, N. L.; Worsnop, D. R.

    2010-09-01

    As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m-3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA

  10. Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

    Science.gov (United States)

    Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

    2011-10-01

    When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

  11. Sample handling and contamination encountered when coupling offline normal phase high performance liquid chromatography fraction collection of petroleum samples to Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Oro, Nicole E; Whittal, Randy M; Lucy, Charles A

    2012-09-05

    Normal phase high performance liquid chromatography (HPLC) is used to separate a gas oil petroleum sample, and the fractions are collected offline and analyzed on a high resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FT-ICR MS). The separation prior to MS analysis dilutes the sample significantly; therefore the fractions need to be prepared properly to achieve the best signal possible. The methods used to prepare the HPLC fractions for MS analysis are described, with emphasis placed on increasing the concentration of analyte species. The dilution effect also means that contamination in the MS spectra needs to be minimized. The contamination from molecular sieves, plastics, soap, etc. and interferences encountered during the offline fraction collection process are described and eliminated. A previously unreported MS contamination of iron formate clusters with a 0.8 mass defect in positive mode electrospray is also described. This interference resulted from the stainless steel tubing in the HPLC system. Contamination resulting from what has tentatively been assigned as palmitoylglycerol and stearoylglycerol was also observed; these compounds have not previously been reported as contaminant peaks. Copyright © 2012 Elsevier B.V. All rights reserved.

  12. Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2012-04-01

    Full Text Available Atmospheric water soluble organic nitrogen (WSON is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W, which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+, CHON compounds that contained sulfur (CHONS+, CHON compounds that contained phosphorus (CHONP+, CHON compounds that contained both sulfur and phosphorus (CHONSP+, and compounds that contained only carbon, hydrogen, and nitrogen (CHN+. Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March which have anthropogenic air mass origins and samples collected during the warm season (April to September with remote

  13. Compression Ratio Ion Mobility Programming (CRIMP) Accumulation and Compression of Billions of Ions for Ion Mobility-Mass Spectrometry Using Traveling Waves in Structures for Lossless Ion Manipulations (SLIM)

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Liulin; Garimella, Venkata BS; Hamid, Ahmed M.; Webb, Ian K.; Attah, Isaac K.; Norheim, Randolph V.; Prost, Spencer A.; Zheng, Xueyun; Sandoval, Jeremy A.; Baker, Erin M.; Ibrahim, Yehia M.; Smith, Richard D.

    2017-05-25

    We report on the implementation of a traveling wave (TW) based compression ratio ion mobility programming (CRIMP) approach within Structures for Lossless Ion Manipulations (SLIM) that enables both greatly enlarged trapped ion charge capacities and also their subsequent efficient compression for use in ion mobility (IM) separations. Ion accumulation is conducted in a long serpentine path TW SLIM region after which CRIMP allows the large ion populations to be ‘squeezed’. The compression process occurs at an interface between two SLIM regions, one operating conventionally and the second having an intermittently pausing or ‘stuttering’ TW, allowing the contents of multiple bins of ions from the first region to be merged into a single bin in the second region. In this initial work stationary voltages in the second region were used to block ions from exiting the first (trapping) region, and the resumption of TWs in the second region allows ions to exit, and the population to also be compressed if CRIMP is applied. In our initial evaluation we show that the number of charges trapped for a 40 s accumulation period was ~5×109, more than two orders of magnitude greater than the previously reported charge capacity using an ion funnel trap. We also show that over 1×109 ions can be accumulated with high efficiency in the present device, and that the extent of subsequent compression is only limited by the space charge capacity of the trapping region. Lower compression ratios allow increased IM peak heights without significant loss of signal, while excessively large compression ratios can lead to ion losses and other artifacts. Importantly, we show that extended ion accumulation in conjunction with CRIMP and multiple passes provides the basis for a highly desirable combination of ultra-high sensitivity and ultra-high resolution IM separations using SLIM.

  14. Dustbuster: a New Generation Impact-ionization Time-of-flight Mass Spectrometer for in situ Analysis of Cosmic Dust

    Science.gov (United States)

    Austin, D. E.; Ahrens, T. J.; Beauchamp, J. L.

    2000-10-01

    We have developed and tested a small impact-ionization time-of-flight mass spectrometer for analysis of cosmic dust, suitable for use on deep space missions. This mass spectrometer, named Dustbuster, incorporates a large target area and a reflectron, simultaneously optimizing mass resolution, sensitivity, and collection efficiency. Dust particles hitting the 65-cm2 target plate are partially ionized. The resulting ions are accelerated through a modified reflectron that focuses the ions in space and time to produce high-resolution spectra. The instrument, shown below, measures 10 x 10 x 20 cm, has a mass of 500 g, and consumes little power. Laser desorption ionization of metal and mineral samples (embedded in the impact plate) simulates particle impacts for instrument performance tests. Mass resolution in these experiments is near 200, permitting resolution of isotopes. The mass spectrometer can be combined with other instrument components to determine dust particle trajectories and sizes. This project was funded by NASA's Planetary Instrument Definition and Development Program.

  15. High Energy Ion Acceleration by Extreme Laser Radiation Pressure

    Science.gov (United States)

    2017-03-14

    published in the internationally leading journal Physical Review Letters. We continued to progress this pionee 15.  SUBJECT TERMS ion therapy, heavy ion ...Thomson parabola spectrometer: To separate and provide a measurement of the charge -to-mass ratio and energy spectrum of the different ion species...AFRL-AFOSR-UK-TR-2017-0015 High energy ion acceleration by extreme laser radiation pressure Paul McKenna UNIVERSITY OF STRATHCLYDE VIZ ROYAL COLLEGE

  16. Dynamic Secondary Ion Mass Spectrometry | Materials Science | NREL

    Science.gov (United States)

    Ion Mass Spectrometry (SIMS) uses a continuous, focused beam of primary ions to remove material from the surface of a sample by sputtering. The fraction of sputtered material that is ionized is extracted Identifies all elements or isotopes present in a material, from hydrogen to uranium. Different primary-ion

  17. PENTATRAP. A novel Penning-trap system for high-precision mass measurements

    Energy Technology Data Exchange (ETDEWEB)

    Doerr, Andreas

    2015-01-21

    The novel Penning-trap mass spectrometer PENTATRAP aims at mass-ratio determinations of medium-heavy to heavy ions with relative uncertainties below 10{sup -11}. From the mass ratios of certain ion species, the corresponding mass differences will be determined with sub-eV/c{sup 2} uncertainties. These mass differences are relevant for neutrino-mass experiments, a test of special relativity and tests of bound-state QED. Means to obtain the required precision are very stable trapping fields, the use of highly-charged ions produced by EBITs, a non-destructive cyclotron-frequency determination scheme employing detectors with single-ion sensitivity and a five-trap tower, that allows for measurement schemes being insensitive to magnetic field drifts. Within this thesis, part of the detection electronics was set up and tested under experimental conditions. A single-trap setup was realized. A Faraday cup in the trap tower enabled the proper adjustment of the settings of the beamline connecting the EBIT and the Penning-trap system, resulting in the first trapping of ions at PENTATRAP. A stabilization of switched voltages in the beamline and detailed studies of ion bunch characteristics allowed for reproducible loading of only a few ions. Detection of the axial oscillation of the trapped ions gave hints that in some cases, even single ions had been trapped. Furthermore, valuable conclusions about necessary modifications of the setup could be drawn.

  18. Performance of high-resolution position-sensitive detectors developed for storage-ring decay experiments

    International Nuclear Information System (INIS)

    Yamaguchi, T.; Suzaki, F.; Izumikawa, T.; Miyazawa, S.; Morimoto, K.; Suzuki, T.; Tokanai, F.; Furuki, H.; Ichihashi, N.; Ichikawa, C.; Kitagawa, A.; Kuboki, T.; Momota, S.; Nagae, D.; Nagashima, M.; Nakamura, Y.; Nishikiori, R.; Niwa, T.; Ohtsubo, T.; Ozawa, A.

    2013-01-01

    Highlights: • Position-sensitive detectors were developed for storage-ring decay spectroscopy. • Fiber scintillation and silicon strip detectors were tested with heavy ion beams. • A new fiber scintillation detector showed an excellent position resolution. • Position and energy detection by silicon strip detectors enable full identification. -- Abstract: As next generation spectroscopic tools, heavy-ion cooler storage rings will be a unique application of highly charged RI beam experiments. Decay spectroscopy of highly charged rare isotopes provides us important information relevant to the stellar conditions, such as for the s- and r-process nucleosynthesis. In-ring decay products of highly charged RI will be momentum-analyzed and reach a position-sensitive detector set-up located outside of the storage orbit. To realize such in-ring decay experiments, we have developed and tested two types of high-resolution position-sensitive detectors: silicon strips and scintillating fibers. The beam test experiments resulted in excellent position resolutions for both detectors, which will be available for future storage-ring experiments

  19. Development and testing of a double-focusing, static, axisymmetric mass spectrometer

    International Nuclear Information System (INIS)

    Ritter, G.

    1979-04-01

    The developed mass spectrometer affords very high acceptance (cm 2 sr) compared with conventional mass spectrometers owing to its large solid angle of 0.178 sr. The ion optical properties of the instrument were tested by bombarding various targets (Al, Ni, Ti, Cu, Si) with potassium or caesium ions from a thermionic ion source with energies of 1, 2 and 3 keV and recording mass spectra of positive and negative sputtered ions. The ion optical beam path was calculated analytically (magnet system) in part and numerically in part (energy analyzer, einzel lenses and detector system) and represented in graph form. The results obtained from the mass spectra showed that the magnet system with its twelve permanent magnets is too irregular to produce mass linses with good resolution. Furthermore, it was found that the maximum primary energy of the alkali ions that was possible in this mass spectrometer owing to the breakdown strength was not sufficient to record surface-specific mass spectra since the target surface was covered within a very short time with an at least monatomic layer of alkali ions from the thermionic ion source. (orig./HP) [de

  20. An RF ion source based primary ion gun for secondary ion mass spectroscopy

    International Nuclear Information System (INIS)

    Menon, Ranjini; Nabhiraj, P.Y.; Bhandari, R.K.

    2011-01-01

    In this article we present the design, development and characterization of an RF plasma based ion gun as a primary ion gun for SIMS application. RF ion sources, in particular Inductively Coupled Plasma (ICP) ion sources are superior compared to LMIS and duoplasmtron ion sources since they are filamentless, can produce ions of gaseous elements. At the same time, ICP ion sources offer high angular current density which is an important factor in producing high current in small spot size on the target. These high current microprobes improve the signal to noise ratio by three orders as compared to low current ion sources such as LMIS. In addition, the high current microprobes have higher surface and depth profiling speeds. In this article we describe a simple ion source in its very basic form, two lens optical column and characteristics of microprobe