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.

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

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.

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

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.

INTRIGOSS: A new Library of High Resolution Synthetic Spectra

Science.gov (United States)

Franchini, Mariagrazia; Morossi, Carlo; Di Marcancantonio, Paolo; Chavez, Miguel; GES-Builders

2018-01-01

INTRIGOSS (INaf Trieste Grid Of Synthetic Spectra) is a new High Resolution (HiRes) synthetic spectral library designed for studying F, G, and K stars. The library is based on atmosphere models computed with specified individual element abundances via ATLAS12 code. Normalized SPectra (NSP) and surface Flux SPectra (FSP), in the 4800-5400 Å wavelength range, were computed by means of the SPECTRUM code. The synthetic spectra are computed with an atomic and bi-atomic molecular line list including "bona fide" Predicted Lines (PLs) built by tuning loggf to reproduce very high SNR Solar spectrum and the UVES-U580 spectra of five cool giants extracted from the Gaia-ESO survey (GES). The astrophysical gf-values were then assessed by using more than 2000 stars with homogenous and accurate atmosphere parameters and detailed chemical composition from GES. The validity and greater accuracy of INTRIGOSS NSPs and FSPs with respect to other available spectral libraries is discussed. INTRIGOSS will be available on the web and will be a valuable tool for both stellar atmospheric parameters and stellar population studies.

Production cross-sections for high mass particles and transverse momentum spectra

International Nuclear Information System (INIS)

Arnold, R.C.; Halzen, F.

1977-06-01

The concept of transverse-mass (msub(T)) scaling is examined. It is suggested that: (1) experimental data on pion transverse momentum (psub(T)) spectra provide a reliable guide to expectations for high mass particle production; (2) dimensional scaling, e.g. implied by quark-gluon dynamics, yields an estimate of msub(T) -4 spectra at ultra-high energies; however, stronger damping is expected at currently accessible energies; (3) values increase linearly with the produced particle mass. The results of msub(T) scaling are compared with estimates for high mass production in the context of the Drell-Yan model. (author)

Automatic identification of mass spectra

International Nuclear Information System (INIS)

Drabloes, F.

1992-01-01

Several approaches to preprocessing and comparison of low resolution mass spectra have been evaluated by various test methods related to library search. It is shown that there is a clear correlation between the nature of any contamination of a spectrum, the basic principle of the transformation or distance measure, and the performance of the identification system. The identification of functionality from low resolution spectra has also been evaluated using several classification methods. It is shown that there is an upper limit to the success of this approach, but also that this can be improved significantly by using a very limited amount of additional information. 10 refs

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

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.

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.

Ga+ TOF-SIMS lineshape analysis for resolution enhancement of MALDI MS spectra of a peptide mixture

International Nuclear Information System (INIS)

Malyarenko, D.I.; Chen, H.; Wilkerson, A.L.; Tracy, E.R.; Cooke, W.E.; Manos, D.M.; Sasinowski, M.; Semmes, O.J.

2004-01-01

The use of mass spectrometry to obtain molecular profiles indicative of alteration of concentrations of peptides in body fluids is currently the subject of intense investigation. For surface-based time-of-flight mass spectrometry the reliability and specificity of such profiling methods depend both on the resolution of the measuring instrument and on the preparation of samples. The present work is a part of a program to use Ga + beam TOF-SIMS alone, and as an adjunct to MALDI, in the development of reliable protein and peptide markers for diseases. Here, we describe techniques to prepare samples of relatively high-mass peptides, which serve as calibration standards and proxies for biomarkers. These are: Arg8-vasopressin, human angiotensin II, and somatostatin. Their TOF-SIMS spectra show repeatable characteristic features, with mass resolution exceeding 2000, including parent peaks and chemical adducts. The lineshape analysis for high-resolution parent peaks is shown to be useful for filter construction and deconvolution of inferior resolution SELDI-TOF spectra of calibration peptide mixture

High-resolution x-ray photoemission spectra of silver

DEFF Research Database (Denmark)

Barrie, A.; Christensen, N. E.

1976-01-01

An electron spectrometer fitted with an x-ray monochromator for Al Kα1,2 radiation (1486.6 eV) has been used to record high-resolution x-ray photoelectron spectra for the 4d valence band as well as the 3d spin doublet in silver. The core-level spectrum has a line shape that can be described...... successfully in terms of the many-body theory of Mahan, Nozières, and De Dominicis. The 4d spectrum agrees well with predictions based on a relativistic-augmented-plane-wave band-structure calculation....

High resolution atomic spectra of rare earths : progress report

International Nuclear Information System (INIS)

Saksena, G.D.; Ahmad, S.A.

1976-01-01

High resolution studies of atomic spectra of neodymium and gadolinium are being carried out on a recording Fabry-Perot spectrometer. The present progress report concerns work done on new assignments as well as confirmation of recently assigned electronic configurations and evaluation of isotope shifts of energy levels which have been possible from the isotope shift data obtained for several transitions of NdI, NdII and GdI, GdII respectively. (author)

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.

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.

High-resolution pyrimidine- and ribose-specific 4D HCCH-COSY spectra of RNA using the filter diagonalization method

International Nuclear Information System (INIS)

Douglas, Justin T.; Latham, Michael P.; Armstrong, Geoffrey S.; Bendiak, Brad; Pardi, Arthur

2008-01-01

The NMR spectra of nucleic acids suffer from severe peak overlap, which complicates resonance assignments. 4D NMR experiments can overcome much of the degeneracy in 2D and 3D spectra; however, the linear increase in acquisition time with each new dimension makes it impractical to acquire high-resolution 4D spectra using standard Fourier transform (FT) techniques. The filter diagonalization method (FDM) is a numerically efficient algorithm that fits the entire multi-dimensional time-domain data to a set of multi-dimensional oscillators. Selective 4D constant-time HCCH-COSY experiments that correlate the H5-C5-C6-H6 base spin systems of pyrimidines or the H1'-C1'-C2'-H2' spin systems of ribose sugars were acquired on the 13 C-labeled iron responsive element (IRE) RNA. FDM-processing of these 4D experiments recorded with only 8 complex points in the indirect dimensions showed superior spectral resolution than FT-processed spectra. Practical aspects of obtaining optimal FDM-processed spectra are discussed. The results here demonstrate that FDM-processing can be used to obtain high-resolution 4D spectra on a medium sized RNA in a fraction of the acquisition time normally required for high-resolution, high-dimensional spectra

Line broadening interference for high-resolution nuclear magnetic resonance spectra under inhomogeneous magnetic fields

International Nuclear Information System (INIS)

Wei, Zhiliang; Yang, Jian; Lin, Yanqin; Chen, Zhong; Chen, Youhe

2015-01-01

Nuclear magnetic resonance spectroscopy serves as an important tool for analyzing chemicals and biological metabolites. However, its performance is subject to the magnetic-field homogeneity. Under inhomogeneous fields, peaks are broadened to overlap each other, introducing difficulties for assignments. Here, we propose a method termed as line broadening interference (LBI) to provide high-resolution information under inhomogeneous magnetic fields by employing certain gradients in the indirect dimension to interfere the magnetic-field inhomogeneity. The conventional spectral-line broadening is thus interfered to be non-diagonal, avoiding the overlapping among adjacent resonances. Furthermore, an inhomogeneity correction algorithm is developed based on pattern recognition to recover the high-resolution information from LBI spectra. Theoretical deductions are performed to offer systematic and detailed analyses on the proposed method. Moreover, experiments are conducted to prove the feasibility of the proposed method for yielding high-resolution spectra in inhomogeneous magnetic fields

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

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.

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.

High-resolution spectra of comet C/2013 R1 (Lovejoy)

Science.gov (United States)

Rousselot, P.; Decock, A.; Korsun, P. P.; Jehin, E.; Kulyk, I.; Manfroid, J.; Hutsemékers, D.

2015-08-01

Context. High-resolution spectra of comets permit deriving the physical properties of the coma. In the optical range, relative production rates can be computed, and information about isotopic ratios and the origin of oxygen atoms can be obtained. Aims: The main objective of the work presented here was to obtain information about the chemical composition of comet C/2013 R1 (Lovejoy), a bright and long-period comet that passed perihelion (0.81 au) on 22 December 2013. Methods: We used the HARPS-North echelle spectrograph at the 3.5 m telescope TNG to obtain high-resolution spectra of comet C/2013 R1 (Lovejoy) in the optical range immediately after its perihelion passage during four consecutive nights in the period December 23 to 26, 2013. Results: Our results demonstrate the ability of HARPS-North to efficiently obtain cometary spectra. Very faint emission lines, such as those of 15NH2, have been detected, leading to a rough estimate of the 14N/15N ratio in NH2. The 12C/13C ratio was measured in the C2 lines and is equal to 80 ± 30. The oxygen lines were studied as well (green to red line intensity ratios and widths), confirming that H2O is the main parent molecule that photodissociates to produce oxygen atoms. This suggests that this comet has a high CO2 abundance. Relative production rates for C2 and NH2 were computed, but we found no significant deviation from a typical NH2/C2 ratio. Based on observations made with the Italian Telescopio Nazionale Galileo (TNG) operated on the island of La Palma by the Fundación Galileo Galilei of the INAF (Istituto Nazionale di Astrofisica) at the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias.

High-resolution proton and carbon-13 NMR of membranes: why sonicate?

International Nuclear Information System (INIS)

Oldfield, E.; Bowers, J.L.; Forbes, J.

1987-01-01

The authors have obtained high-field (11.7-T) proton and carbon-13 Fourier transform (FT) nuclear magnetic resonance (NMR) spectra of egg lecithin and egg lecithin-chloresterol (1:1) multibilayers, using magic-angle sample spinning (MASS) techniques, and sonicated egg lecithin and egg lecithin-cholesterol (1:1) vesicles, using conventional FT NMR methods. Resolution of the proton and carbon-13 MASS NMR spectra of the pure egg lecithin samples is essentially identical with that of sonicated samples, but spectra of the unsonicated lipid, using MASS, can be obtained very much faster than with the more dilute, sonicated systems. With the 1:1 lecithin-cholesterol system, proton MASS NMR spectra are virtually identical with conventional FT spectra of sonicated samples, while the 13 C NMR, the authors demonstrate that most 13 C nuclei in the cholesterol moiety can be monitored, even though these same nuclei are essentially invisible, i.e., are severely broadened, in the corresponding sonicated systems. In addition, 13 C MASS NMR spectra can again be recorded much faster than with sonicated samples, due to concentration effects. Taken together, these results strongly suggest there will seldom be need in the future to resort to ultransonic disruption of lipid bilayer membranes in order to obtain high-resolution proton or carbon-13 NMR spectra

A high-resolution atlas of composite Sloan Digital Sky Survey galaxy spectra

Science.gov (United States)

Dobos, László; Csabai, István.; Yip, Ching-Wa; Budavári, Tamás.; Wild, Vivienne; Szalay, Alexander S.

2012-02-01

In this work we present an atlas of composite spectra of galaxies based on the data of the Sloan Digital Sky Survey Data Release 7 (SDSS DR7). Galaxies are classified by colour, nuclear activity and star formation activity to calculate average spectra of high signal-to-noise ratio (S/N) and resolution (? at Δλ= 1 Å), using an algorithm that is robust against outliers. Besides composite spectra, we also compute the first five principal components of the distributions in each galaxy class to characterize the nature of variations of individual spectra around the averages. The continua of the composite spectra are fitted with BC03 stellar population synthesis models to extend the wavelength coverage beyond the coverage of the SDSS spectrographs. Common derived parameters of the composites are also calculated: integrated colours in the most popular filter systems, line-strength measurements and continuum absorption indices (including Lick indices). These derived parameters are compared with the distributions of parameters of individual galaxies, and it is shown on many examples that the composites of the atlas cover much of the parameter space spanned by SDSS galaxies. By co-adding thousands of spectra, a total integration time of several months can be reached, which results in extremely low noise composites. The variations in redshift not only allow for extending the spectral coverage bluewards to the original wavelength limit of the SDSS spectrographs, but also make higher spectral resolution achievable. The composite spectrum atlas is available online at .

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

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...

High-resolution n = 3 to n = 2 spectra of neonlike silver

International Nuclear Information System (INIS)

Beiersdorfer, P.; Bitter, M.; von Goeler, S.

1986-01-01

Spectra of the n = 3 to n = 2 transitions in neonlike silver emitted from the Princeton Large Torus have been recorded with a high-resolution Bragg-crystal spectrometer. The measurements cover the wavelength region 3.3--4.1 A-circle and include the forbidden 3p→2p electric quadrupole lines. Transitions in the adjacent sodiumlike, magnesiumlike, and aluminumlike charge states of silver have also been observed and identified. The Ly-α spectra of hydrogenlike argon and iron, the Kα spectra of heliumlike argon, potassium, manganese, and iron, and the Kβ spectrum of heliumlike argon fall in the same wavelength region in first or second order and have been measured concurrently. These spectra provide a coherent set of wavelength reference data obtained with the same spectrometer and from the same tokamak. This set is used as a basis to compare wavelength predictions for one- and two-electron systems to each other and to determine the transition energies of the silver lines with great accuracy

MetaUniDec: High-Throughput Deconvolution of Native Mass Spectra

Science.gov (United States)

Reid, Deseree J.; Diesing, Jessica M.; Miller, Matthew A.; Perry, Scott M.; Wales, Jessica A.; Montfort, William R.; Marty, Michael T.

2018-04-01

The expansion of native mass spectrometry (MS) methods for both academic and industrial applications has created a substantial need for analysis of large native MS datasets. Existing software tools are poorly suited for high-throughput deconvolution of native electrospray mass spectra from intact proteins and protein complexes. The UniDec Bayesian deconvolution algorithm is uniquely well suited for high-throughput analysis due to its speed and robustness but was previously tailored towards individual spectra. Here, we optimized UniDec for deconvolution, analysis, and visualization of large data sets. This new module, MetaUniDec, centers around a hierarchical data format 5 (HDF5) format for storing datasets that significantly improves speed, portability, and file size. It also includes code optimizations to improve speed and a new graphical user interface for visualization, interaction, and analysis of data. To demonstrate the utility of MetaUniDec, we applied the software to analyze automated collision voltage ramps with a small bacterial heme protein and large lipoprotein nanodiscs. Upon increasing collisional activation, bacterial heme-nitric oxide/oxygen binding (H-NOX) protein shows a discrete loss of bound heme, and nanodiscs show a continuous loss of lipids and charge. By using MetaUniDec to track changes in peak area or mass as a function of collision voltage, we explore the energetic profile of collisional activation in an ultra-high mass range Orbitrap mass spectrometer. [Figure not available: see fulltext.

Unattented mode monitoring of high resolution gamma-ray spectra

International Nuclear Information System (INIS)

Smith, B.G.R.; Van Dyck, P.; Debraix, P.

1991-01-01

An Isotope Monitoring System (IMS) for unattended spectrum acquisition is described. This consists of a simple low cost flexible software package running on a Compaq 80386 and controlling up to 4 Canberra Packard System 100 multi-channel analyzer (MCA) cards. The IMS permits the independent configuration of each of the 4 MCA cards for different monitoring cycles and for different spectrum acquisition cycles each being based upon different trigger criteria. In this way IMS is able to automatically identify events, time tag them, and acquire and store valid spectra corresponding to those event. An additional feature of IMS permits to run a Multigroup Analysis (MGA) software package for the determination of plutonium isotopic compositions in batch mode. One particular application is discussed which consists of 4 high resolution gamma-ray detector systems connected together to the IMS for unattended spectrum acquisition. The off-line batch mode analysis of the spectra using MGA is also discussed

High-resolution K-shell spectra from laser excited molybdenum plasmas

Directory of Open Access Journals (Sweden)

Szabo C.I.

2013-11-01

Full Text Available X-ray spectra from Molybdenum plasmas were recorded by a Cauchois-type cylindrically bent Transmission Crystal Spectrometer (TCS. The absolutely calibrated spectrometer provides an unprecedented resolution of inner shell transitions (K x-ray radiation. This tool allows us to resolve individual lines from different charge states existing inside the laser-produced plasma. The inner shell transitions from highly charged Molybdenum shown in this report have never been resolved before in such detail in a laser-produced plasma.

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.

A high-resolution neutron spectra unfolding method using the Genetic Algorithm technique

CERN Document Server

Mukherjee, B

2002-01-01

The Bonner sphere spectrometers (BSS) are commonly used to determine the neutron spectra within various nuclear facilities. Sophisticated mathematical tools are used to unfold the neutron energy distribution from the output data of the BSS. This paper highlights a novel high-resolution neutron spectra-unfolding method using the Genetic Algorithm (GA) technique. The GA imitates the biological evolution process prevailing in the nature to solve complex optimisation problems. The GA method was utilised to evaluate the neutron energy distribution, average energy, fluence and equivalent dose rates at important work places of a DIDO class research reactor and a high-energy superconducting heavy ion cyclotron. The spectrometer was calibrated with a sup 2 sup 4 sup 1 Am/Be (alpha,n) neutron standard source. The results of the GA method agreed satisfactorily with the results obtained by using the well-known BUNKI neutron spectra unfolding code.

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.)

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.

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).

Analysis of X-ray Spectra of High-Z Elements obtained on Nike with high spectral and spatial resolution

Science.gov (United States)

Aglitskiy, Yefim; Weaver, J. L.; Karasik, M.; Serlin, V.; Obenschain, S. P.; Ralchenko, Yu.

2014-10-01

The spectra of multi-charged ions of Hf, Ta, W, Pt, Au and Bi have been studied on Nike krypton-fluoride laser facility with the help of two kinds of X-ray spectrometers. First, survey instrument covering a spectral range from 0.5 to 19.5 angstroms which allows simultaneous observation of both M- and N- spectra of above mentioned elements with high spectral resolution. Second, an imaging spectrometer with interchangeable spherically bent Quartz crystals that added higher efficiency, higher spectral resolution and high spatial resolution to the qualities of the former one. Multiple spectral lines with X-ray energies as high as 4 keV that belong to the isoelectronic sequences of Fe, Co, Ni, Cu and Zn were identified with the help of NOMAD package developed by Dr. Yu. Ralchenko and colleagues. In our continuous effort to support DOE-NNSA's inertial fusion program, this campaign covered a wide range of plasma conditions that result in production of relatively energetic X-rays. Work supported by the US DOE/NNSA.

High-Quality Medium-Resolution Gamma-Ray Spectra from Certified Reference Uranium and Plutonium Materials

International Nuclear Information System (INIS)

Zsigrai, J.; Muehleisen, A.; ); Weber, A.-L.; Funk, P.; Berlizov, A.; Mintcheva, J.

2015-01-01

The Institute of Transuranium Elements (ITU) has made an effort to record a collection of medium resolution gamma-ray spectra from well-characterized U and Pu certified reference materials CRM-171 (also known as SRM-969), CBNM-271, and Harwell PIDIE standards. The goal of this exercise was twofold: (i) to complement the international database of reference gamma-ray spectra with high-quality data for medium resolution spectrometers, and (ii) to feed Phase I of the U/Pu isotopic inter-comparison exercise that is being jointly organized by the ESARDA NDA Working Group and IAEA. Phase II of the exercise will be fed by similar spectra recorded by Institute for Radiological Protection and Nuclear Safety (IRSN). These activities are supported through a joint Member State Support Programmes (MSSP) task and aimed at delivering reliable methodologies for the determination of U/Pu isotopic composition using medium resolution gamma-spectrometers. The latter have obvious benefits for in-field applications, amongst which are better usability, portability and maintainability. As the spectra will be made available online for software developers and end users, ultimately this will also contribute to sustainability as well as the improved and validated performance of existing U/Pu isotopic codes. The spectra were recorded using the IAEA's standard Lanthanum Bromide (LaBr3(Ce)) (2.0'' x 0.5'') and Cadmium Zink Telluride (CdZnTe) (500 mm''3) detectors and acquisition electronics. Aiming to acquire the highest quality reference data, the spectra were measured for long acquisition times, ensuring very good counting statistics across potentially useful spectral intervals — up to 1 MeV for the CdZnTe and up to 2.6 MeV for the LaBr3(Ce) detectors. Great attention was also paid to ensure that the measurement geometry was stable and reproducible, and the spectra had minimum influence from background radiation and pile-up effects. The paper will briefly

High resolution n = 3 to n = 2 spectra of neon-like silver

International Nuclear Information System (INIS)

Beiersdorfer, P.; Bitter, M.; von Goeler, S.

1986-04-01

Spectra of the n = 3 to n = 2 transitions in neon-like silver emitted from the Princeton Large Torus have been recorded with a high-resolution Bragg-crystal spectrometer. The measurements cover the wavelength region 3.3 to 4.1 A and include the forbidden 3p → 2p electric quadrupole lines. Transitions in the adjacent sodium-like, and aluminum-like charge states of silver have also been observed and identified. The Ly-α spectra of hydrogen-like argon and iron, the Kα spectra of helium-like argon, potassium, manganese, and iron, and the Kβ spectrum of helium-like argon fall in the same wavelength region in first or second order and have been measured concurrently. These spectra provide a coherent set of wavelength reference data obtained with the same spectrometer and from the same tokamak. This set is used as a basis to compare wavelength predictions for one- and two-electron systems to each other and to determine the transition energies of the silver lines with great accuracy

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.

High-Resolution Infrared and Raman Spectra of the Polycrystalline Sinomenine Hydrochloride

Directory of Open Access Journals (Sweden)

Liu Xiao-Dong

2016-01-01

Full Text Available High-resolution infrared and Raman spectra of the polycrystalline sinomenine (SM hydrochloride have been measured to work out its whole really existing vibrational spectral bands. Except for the hydroxyl stretching modes and IR active bands less than 400 cm−1, most normal modes (about 34 are both IR and Raman active. In addition, 8 Raman bands less than 400 cm−1 are tentatively assigned, for the first time to our knowledge, to stretching/bending modes of the aromatic-ring−methoxyls and (SMH+–Cl− ions, respectively.

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...

Measurements of spatially resolved high resolution spectra of laser-produced plasmas. FY 83 annual report

International Nuclear Information System (INIS)

Feldman, U.

1984-01-01

A high resolution grazing incidence spectrograph, provided by the Naval Research Laboratory and the Goddard Space Flight Center, has been installed on the Omega laser facility of the Laboratory for Laser Energetics (LLE) at the University of Rochester. This 3 meter instrument, with a 1200 lines/mm grating blazed at 2 0 35', has produced extremely high quality spectra in the wavelength region 10 A to 100 A. Spectra have been obtained from glass microballoon targets that are coated with a variety of high-Z materials. Transitions from the Na-like and Ne-like ionization stages of Fe, Ni, Cu, and Kr have been identified

LSD-based analysis of high-resolution stellar spectra

Science.gov (United States)

Tsymbal, V.; Tkachenko, A.; Van, Reeth T.

2014-11-01

We present a generalization of the method of least-squares deconvolution (LSD), a powerful tool for extracting high S/N average line profiles from stellar spectra. The generalization of the method is effected by extending it towards the multiprofile LSD and by introducing the possibility to correct the line strengths from the initial mask. We illustrate the new approach by two examples: (a) the detection of astroseismic signatures from low S/N spectra of single stars, and (b) disentangling spectra of multiple stellar objects. The analysis is applied to spectra obtained with 2-m class telescopes in the course of spectroscopic ground-based support for space missions such as CoRoT and Kepler. Usually, rather high S/N is required, so smaller telescopes can only compete successfully with more advanced ones when one can apply a technique that enables a remarkable increase in the S/N of the spectra which they observe. Since the LSD profiles have a potential for reconstruction what is common in all the spectral profiles, it should have a particular practical application to faint stars observed with 2-m class telescopes and whose spectra show remarkable LPVs.

TSAR: a program for automatic resonance assignment using 2D cross-sections of high dimensionality, high-resolution spectra

Energy Technology Data Exchange (ETDEWEB)

Zawadzka-Kazimierczuk, Anna; Kozminski, Wiktor [University of Warsaw, Faculty of Chemistry (Poland); Billeter, Martin, E-mail: martin.billeter@chem.gu.se [University of Gothenburg, Biophysics Group, Department of Chemistry and Molecular Biology (Sweden)

2012-09-15

While NMR studies of proteins typically aim at structure, dynamics or interactions, resonance assignments represent in almost all cases the initial step of the analysis. With increasing complexity of the NMR spectra, for example due to decreasing extent of ordered structure, this task often becomes both difficult and time-consuming, and the recording of high-dimensional data with high-resolution may be essential. Random sampling of the evolution time space, combined with sparse multidimensional Fourier transform (SMFT), allows for efficient recording of very high dimensional spectra ({>=}4 dimensions) while maintaining high resolution. However, the nature of this data demands for automation of the assignment process. Here we present the program TSAR (Tool for SMFT-based Assignment of Resonances), which exploits all advantages of SMFT input. Moreover, its flexibility allows to process data from any type of experiments that provide sequential connectivities. The algorithm was tested on several protein samples, including a disordered 81-residue fragment of the {delta} subunit of RNA polymerase from Bacillus subtilis containing various repetitive sequences. For our test examples, TSAR achieves a high percentage of assigned residues without any erroneous assignments.

Application of the Oslo method to high resolution gamma spectra

Science.gov (United States)

Simon, A.; Guttormsen, M.; Larsen, A. C.; Beausang, C. W.; Humby, P.

2015-10-01

Hauser-Feshbach statistical model is a widely used tool for calculation of the reaction cross section, in particular for astrophysical processes. The HF model requires as an input an optical potential, gamma-strength function (GSF) and level density (LD) to properly model the statistical properties of the nucleus. The Oslo method is a well established technique to extract GSFs and LDs from experimental data, typically used for gamma-spectra obtained with scintillation detectors. Here, the first application of the Oslo method to high-resolution data obtained using the Ge detectors of the STARLITER setup at TAMU is discussed. The GSFs and LDs extracted from (p,d) and (p,t) reactions on 152154 ,Sm targets will be presented.

Neural network radiative transfer solvers for the generation of high resolution solar irradiance spectra parameterized by cloud and aerosol parameters

International Nuclear Information System (INIS)

Taylor, M.; Kosmopoulos, P.G.; Kazadzis, S.; Keramitsoglou, I.; Kiranoudis, C.T.

2016-01-01

This paper reports on the development of a neural network (NN) model for instantaneous and accurate estimation of solar radiation spectra and budgets geared toward satellite cloud data using a ≈2.4 M record, high-spectral resolution look up table (LUT) generated with the radiative transfer model libRadtran. Two NN solvers, one for clear sky conditions dominated by aerosol and one for cloudy skies, were trained on a normally-distributed and multiparametric subset of the LUT that spans a very broad class of atmospheric and meteorological conditions as inputs with corresponding high resolution solar irradiance target spectra as outputs. The NN solvers were tested by feeding them with a large (10 K record) “off-grid” random subset of the LUT spanning the training data space, and then comparing simulated outputs with target values provided by the LUT. The NN solvers demonstrated a capability to interpolate accurately over the entire multiparametric space. Once trained, the NN solvers allow for high-speed estimation of solar radiation spectra with high spectral resolution (1 nm) and for a quantification of the effect of aerosol and cloud optical parameters on the solar radiation budget without the need for a massive database. The cloudy sky NN solver was applied to high spatial resolution (54 K pixel) cloud data extracted from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) onboard the geostationary Meteosat Second Generation 3 (MSG3) satellite and demonstrated that coherent maps of spectrally-integrated global horizontal irradiance at this resolution can be produced on the order of 1 min. - Highlights: • Neural network radiative transfer solvers for generation of solar irradiance spectra. • Sensitivity analysis of irradiance spectra with respect to aerosol and cloud parameters. • Regional maps of total global horizontal irradiance for cloudy sky conditions. • Regional solar radiation maps produced directly from MSG3/SEVIRI satellite inputs.

kspectrum: an open-source code for high-resolution molecular absorption spectra production

International Nuclear Information System (INIS)

Eymet, V.; Coustet, C.; Piaud, B.

2016-01-01

We present the kspectrum, scientific code that produces high-resolution synthetic absorption spectra from public molecular transition parameters databases. This code was originally required by the atmospheric and astrophysics communities, and its evolution is now driven by new scientific projects among the user community. Since it was designed without any optimization that would be specific to any particular application field, its use could also be extended to other domains. kspectrum produces spectral data that can subsequently be used either for high-resolution radiative transfer simulations, or for producing statistic spectral model parameters using additional tools. This is a open project that aims at providing an up-to-date tool that takes advantage of modern computational hardware and recent parallelization libraries. It is currently provided by Méso-Star (http://www.meso-star.com) under the CeCILL license, and benefits from regular updates and improvements. (paper)

Towards automatic metabolomic profiling of high-resolution one-dimensional proton NMR spectra

International Nuclear Information System (INIS)

Mercier, Pascal; Lewis, Michael J.; Chang, David; Baker, David; Wishart, David S.

2011-01-01

Nuclear magnetic resonance (NMR) and Mass Spectroscopy (MS) are the two most common spectroscopic analytical techniques employed in metabolomics. The large spectral datasets generated by NMR and MS are often analyzed using data reduction techniques like Principal Component Analysis (PCA). Although rapid, these methods are susceptible to solvent and matrix effects, high rates of false positives, lack of reproducibility and limited data transferability from one platform to the next. Given these limitations, a growing trend in both NMR and MS-based metabolomics is towards targeted profiling or “quantitative” metabolomics, wherein compounds are identified and quantified via spectral fitting prior to any statistical analysis. Despite the obvious advantages of this method, targeted profiling is hindered by the time required to perform manual or computer-assisted spectral fitting. In an effort to increase data analysis throughput for NMR-based metabolomics, we have developed an automatic method for identifying and quantifying metabolites in one-dimensional (1D) proton NMR spectra. This new algorithm is capable of using carefully constructed reference spectra and optimizing thousands of variables to reconstruct experimental NMR spectra of biofluids using rules and concepts derived from physical chemistry and NMR theory. The automated profiling program has been tested against spectra of synthetic mixtures as well as biological spectra of urine, serum and cerebral spinal fluid (CSF). Our results indicate that the algorithm can correctly identify compounds with high fidelity in each biofluid sample (except for urine). Furthermore, the metabolite concentrations exhibit a very high correlation with both simulated and manually-detected values.

Towards automatic metabolomic profiling of high-resolution one-dimensional proton NMR spectra

Energy Technology Data Exchange (ETDEWEB)

Mercier, Pascal; Lewis, Michael J.; Chang, David, E-mail: dchang@chenomx.com [Chenomx Inc (Canada); Baker, David [Pfizer Inc (United States); Wishart, David S. [University of Alberta, Department of Computing Science and Biological Sciences (Canada)

2011-04-15

Nuclear magnetic resonance (NMR) and Mass Spectroscopy (MS) are the two most common spectroscopic analytical techniques employed in metabolomics. The large spectral datasets generated by NMR and MS are often analyzed using data reduction techniques like Principal Component Analysis (PCA). Although rapid, these methods are susceptible to solvent and matrix effects, high rates of false positives, lack of reproducibility and limited data transferability from one platform to the next. Given these limitations, a growing trend in both NMR and MS-based metabolomics is towards targeted profiling or 'quantitative' metabolomics, wherein compounds are identified and quantified via spectral fitting prior to any statistical analysis. Despite the obvious advantages of this method, targeted profiling is hindered by the time required to perform manual or computer-assisted spectral fitting. In an effort to increase data analysis throughput for NMR-based metabolomics, we have developed an automatic method for identifying and quantifying metabolites in one-dimensional (1D) proton NMR spectra. This new algorithm is capable of using carefully constructed reference spectra and optimizing thousands of variables to reconstruct experimental NMR spectra of biofluids using rules and concepts derived from physical chemistry and NMR theory. The automated profiling program has been tested against spectra of synthetic mixtures as well as biological spectra of urine, serum and cerebral spinal fluid (CSF). Our results indicate that the algorithm can correctly identify compounds with high fidelity in each biofluid sample (except for urine). Furthermore, the metabolite concentrations exhibit a very high correlation with both simulated and manually-detected values.

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

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

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.

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/).

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.

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...

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.

A new automated assign and analysing method for high-resolution rotationally resolved spectra using genetic algorithms

NARCIS (Netherlands)

Meerts, W.L.; Schmitt, M.

2006-01-01

This paper describes a numerical technique that has recently been developed to automatically assign and fit high-resolution spectra. The method makes use of genetic algorithms (GA). The current algorithm is compared with previously used analysing methods. The general features of the GA and its

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

High resolution krypton M/sub 4,5/ x-ray emission spectra

International Nuclear Information System (INIS)

Perera, R.C.C.; Hettrick, M.C.; Lindle, D.W.

1987-10-01

High resolution M/sub 4,5/ (3d → 4p) x-ray emission spectra from a krypton plasma were measured using a recently developed grazing-incidence reflection-grating monochromator/spectrometer with very high flux rates at extreme ultraviolet and soft x-ray wave lengths. The nominal resolving power of the instrument, E/ΔE, is about 300 in this energy range (∼80 eV). Three dipole-allowed 3d → 4p emission lines were observed at 80.98 eV, 80.35 eV and 79.73 eV. A broad peak at about 82.3 eV is tentatively assigned to transitions resulting from Kr 2+ , and effects of excitation energy on M/sub 4,5/ x-ray emission were observed. 9 refs., 3 figs., 1 tab

High resolution spectroscopy of six new extreme helium stars

Science.gov (United States)

Heber, U.; Jones, G.; Drilling, J. S.

1986-01-01

High resolution spectra of six newly discovered extreme helium stars are presented. LSS 5121 is shown to be a spectroscopical twin of the hot extreme helium star HD 160641. A preliminary LTE analysis of LSS 3184 yielded an effective temperature of 22,000 K and a surface gravity of log g = 3.2. Four stars form a new subgroup, classified by sharp-lined He I spectra and pronounced O II spectra, and it is conjectured that these lie close to the Eddington limit. The whole group of extreme helium stars apparently is inhomogeneous with respect to luminosity to mass ratio and chemical composition.

De novo analysis of electron impact mass spectra using fragmentation trees

International Nuclear Information System (INIS)

Hufsky, Franziska; Rempt, Martin; Rasche, Florian; Pohnert, Georg; Böcker, Sebastian

2012-01-01

Highlights: ► We present a method for de novo analysis of accurate mass EI mass spectra of small molecules. ► This method identifies the molecular ion and thus the molecular formula where the molecular ion is present in the spectrum. ► Fragmentation trees are constructed by automated signal extraction and evaluation. ► These trees explain relevant fragmentation reactions. ► This method will be very helpful in the automated analysis of unknown metabolites. - Abstract: The automated fragmentation analysis of high resolution EI mass spectra based on a fragmentation tree algorithm is introduced. Fragmentation trees are constructed from EI spectra by automated signal extraction and evaluation. These trees explain relevant fragmentation reactions and assign molecular formulas to fragments. The method enables the identification of the molecular ion and the molecular formula of a metabolite if the molecular ion is present in the spectrum. These identifications are independent of existing library knowledge and, thus, support assignment and structural elucidation of unknown compounds. The method works even if the molecular ion is of very low abundance or hidden under contaminants with higher masses. We apply the algorithm to a selection of 50 derivatized and underivatized metabolites and demonstrate that in 78% of cases the molecular ion can be correctly assigned. The automatically constructed fragmentation trees correspond very well to published mechanisms and allow the assignment of specific relevant fragments and fragmentation pathways even in the most complex EI-spectra in our dataset. This method will be very helpful in the automated analysis of metabolites that are not included in common libraries and it thus has the potential to support the explorative character of metabolomics studies.

Optical and Near-infrared Spectra of σ Orionis Isolated Planetary-mass Objects

Energy Technology Data Exchange (ETDEWEB)

Zapatero Osorio, M. R. [Centro de Astrobiología (CSIC-INTA), Crta. Ajalvir km 4, E-28850 Torrejón de Ardoz, Madrid (Spain); Béjar, V. J. S. [Instituto de Astrofísica de Canarias, C/. Vía Láctea s/n, E-38205 La Laguna, Tenerife (Spain); Ramírez, K. Peña, E-mail: mosorio@cab.inta-csic.es, E-mail: vbejar@iac.es, E-mail: karla.pena@uantof.cl [Unidad de Astronomía de la Universidad de Antofagasta, Av. U. de Antofagasta. 02800 Antofagasta (Chile)

2017-06-10

We have obtained low-resolution optical (0.7–0.98 μ m) and near-infrared (1.11–1.34 μ m and 0.8–2.5 μ m) spectra of 12 isolated planetary-mass candidates ( J = 18.2–19.9 mag) of the 3 Myr σ Orionis star cluster with the aim of determining the spectroscopic properties of very young, substellar dwarfs and assembling a complete cluster mass function. We have classified our targets by visual comparison with high- and low-gravity standards and by measuring newly defined spectroscopic indices. We derived L0–L4.5 and M9–L2.5 using high- and low-gravity standards, respectively. Our targets reveal clear signposts of youth, thus corroborating their cluster membership and planetary masses (6–13 M {sub Jup}). These observations complete the σ Orionis mass function by spectroscopically confirming the planetary-mass domain to a confidence level of ∼75%. The comparison of our spectra with BT-Settl solar metallicity model atmospheres yields a temperature scale of 2350–1800 K and a low surface gravity of log g ≈ 4.0 [cm s{sup −2}], as would be expected for young planetary-mass objects. We discuss the properties of the cluster’s least-massive population as a function of spectral type. We have also obtained the first optical spectrum of S Ori 70, a T dwarf in the direction of σ Orionis. Our data provide reference optical and near-infrared spectra of very young L dwarfs and a mass function that may be used as templates for future studies of low-mass substellar objects and exoplanets. The extrapolation of the σ Orionis mass function to the solar neighborhood may indicate that isolated planetary-mass objects with temperatures of ∼200–300 K and masses in the interval 6–13 M {sub Jup} may be as numerous as very low-mass stars.

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....

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

High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

Energy Technology Data Exchange (ETDEWEB)

Romonosky, Dian E.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

2015-03-19

A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents

HIGH RESOLUTION OPTICAL AND NIR SPECTRA OF HBC 722

Energy Technology Data Exchange (ETDEWEB)

Lee, Jeong-Eun; Park, Sunkyung [School of Space Research, Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 446-701 (Korea, Republic of); Green, Joel D.; Cochran, William D. [Department of Astronomy, University of Texas at Austin, TX (United States); Kang, Wonseok; Lee, Sang-Gak [National Youth Space Center, 200 Deokheungyangjjok-gil, Dongil-myeon, Goheung-gun, Jeollanam-do 548-951 (Korea, Republic of); Sung, Hyun-Il, E-mail: jeongeun.lee@khu.ac.kr, E-mail: sunkyung@khu.ac.kr, E-mail: joel@astro.as.utexas.edu, E-mail: wdc@astro.as.utexas.edu, E-mail: wskang@kywa.or.kr, E-mail: sanggak@kywa.or.kr, E-mail: hisung@kasi.re.kr [Korea Astronomy and Space Science Institute, 776 Daedeok-daero, Yuseong-gu, Daejeon 305-348 (Korea, Republic of)

2015-07-01

We present the results of high resolution (R ≥ 30,000) optical and near-IR spectroscopic monitoring observations of HBC 722, a recent FU Orionis object that underwent an accretion burst in 2010. We observed HBC 722 in the optical/near-IR with the Bohyunsan Optical Echelle Spectrograph, Hobby–Eberly Telescope-HRS, and Immersion Grating Infrared Spectrograph, at various points in the outburst. We found atomic lines with strongly blueshifted absorption features or P Cygni profiles, both evidence of a wind driven by the accretion. Some lines show a broad double-peaked absorption feature, evidence of disk rotation. However, the wind-driven and disk-driven spectroscopic features are anti-correlated in time; the disk features became strong as the wind features disappeared. This anti-correlation might indicate that the rebuilding of the inner disk was interrupted by the wind pressure during the first 2 years. The half-width at half-depth of the double-peaked profiles decreases with wavelength, indicative of the Keplerian rotation; the optical spectra with the disk feature are fitted by a G5 template stellar spectrum convolved with a rotation velocity of 70 km s{sup −1} while the near-IR disk features are fitted by a K5 template stellar spectrum convolved with a rotation velocity of 50 km s{sup −1}. Therefore, the optical and near-IR spectra seem to trace the disk at 39 and 76 R{sub ⊙}, respectively. We fit a power-law temperature distribution in the disk, finding an index of 0.8, comparable to optically thick accretion disk models.

NLTE ANALYSIS OF HIGH-RESOLUTION H -BAND SPECTRA. I. NEUTRAL SILICON

Energy Technology Data Exchange (ETDEWEB)

Zhang, Junbo; Shi, Jianrong; Liu, Chao [Key Laboratory of Optical Astronomy, National Astronomical Observatories, Chinese Academy of Sciences, A20 Datun Road, Chaoyang District, Beijing 100012 (China); Pan, Kaike [Apache Point Observatory and New Mexico State University, P.O. Box 59, Sunspot, NM, 88349-0059 (United States); Prieto, Carlos Allende, E-mail: sjr@bao.ac.cn [Instituto de Astrofísica de Canarias, E-38205 La Laguna, Tenerife (Spain)

2016-12-20

We investigated the reliability of our silicon atomic model and the influence of non-local thermodynamical equilibrium (NLTE) on the formation of neutral silicon (Si i) lines in the near-infrared (near-IR) H -band. We derived the differential Si abundances for 13 sample stars with high-resolution H -band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE), as well as from optical spectra, both under local thermodynamical equilibrium (LTE) and NLTE conditions. We found that the differences between the Si abundances derived from the H -band and from optical lines for the same stars are less than 0.1 dex when the NLTE effects are included, and that NLTE reduces the line-to-line scatter in the H -band spectra for most sample stars. These results suggest that our Si atomic model is appropriate for studying the formation of H -band Si lines. Our calculations show that the NLTE corrections of the Si i H -band lines are negative, i.e., the final Si abundances will be overestimated in LTE. The corrections for strong lines depend on surface gravity, and tend to be larger for giants, reaching ∼−0.2 dex in our sample, and up to ∼−0.4 dex in extreme cases of APOGEE targets. Thus, the NLTE effects should be included in deriving silicon abundances from H -band Si i lines, especially for the cases where only strong lines are available.

Temperature dependence of high-resolution resonant photoemission spectra of CeSi

International Nuclear Information System (INIS)

Mimura, Kojiro; Noguchi, Satoru; Suzuki, Mitsuharu; Higashiguchi, Mitsuharu; Shimada, Kenya; Ichikawa, Kouichi; Taguchi, Yukihiro; Namatame, Hirofumi; Taniguchi, Masaki; Aita, Osamu

2005-01-01

High-resolution Ce 4d-4f resonant photoemission spectra near the Fermi level of CeSi with the Neel temperature of 5.9K have been measured at temperatures from 5.6 to 200K, in order to investigate the competition between the Ruderman-Kittel-Kasuya-Yoshida (RKKY) interaction and the Kondo effect. As temperature is decreasing down to 30K, the intensity due to the Ce 4f 5/2 1 final state increases because of the evolution of the heavy Fermion behaviour caused by the Kondo effect. The intensity, however, decreases gradually from 30 to 5.6K. This indicates that the heavy Fermion behaviour is strongly suppressed by the anti-ferromagnetic ordering due to the RKKY interaction

Kinetic energy spectra, vertical resolution and dissipation in high-resolution atmospheric simulations.

Science.gov (United States)

Skamarock, W. C.

2017-12-01

We have performed week-long full-physics simulations with the MPAS global model at 15 km cell spacing using vertical mesh spacings of 800, 400, 200 and 100 meters in the mid-troposphere through the mid-stratosphere. We find that the horizontal kinetic energy spectra in the upper troposphere and stratosphere does not converge with increasing vertical resolution until we reach 200 meter level spacing. Examination of the solutions indicates that significant inertia-gravity waves are not vertically resolved at the lower vertical resolutions. Diagnostics from the simulations indicate that the primary kinetic energy dissipation results from the vertical mixing within the PBL parameterization and from the gravity-wave drag parameterization, with smaller but significant contributions from damping in the vertical transport scheme and from the horizontal filters in the dynamical core. Most of the kinetic energy dissipation in the free atmosphere occurs within breaking mid-latitude baroclinic waves. We will briefly review these results and their implications for atmospheric model configuration and for atmospheric dynamics, specifically that related to the dynamics associated with the mesoscale kinetic energy spectrum.

Parametrization relating the fermionic mass spectra

International Nuclear Information System (INIS)

Kleppe, A.

1993-01-01

When parametrizing the fermionic mass spectra in terms of the unit matrix and a recursive matrix scrR 0 , which corresponds to an underlying scaling pattern in the mass spectra, each fermionic sector is characterized by three parameters: k, α, and R. Using the set of relations displayed by the parameters of the different sectors, it is possible to formulate a ''family Lagrangian'' which for each sector encompasses all the families. Relations between quark masses are furthermore deduced from these ''family Lagrangians.'' Using the relations between the parameters of the different charge sectors, it is also possible to ''derive'' the quark mass spectra from the (charged) leptonic mass spectrum

Structure Annotation and Quantification of Wheat Seed Oxidized Lipids by High-Resolution LC-MS/MS.

Science.gov (United States)

Riewe, David; Wiebach, Janine; Altmann, Thomas

2017-10-01

Lipid oxidation is a process ubiquitous in life, but the direct and comprehensive analysis of oxidized lipids has been limited by available analytical methods. We applied high-resolution liquid chromatography-mass spectrometry (LC-MS) and tandem mass spectrometry (MS/MS) to quantify oxidized lipids (glycerides, fatty acids, phospholipids, lysophospholipids, and galactolipids) and implemented a platform-independent high-throughput-amenable analysis pipeline for the high-confidence annotation and acyl composition analysis of oxidized lipids. Lipid contents of 90 different naturally aged wheat ( Triticum aestivum ) seed stocks were quantified in an untargeted high-resolution LC-MS experiment, resulting in 18,556 quantitative mass-to-charge ratio features. In a posthoc liquid chromatography-tandem mass spectrometry experiment, high-resolution MS/MS spectra (5 mD accuracy) were recorded for 8,957 out of 12,080 putatively monoisotopic features of the LC-MS data set. A total of 353 nonoxidized and 559 oxidized lipids with up to four additional oxygen atoms were annotated based on the accurate mass recordings (1.5 ppm tolerance) of the LC-MS data set and filtering procedures. MS/MS spectra available for 828 of these annotations were analyzed by translating experimentally known fragmentation rules of lipids into the fragmentation of oxidized lipids. This led to the identification of 259 nonoxidized and 365 oxidized lipids by both accurate mass and MS/MS spectra and to the determination of acyl compositions for 221 nonoxidized and 295 oxidized lipids. Analysis of 15-year aged wheat seeds revealed increased lipid oxidation and hydrolysis in seeds stored in ambient versus cold conditions. © 2017 The author(s). All Rights Reserved.

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)

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.

High-resolution gas-phase spectroscopy of a single-bond axle rotary motor

NARCIS (Netherlands)

Maltseva, Elena; Amirjalayer, Saeed; Cnossen, Arjen; Browne, Wesley R.; Feringa, Ben L.; Buma, Wybren Jan

2017-01-01

High-resolution laser spectroscopy in combination with molecular beams and mass-spectrometry has been applied to study samples of a prototypical rotary motor. Vibrationally well-resolved excitation spectra have been recorded that are assigned, however, to a structural isomer of the original rotary

Assessment of modern spectral analysis methods to improve wavenumber resolution of F-K spectra

International Nuclear Information System (INIS)

Shirley, T.E.; Laster, S.J.; Meek, R.A.

1987-01-01

The improvement in wavenumber spectra obtained by using high resolution spectral estimators is examined. Three modern spectral estimators were tested, namely the Autoregressive/Maximum Entropy (AR/ME) method, the Extended Prony method, and an eigenstructure method. They were combined with the conventional Fourier method by first transforming each trace with a Fast Fourier Transform (FFT). A high resolution spectral estimator was applied to the resulting complex spatial sequence for each frequency. The collection of wavenumber spectra thus computed comprises a hybrid f-k spectrum with high wavenumber resolution and less spectral ringing. Synthetic and real data records containing 25 traces were analyzed by using the hybrid f-k method. The results show an FFT-AR/ME f-k spectrum has noticeably better wavenumber resolution and more spectral dynamic range than conventional spectra when the number of channels is small. The observed improvement suggests the hybrid technique is potentially valuable in seismic data analysis

High resolution observed in 800 MHz DNP spectra of extremely rigid type III secretion needles

International Nuclear Information System (INIS)

Fricke, Pascal; Mance, Deni; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Baldus, Marc; Lange, Adam

2016-01-01

The cryogenic temperatures at which dynamic nuclear polarization (DNP) solid-state NMR experiments need to be carried out cause line-broadening, an effect that is especially detrimental for crowded protein spectra. By increasing the magnetic field strength from 600 to 800 MHz, the resolution of DNP spectra of type III secretion needles (T3SS) could be improved by 22 %, indicating that inhomogeneous broadening is not the dominant effect that limits the resolution of T3SS needles under DNP conditions. The outstanding spectral resolution of this system under DNP conditions can be attributed to its low overall flexibility.

High resolution observed in 800 MHz DNP spectra of extremely rigid type III secretion needles

Energy Technology Data Exchange (ETDEWEB)

Fricke, Pascal [Leibniz-Institut für Molekulare Pharmakologie, Department of Molecular Biophysics (Germany); Mance, Deni [Utrecht University, NMR Research Group, Bijvoet Center for Biomolecular Research (Netherlands); Chevelkov, Veniamin [Leibniz-Institut für Molekulare Pharmakologie, Department of Molecular Biophysics (Germany); Giller, Karin; Becker, Stefan [Max Planck Institute for Biophysical Chemistry, Department of NMR-Based Structural Biology (Germany); Baldus, Marc [Utrecht University, NMR Research Group, Bijvoet Center for Biomolecular Research (Netherlands); Lange, Adam, E-mail: alange@fmp-berlin.de [Leibniz-Institut für Molekulare Pharmakologie, Department of Molecular Biophysics (Germany)

2016-08-15

The cryogenic temperatures at which dynamic nuclear polarization (DNP) solid-state NMR experiments need to be carried out cause line-broadening, an effect that is especially detrimental for crowded protein spectra. By increasing the magnetic field strength from 600 to 800 MHz, the resolution of DNP spectra of type III secretion needles (T3SS) could be improved by 22 %, indicating that inhomogeneous broadening is not the dominant effect that limits the resolution of T3SS needles under DNP conditions. The outstanding spectral resolution of this system under DNP conditions can be attributed to its low overall flexibility.

NLTE ANALYSIS OF HIGH-RESOLUTION H -BAND SPECTRA. II. NEUTRAL MAGNESIUM

Energy Technology Data Exchange (ETDEWEB)

Zhang, Junbo; Shi, Jianrong; Liu, Chao [Key Laboratory of Optical Astronomy, National Astronomical Observatories, Chinese Academy of Sciences, A20 Datun Road, Chaoyang District, Beijing 100012 (China); Pan, Kaike [Apache Point Observatory and New Mexico State University, P.O. Box 59, Sunspot, NM 88349-0059 (United States); Prieto, Carlos Allende, E-mail: sjr@bao.ac.cn [Instituto de Astrofísica de Canarias, E-38205 La Laguna, Tenerife (Spain)

2017-01-20

Aiming at testing the validity of our magnesium atomic model and investigating the effects of non-local thermodynamical equilibrium (NLTE) on the formation of the H -band neutral magnesium lines, we derive the differential Mg abundances from selected transitions for 13 stars either adopting or relaxing the assumption of local thermodynamical equilibrium (LTE). Our analysis is based on high-resolution and high signal-to-noise ratio H -band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) and optical spectra from several instruments. The absolute differences between the Mg abundances derived from the two wavelength bands are always less than 0.1 dex in the NLTE analysis, while they are slightly larger for the LTE case. This suggests that our Mg atomic model is appropriate for investigating the NLTE formation of the H -band Mg lines. The NLTE corrections for the Mg i H -band lines are sensitive to the surface gravity, becoming larger for smaller log g values, and strong lines are more susceptible to departures from LTE. For cool giants, NLTE corrections tend to be negative, and for the strong line at 15765 Å they reach −0.14 dex in our sample, and up to −0.22 dex for other APOGEE stars. Our results suggest that it is important to include NLTE corrections in determining Mg abundances from the H -band Mg i transitions, especially when strong lines are used.

[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.

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

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

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-NO_x, 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-NO_x SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

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.

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.

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.

Contradictions about Fine Structures in Meson Spectra and Proposed High-Resolution Hadron Spectrometer Using 'Interactive' Solid-State Hydrogen Target

International Nuclear Information System (INIS)

Maglich, Bogdan C.

2004-01-01

High resolution has been discouraged in meson spectrometry for 4 decades by the Doctrine of Experiments Incompatible with Theory (DEIT). DEIT a priori rejects narrow hadron resonances on the paradigm that only broad hadron peaks, Γ≥ 100 MeV, can exist -- in spite of the accumulated evidence to the contrary. The facts are: Mesons 2 orders of magnitude narrower than 'allowed' for hadrons, have been confirmed; a new one was announced at this conference. Narrow meson structures have been repeatedly reported at high momentum transfer, vertical bar t vertical bar >0.2, while they are absent at the low transfer, vertical bar t vertical bar ∼0.01, where 99% of the experiments are performed. Modification of meson mass and width as a function of the density of nuclear matter in which they are produced, have been recently reported.We postulate for meson spectra: (1) Intrinsic ('true') width, Γ, is different from the observable ('apparent') width, Γ': Γ< Γ' (2) Γ of all meson states are narrow and can be observed only at or near the maximum vertical bar t vertical bar reachable in the reaction, and (3) Γ of all meson resonances are subject to broadening as vertical bar t vertical bar decreases. Since both Γ' and the production σ are inversely proportional to vertical bar t vertical ar, most of the observed spectra are produced at the lowest vertical bar t vertical bar <0.01 and thus the peaks appear broad. We have conceptually designed a novel type hadron spectrometer with an order of magnitude better resolution (0.1 MeV). It would operate at 2 orders of magnitude higher vertical bar t vertical bar (0.3< vertical bar t vertical bar <1 (GeV/c)2, than most experiments to date (vertical bar t vertical bar <0.01). Mesons in the mass region 0.5 < Mx<5 GeV would be produced in πP→PX (baryons in PP→PP*) in a 'solid state hydrogen target' consisting of an array of plastic scintillator fibers, CH; collisions with C are electronically rejected. Missing mass of P is

A new method of measuring centre-of-mass velocities of radially pulsating stars from high-resolution spectroscopy

Science.gov (United States)

Britavskiy, N.; Pancino, E.; Tsymbal, V.; Romano, D.; Fossati, L.

2018-03-01

We present a radial velocity analysis of 20 solar neighbourhood RR Lyrae and three Population II Cepheid variables. We obtained high-resolution, moderate-to-high signal-to-noise ratio spectra for most stars; these spectra covered different pulsation phases for each star. To estimate the gamma (centre-of-mass) velocities of the programme stars, we use two independent methods. The first, `classic' method is based on RR Lyrae radial velocity curve templates. The second method is based on the analysis of absorption-line profile asymmetry to determine both pulsational and gamma velocities. This second method is based on the least-squares deconvolution (LSD) technique applied to analyse the line asymmetry that occurs in the spectra. We obtain measurements of the pulsation component of the radial velocity with an accuracy of ±3.5 km s-1. The gamma velocity was determined with an accuracy of ±10 km s-1, even for those stars having a small number of spectra. The main advantage of this method is the possibility of obtaining an estimation of gamma velocity even from one spectroscopic observation with uncertain pulsation phase. A detailed investigation of LSD profile asymmetry shows that the projection factor p varies as a function of the pulsation phase - this is a key parameter, which converts observed spectral line radial velocity variations into photospheric pulsation velocities. As a by-product of our study, we present 41 densely spaced synthetic grids of LSD profile bisectors based on atmospheric models of RR Lyr covering all pulsation phases.

Towards automated discrimination of lipids versus peptides from full scan mass spectra

Directory of Open Access Journals (Sweden)

Piotr Dittwald

2014-09-01

Full Text Available Although physicochemical fractionation techniques play a crucial role in the analysis of complex mixtures, they are not necessarily the best solution to separate specific molecular classes, such as lipids and peptides. Any physical fractionation step such as, for example, those based on liquid chromatography, will introduce its own variation and noise. In this paper we investigate to what extent the high sensitivity and resolution of contemporary mass spectrometers offers viable opportunities for computational separation of signals in full scan spectra. We introduce an automatic method that can discriminate peptide from lipid peaks in full scan mass spectra, based on their isotopic properties. We systematically evaluate which features maximally contribute to a peptide versus lipid classification. The selected features are subsequently used to build a random forest classifier that enables almost perfect separation between lipid and peptide signals without requiring ion fragmentation and classical tandem MS-based identification approaches. The classifier is trained on in silico data, but is also capable of discriminating signals in real world experiments. We evaluate the influence of typical data inaccuracies of common classes of mass spectrometry instruments on the optimal set of discriminant features. Finally, the method is successfully extended towards the classification of individual lipid classes from full scan mass spectral features, based on input data defined by the Lipid Maps Consortium.

Annotating and Interpreting Linear and Cyclic Peptide Tandem Mass Spectra.

Science.gov (United States)

Niedermeyer, Timo Horst Johannes

2016-01-01

Nonribosomal peptides often possess pronounced bioactivity, and thus, they are often interesting hit compounds in natural product-based drug discovery programs. Their mass spectrometric characterization is difficult due to the predominant occurrence of non-proteinogenic monomers and, especially in the case of cyclic peptides, the complex fragmentation patterns observed. This makes nonribosomal peptide tandem mass spectra annotation challenging and time-consuming. To meet this challenge, software tools for this task have been developed. In this chapter, the workflow for using the software mMass for the annotation of experimentally obtained peptide tandem mass spectra is described. mMass is freely available (http://www.mmass.org), open-source, and the most advanced and user-friendly software tool for this purpose. The software enables the analyst to concisely annotate and interpret tandem mass spectra of linear and cyclic peptides. Thus, it is highly useful for accelerating the structure confirmation and elucidation of cyclic as well as linear peptides and depsipeptides.

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...

Marvel Analysis of the Measured High-resolution Rovibronic Spectra of TiO

Science.gov (United States)

McKemmish, Laura K.; Masseron, Thomas; Sheppard, Samuel; Sandeman, Elizabeth; Schofield, Zak; Furtenbacher, Tibor; Császár, Attila G.; Tennyson, Jonathan; Sousa-Silva, Clara

2017-02-01

Accurate, experimental rovibronic energy levels, with associated labels and uncertainties, are reported for 11 low-lying electronic states of the diatomic {}48{{Ti}}16{{O}} molecule, determined using the Marvel (Measured Active Rotational-Vibrational Energy Levels) algorithm. All levels are based on lines corresponding to critically reviewed and validated high-resolution experimental spectra taken from 24 literature sources. The transition data are in the 2-22,160 cm-1 region. Out of the 49,679 measured transitions, 43,885 are triplet-triplet, 5710 are singlet-singlet, and 84 are triplet-singlet transitions. A careful analysis of the resulting experimental spectroscopic network (SN) allows 48,590 transitions to be validated. The transitions determine 93 vibrational band origins of {}48{{Ti}}16{{O}}, including 71 triplet and 22 singlet ones. There are 276 (73) triplet-triplet (singlet-singlet) band-heads derived from Marvel experimental energies, 123(38) of which have never been assigned in low- or high-resolution experiments. The highest J value, where J stands for the total angular momentum, for which an energy level is validated is 163. The number of experimentally derived triplet and singlet {}48{{Ti}}16{{O}} rovibrational energy levels is 8682 and 1882, respectively. The lists of validated lines and levels for {}48{{Ti}}16{{O}} are deposited in the supporting information to this paper.

Scaling properties of the transverse mass spectra

International Nuclear Information System (INIS)

Schaffner-Bielich, J.

2002-01-01

Motivated from the formation of an initial state of gluon-saturated matter, we discuss scaling relations for the transverse mass spectra at BNL's relativistic heavy-ion collider (RHIC). We show on linear plots, that the transverse mass spectra for various hadrons can be described by an universal function in m t . The transverse mass spectra for different centralities can be rescaled into each other. Finally, we demonstrate that m t -scaling is also present in proton-antiproton collider data and compare it to m t -scaling at RHIC. (orig.)

Discovery of putative salivary biomarkers for Sjögren's syndrome using high resolution mass spectrometry and bioinformatics.

Science.gov (United States)

Zoukhri, Driss; Rawe, Ian; Singh, Mabi; Brown, Ashley; Kublin, Claire L; Dawson, Kevin; Haddon, William F; White, Earl L; Hanley, Kathleen M; Tusé, Daniel; Malyj, Wasyl; Papas, Athena

2012-03-01

The purpose of the current study was to determine if saliva contains biomarkers that can be used as diagnostic tools for Sjögren's syndrome (SjS). Twenty seven SjS patients and 27 age-matched healthy controls were recruited for these studies. Unstimulated glandular saliva was collected from the Wharton's duct using a suction device. Two µl of salvia were processed for mass spectrometry analyses on a prOTOF 2000 matrix-assisted laser desorption/ionization orthogonal time of flight (MALDI O-TOF) mass spectrometer. Raw data were analyzed using bioinformatic tools to identify biomarkers. MALDI O-TOF MS analyses of saliva samples were highly reproducible and the mass spectra generated were very rich in peptides and peptide fragments in the 750-7,500 Da range. Data analysis using bioinformatic tools resulted in several classification models being built and several biomarkers identified. One model based on 7 putative biomarkers yielded a sensitivity of 97.5%, specificity of 97.8% and an accuracy of 97.6%. One biomarker was present only in SjS samples and was identified as a proteolytic peptide originating from human basic salivary proline-rich protein 3 precursor. We conclude that salivary biomarkers detected by high-resolution mass spectrometry coupled with powerful bioinformatic tools offer the potential to serve as diagnostic/prognostic tools for SjS.

Resolution of co-eluting compounds of Cannabis Sativa in comprehensive two-dimensional gas chromatography/mass spectrometry detection with Multivariate Curve Resolution-Alternating Least Squares.

Science.gov (United States)

Omar, Jone; Olivares, Maitane; Amigo, José Manuel; Etxebarria, Nestor

2014-04-01

Comprehensive Two Dimensional Gas Chromatography - Mass Spectrometry (GC × GC/qMS) analysis of Cannabis sativa extracts shows a high complexity due to the large variety of terpenes and cannabinoids and to the fact that the complete resolution of the peaks is not straightforwardly achieved. In order to support the resolution of the co-eluted peaks in the sesquiterpene and the cannabinoid chromatographic region the combination of Multivariate Curve Resolution and Alternating Least Squares algorithms was satisfactorily applied. As a result, four co-eluting areas were totally resolved in the sesquiterpene region and one in the cannabinoid region in different samples of Cannabis sativa. The comparison of the mass spectral profiles obtained for each resolved peak with theoretical mass spectra allowed the identification of some of the co-eluted peaks. Finally, the classification of the studied samples was achieved based on the relative concentrations of the resolved peaks. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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

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.

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.

High-resolution coherent three-dimensional spectroscopy of Br2.

Science.gov (United States)

Chen, Peter C; Wells, Thresa A; Strangfeld, Benjamin R

2013-07-25

In the past, high-resolution spectroscopy has been limited to small, simple molecules that yield relatively uncongested spectra. Larger and more complex molecules have a higher density of peaks and are susceptible to complications (e.g., effects from conical intersections) that can obscure the patterns needed to resolve and assign peaks. Recently, high-resolution coherent two-dimensional (2D) spectroscopy has been used to resolve and sort peaks into easily identifiable patterns for molecules where pattern-recognition has been difficult. For very highly congested spectra, however, the ability to resolve peaks using coherent 2D spectroscopy is limited by the bandwidth of instrumentation. In this article, we introduce and investigate high-resolution coherent three-dimensional spectroscopy (HRC3D) as a method for dealing with heavily congested systems. The resulting patterns are unlike those in high-resolution coherent 2D spectra. Analysis of HRC3D spectra could provide a means for exploring the spectroscopy of large and complex molecules that have previously been considered too difficult to study.

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.

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3-micrometers Region: Role of Periphery

Science.gov (United States)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2017-01-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3-micrometers absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 per cm range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3-micrometers region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3-micrometers band, and on features such as the two-component emission character of this band and the 3-micrometers emission plateau.

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.

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

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

SPECTRA OF STRONG MAGNETOHYDRODYNAMIC TURBULENCE FROM HIGH-RESOLUTION SIMULATIONS

International Nuclear Information System (INIS)

Beresnyak, Andrey

2014-01-01

Magnetohydrodynamic (MHD) turbulence is present in a variety of solar and astrophysical environments. Solar wind fluctuations with frequencies lower than 0.1 Hz are believed to be mostly governed by Alfvénic turbulence with particle transport depending on the power spectrum and the anisotropy of such turbulence. Recently, conflicting spectral slopes for the inertial range of MHD turbulence have been reported by different groups. Spectral shapes from earlier simulations showed that MHD turbulence is less scale-local compared with hydrodynamic turbulence. This is why higher-resolution simulations, and careful and rigorous numerical analysis is especially needed for the MHD case. In this Letter, we present two groups of simulations with resolution up to 4096 3 , which are numerically well-resolved and have been analyzed with an exact and well-tested method of scaling study. Our results from both simulation groups indicate that the asymptotic power spectral slope for all energy-related quantities, such as total energy and residual energy, is around –1.7, close to Kolmogorov's –5/3. This suggests that residual energy is a constant fraction of the total energy and that in the asymptotic regime of Alfvénic turbulence magnetic and kinetic spectra have the same scaling. The –1.5 slope for energy and the –2 slope for residual energy, which have been suggested earlier, are incompatible with our numerics

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

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.

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

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...

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.

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE 3 μ m REGION: ROLE OF PERIPHERY

Energy Technology Data Exchange (ETDEWEB)

Maltseva, Elena; Petrignani, Annemieke; Buma, Wybren Jan [University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Candian, Alessandra; Mackie, Cameron J.; Tielens, Alexander G. G. M. [Leiden Observatory, Niels Bohrweg 2, 2333 CA Leiden (Netherlands); Huang, Xinchuan [SETI Institute, 189 Bernardo Avenue, Suite 100, Mountain View, CA 94043 (United States); Lee, Timothy J. [NASA Ames Research Center, Moffett Field, California 94035-1000 (United States); Oomens, Jos, E-mail: w.j.buma@uva.nl [Radboud University, Toernooiveld 7, 6525 ED Nijmegen (Netherlands)

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μ m absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm{sup −1} range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μ m region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μ m band, and on features such as the two-component emission character of this band and the 3 μ m emission plateau.

Physical properties of the interstellar medium using high-resolution Chandra spectra: O K-edge absorption

Energy Technology Data Exchange (ETDEWEB)

Gatuzz, E.; Mendoza, C. [Centro de Física, Instituto Venezolano de Investigaciones Científicas (IVIC), P.O. Box 20632, Caracas 1020A (Venezuela, Bolivarian Republic of); García, J. [Harvard-Smithsonian Center for Astrophysics, MS-6, 60 Garden Street, Cambridge, MA 02138 (United States); Kallman, T. R. [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Bautista, M. A.; Gorczyca, T. W., E-mail: egatuzz@ivic.gob.ve, E-mail: claudio@ivic.gob.ve, E-mail: javier@head.cfa.harvard.edu, E-mail: manuel.bautista@wmich.edu, E-mail: thomas.gorczyca@wmich.edu, E-mail: timothy.r.kallman@nasa.gov [Department of Physics, Western Michigan University, Kalamazoo, MI 49008 (United States)

2014-08-01

Chandra high-resolution spectra toward eight low-mass Galactic binaries have been analyzed with a photoionization model that is capable of determining the physical state of the interstellar medium. Particular attention is given to the accuracy of the atomic data. Hydrogen column densities are derived with a broadband fit that takes into account pileup effects, and in general are in good agreement with previous results. The dominant features in the oxygen-edge region are O I and O II Kα absorption lines whose simultaneous fits lead to average values of the ionization parameter of log ξ = –2.90 and oxygen abundance of A{sub O} = 0.70. The latter is given relative to the standard by Grevesse and Sauval, but rescaling with the revision by Asplund et al. would lead to an average abundance value fairly close to solar. The low average oxygen column density (N{sub O} = 9.2 × 10{sup 17} cm{sup –2}) suggests a correlation with the low ionization parameters, the latter also being in evidence in the column density ratios N(O II)/N(O I) and N(O III)/N(O I) that are estimated to be less than 0.1. We do not find conclusive evidence for absorption by any other compound but atomic oxygen in our oxygen-edge region analysis.

Interpreting peptide mass spectra by VEMS

DEFF Research Database (Denmark)

Mathiesen, Rune; Lundsgaard, M.; Welinder, Karen G.

2003-01-01

the calculated and the experimental mass spectrum of the called peptide. The program package includes four accessory programs. VEMStrans creates protein databases in FASTA format from EST or cDNA sequence files. VEMSdata creates a virtual peptide database from FASTA files. VEMSdist displays the distribution......Most existing Mass Spectra (MS) analysis programs are automatic and provide limited opportunity for editing during the interpretation. Furthermore, they rely entirely on publicly available databases for interpretation. VEMS (Virtual Expert Mass Spectrometrist) is a program for interactive analysis...... of peptide MS/MS spectra imported in text file format. Peaks are annotated, the monoisotopic peaks retained, and the b-and y-ion series identified in an interactive manner. The called peptide sequence is searched against a local protein database for sequence identity and peptide mass. The report compares...

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

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

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.

Mass Spectra-Based Framework for Automated Structural Elucidation of Metabolome Data to Explore Phytochemical Diversity

Science.gov (United States)

Matsuda, Fumio; Nakabayashi, Ryo; Sawada, Yuji; Suzuki, Makoto; Hirai, Masami Y.; Kanaya, Shigehiko; Saito, Kazuki

2011-01-01

A novel framework for automated elucidation of metabolite structures in liquid chromatography–mass spectrometer metabolome data was constructed by integrating databases. High-resolution tandem mass spectra data automatically acquired from each metabolite signal were used for database searches. Three distinct databases, KNApSAcK, ReSpect, and the PRIMe standard compound database, were employed for the structural elucidation. The outputs were retrieved using the CAS metabolite identifier for identification and putative annotation. A simple metabolite ontology system was also introduced to attain putative characterization of the metabolite signals. The automated method was applied for the metabolome data sets obtained from the rosette leaves of 20 Arabidopsis accessions. Phenotypic variations in novel Arabidopsis metabolites among these accessions could be investigated using this method. PMID:22645535

Mass spectra-based framework for automated structural elucidation of metabolome data to explore phytochemical diversity

Directory of Open Access Journals (Sweden)

Fumio eMatsuda

2011-08-01

Full Text Available A novel framework for automated elucidation of metabolite structures in liquid chromatography-mass spectrometer (LC-MS metabolome data was constructed by integrating databases. High-resolution tandem mass spectra data automatically acquired from each metabolite signal were used for database searches. Three distinct databases, KNApSAcK, ReSpect, and the PRIMe standard compound database, were employed for the structural elucidation. The outputs were retrieved using the CAS metabolite identifier for identification and putative annotation. A simple metabolite ontology system was also introduced to attain putative characterization of the metabolite signals. The automated method was applied for the metabolome data sets obtained from the rosette leaves of 20 Arabidopsis accessions. Phenotypic variations in novel Arabidopsis metabolites among these accessions could be investigated using this method.

Low resolution infrared spectra of quasars

International Nuclear Information System (INIS)

Soifer, B.T.; Neugebauer, G.; Oke, J.B.; Matthews, K.

1980-01-01

Low resolution spectra of a significant sample of quasars show that the Paschen α and Balmer line ratios do not agree with the radiative recombination case B result and vary widely within the quasars sampled. The range in Pα:Hβ ratios is a factor of approximately 6, while the range in Lyα:Hα ratios is a factor of approximately 5. For the Pα:Balmer series, the deviations from case B recombination are not consistent with reddening, but appear, within large dispersions, to be consistent with optical depth effects in the Balmer lines affecting the line ratios. The Lyα:Hα ratio is, however, correlated with the continuum spectral index, and can be explained as due to reddening affecting both the lines and continuum. Recent observational results based on a joint infrared/optical survey of the hydrogen line spectra of a significant number of the brightest low and high redshift quasars are summarised. This survey includes 12 quasars in the redshift range 0.07 1.5, where Hα and/or Hβ is redshifted into the 1.65μm or 2.2μm atmospheric windows. (Auth.)

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.

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

High Resolution Spectra of Carbon Monoxide, Propane and Ammonia for Atmospheric Remote Sensing

Science.gov (United States)

Beale, Christopher Andrew

Spectroscopy is a critical tool for analyzing atmospheric data. Identification of atmospheric parameters such as temperature, pressure and the existence and concentrations of constituent gases via remote sensing techniques are only possible with spectroscopic data. These form the basis of model atmospheres which may be compared to observations to determine such parameters. To this end, this dissertation explores the spectroscopy of three molecules: ammonia, propane and carbon monoxide. Infrared spectra have been recorded for ammonia in the region 2400-9000 cm-1. These spectra were recorded at elevated temperatures (from 293-973 K) using a Fourier Transform Spectrometer (FTS). Comparison between the spectra recorded at different temperatures yielded experimental lower state energies. These spectra resulted in the measurement of roughly 30000 lines and about 3000 quantum assignments. In addition spectra of propane were recorded at elevated temperatures (296-700 K) using an FTS. Atmospheres with high temperatures require molecular data at appropriate conditions. This dissertation describes collection of such data and the potential application to atmospheres in our solar system, such as auroral regions in Jupiter, to those of planets orbiting around other stars and cool sub-stellar objects known as brown dwarfs. The spectra of propane and ammonia provide the highest resolution and most complete experimental study of these gases in their respective spectral regions at elevated temperatures. Detection of ammonia in an exoplanet or detection of propane in the atmosphere of Jupiter will most likely rely on the work presented here. The best laboratory that we have to study atmospheres is our own planet. The same techniques that are applied to these alien atmospheres originated on Earth. As such it is appropriate to discuss remote sensing of our own atmosphere. This idea is explored through analysis of spectroscopic data recorded by an FTS on the Atmospheric Chemistry

The supersoft X-ray source in V5116 Sagittarii. I. The high resolution spectra

Science.gov (United States)

Sala, G.; Ness, J. U.; Hernanz, M.; Greiner, J.

2017-05-01

Context. Classical nova explosions occur on the surface of an accreting white dwarf in a binary system. After ejection of a fraction of the envelope and when the expanding shell becomes optically thin to X-rays, a bright source of supersoft X-rays arises, powered by residual H burning on the surface of the white dwarf. While the general picture of the nova event is well established, the details and balance of accretion and ejection processes in classical novae are still full of unknowns. The long-term balance of accreted matter is of special interest for massive accreting white dwarfs, which may be promising supernova Ia progenitor candidates. Nova V5116 Sgr 2005b was observed as a bright and variable supersoft X-ray source by XMM-Newton in March 2007, 610 days after outburst. The light curve showed a periodicity consistent with the orbital period. During one third of the orbit the luminosity was a factor of seven brighter than during the other two thirds of the orbital period. Aims: In the present work we aim to disentangle the X-ray spectral components of V5116 Sgr and their variability. Methods: We present the high resolution spectra obtained with XMM-Newton RGS and Chandra LETGS/HRC-S in March and August 2007. Results: The grating spectrum during the periods of high-flux shows a typical hot white dwarf atmosphere dominated by absorption lines of N VI and N VII. During the low-flux periods, the spectrum is dominated by an atmosphere with the same temperature as during the high-flux period, but with several emission features superimposed. Some of the emission lines are well modeled with an optically thin plasma in collisional equilibrium, rich in C and N, which also explains some excess in the spectra of the high-flux period. No velocity shifts are observed in the absorption lines, with an upper limit set by the spectral resolution of 500 km s-1, consistent with the expectation of a non-expanding atmosphere so late in the evolution of the post-nova. Based on

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

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

HIGH-RESOLUTION XMM-NEWTON SPECTROSCOPY OF THE COOLING FLOW CLUSTER A3112

Energy Technology Data Exchange (ETDEWEB)

Bulbul, G. Esra; Smith, Randall K.; Foster, Adam [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Cottam, Jean; Loewenstein, Michael; Mushotzky, Richard; Shafer, Richard, E-mail: ebulbul@cfa.harvard.edu [NASA Goddard Space Flight Center, Greenbelt, MD (United States)

2012-03-01

We examine high signal-to-noise XMM-Newton European Photon Imaging Camera (EPIC) and Reflection Grating Spectrometer (RGS) observations to determine the physical characteristics of the gas in the cool core and outskirts of the nearby rich cluster A3112. The XMM-Newton Extended Source Analysis Software data reduction and background modeling methods were used to analyze the XMM-Newton EPIC data. From the EPIC data, we find that the iron and silicon abundance gradients show significant increase toward the center of the cluster while the oxygen abundance profile is centrally peaked but has a shallower distribution than that of iron. The X-ray mass modeling is based on the temperature and deprojected density distributions of the intracluster medium determined from EPIC observations. The total mass of A3112 obeys the M-T scaling relations found using XMM-Newton and Chandra observations of massive clusters at r{sub 500}. The gas mass fraction f{sub gas} = 0.149{sup +0.036}{sub -0.032} at r{sub 500} is consistent with the seven-year Wilkinson Microwave Anisotropy Probe results. The comparisons of line fluxes and flux limits on the Fe XVII and Fe XVIII lines obtained from high-resolution RGS spectra indicate that there is no spectral evidence for cooler gas associated with the cluster with temperature below 1.0 keV in the central <38'' ({approx}52 kpc) region of A3112. High-resolution RGS spectra also yield an upper limit to the turbulent motions in the compact core of A3112 (206 km s{sup -1}). We find that the contribution of turbulence to total energy is less than 6%. This upper limit is consistent with the energy contribution measured in recent high-resolution simulations of relaxed galaxy clusters.

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

One-dimensional power spectrum and neutrino mass in the spectra of BOSS

International Nuclear Information System (INIS)

Borde, Arnaud

2014-01-01

The framework of the studies presented in this thesis is the one-dimensional power spectrum of the transmitted flux in the Lyman-alpha forests. The Lyman-alpha forest is an absorption pattern seen in the spectra of high redshift quasars corresponding to the absorption of the quasar light by the hydrogen clouds along the line of sight. It is a powerful cosmological tool as it probes relatively small scales, of the order of a few Mpc. It is also sensible to small non-linear effects such as the one induced by massive neutrinos. First, we have developed two independent methods to measure the one-dimensional power spectrum of the transmitted flux in the Lyman-alpha forest. The first method is based on a Fourier transform, and the second on a maximum likelihood estimator. The two methods are independent and have different systematic uncertainties. The determination of the noise level in the data spectra was subject to a novel treatment, because of its significant impact on the derived power spectrum. We applied the two methods to 13,821 quasar spectra from SDSS-III/BOSS DR9 selected from a larger sample of over 60,000 spectra on the basis of their high quality, large signal-to-noise ratio, and good spectral resolution. The power spectra measured using either approach are in good agreement over all twelve redshift bins from =2.2 to =4.4, and scales from 0.001 (km/s)"-"1 to 0.02 (km/s)"-"1. We carefully determined the methodological and instrumental systematic uncertainties of our measurements. Then, we present a suite of cosmological N-body simulations with cold dark matter, baryons and neutrinos aiming at modeling the low-density regions of the IGM as probed by the Lyman-alpha forests at high redshift. The simulations are designed to match the requirements imposed by the quality of BOSS and eBOSS data. They are made using either 768"3 or 192"3 particles of each type, spanning volumes ranging from (25 Mpc/h)"3 for high-resolution simulations to (100 Mpc/h)"3 for large

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.

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

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

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

Decon2LS: An open-source software package for automated processing and visualization of high resolution mass spectrometry data.

Science.gov (United States)

Jaitly, Navdeep; Mayampurath, Anoop; Littlefield, Kyle; Adkins, Joshua N; Anderson, Gordon A; Smith, Richard D

2009-03-17

Data generated from liquid chromatography coupled to high-resolution mass spectrometry (LC-MS)-based studies of a biological sample can contain large amounts of biologically significant information in the form of proteins, peptides, and metabolites. Interpreting this data involves inferring the masses and abundances of biomolecules injected into the instrument. Because of the inherent complexity of mass spectral patterns produced by these biomolecules, the analysis is significantly enhanced by using visualization capabilities to inspect and confirm results. In this paper we describe Decon2LS, an open-source software package for automated processing and visualization of high-resolution MS data. Drawing extensively on algorithms developed over the last ten years for ICR2LS, Decon2LS packages the algorithms as a rich set of modular, reusable processing classes for performing diverse functions such as reading raw data, routine peak finding, theoretical isotope distribution modelling, and deisotoping. Because the source code is openly available, these functionalities can now be used to build derivative applications in relatively fast manner. In addition, Decon2LS provides an extensive set of visualization tools, such as high performance chart controls. With a variety of options that include peak processing, deisotoping, isotope composition, etc, Decon2LS supports processing of multiple raw data formats. Deisotoping can be performed on an individual scan, an individual dataset, or on multiple datasets using batch processing. Other processing options include creating a two dimensional view of mass and liquid chromatography (LC) elution time features, generating spectrum files for tandem MS data, creating total intensity chromatograms, and visualizing theoretical peptide profiles. Application of Decon2LS to deisotope different datasets obtained across different instruments yielded a high number of features that can be used to identify and quantify peptides in the

High-resolution spectroscopy of gases for industrial applications

DEFF Research Database (Denmark)

Fateev, Alexander; Clausen, Sønnik

High-resolution spectroscopy of gases is a powerful technique which has various fundamental and practical applications: in situ simultaneous measurements of gas temperature and gas composition, radiative transfer modeling, validation of existing and developing of new databases and etc. Existing...... databases (e.g. HITRAN, HITEMP or CDSD) can normally be used for absorption spectra calculations at limited temperature/pressure ranges. Therefore experimental measurements of absorption/transmission spectra gases (e.g. CO2, H2O or SO2) at high-resolution and elevated temperatures are essential both...... for analysis of complex experimental data and further development of the databases. High-temperature gas cell facilities available at DTU Chemical Engineering are presented and described. The gas cells and high-resolution spectrometers allow us to perform high-quality reference measurements of gases relevant...

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.

High-resolution spectra of stars in globular clusters. VI - Oxygen-deficient red giant stars in M13

International Nuclear Information System (INIS)

Brown, J.A.; Wallerstein, G.; Oke, J.B.

1991-01-01

From high-resolution, high signal-to-noise spectra, abundances of carbon, nitrogen, and oxygen and the C-12/C-13 ratio for five red giants in M13, including star II-67, which has previously been reported to be deficient in oxygen have been determined. Three of the five stars exhibit substantial oxygen deficiencies; O/Fe values range from +0.5 to less than about 0.3. The sum of the CNO nuclides is the same for all stars, which is interpreted as evidence that mixing of CNO-cycled material into the envelope is the cause of the variations in oxygen abundance. 41 refs

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...

High temperature and high resolution uv photoelectron spectroscopy using supersonic molecular beams

International Nuclear Information System (INIS)

Wang, Lai-Sheng; Reutt-Robey, J.E.; Niu, B.; Lee, Y.T.; Shirley, D.A.

1989-07-01

A high temperature molecular beam source with electron bombardment heating has been built for high resolution photoelectron spectroscopic studies of high temperature species and clusters. This source has the advantages of: producing an intense, continuous, seeded molecular beam, eliminating the interference of the heating mechanism from the photoelectron measurement. Coupling the source with our hemispherical electron energy analyzer, we can obtain very high resolution HeIα (584 angstrom) photoelectron spectra of high temperature species. Vibrationally-resolved photoelectron spectra of PbSe, As 2 , As 4 , and ZnCl 2 are shown to demonstrate the performance of the new source. 25 refs., 8 figs., 1 tab

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.

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

A high resolution solar atlas for fluorescence calculations

Science.gov (United States)

Hearn, M. F.; Ohlmacher, J. T.; Schleicher, D. G.

1983-01-01

The characteristics required of a solar atlas to be used for studying the fluorescence process in comets are examined. Several sources of low resolution data were combined to provide an absolutely calibrated spectrum from 2250 A to 7000A. Three different sources of high resolution data were also used to cover this same spectral range. The low resolution data were then used to put each high resolution spectrum on an absolute scale. The three high resolution spectra were then combined in their overlap regions to produce a single, absolutely calibrated high resolution spectrum over the entire spectral range.

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

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.

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

Energy Technology Data Exchange (ETDEWEB)

Jacovella, U. [Laboratorium für Physikalische Chemie, ETH Zürich, 8093 Zürich (Switzerland); Holland, D. M. P. [STFC, Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Boyé-Péronne, S.; Gans, B. [Institut des Sciences Moléculaires d’Orsay, UMR 8214, CNRS and Université Paris-Sud, F-91405 Orsay (France); Oliveira, N. de; Joyeux, D.; Archer, L. E. [Synchrotron Soleil, L’Orme des Merisiers, F-91192 Gif-sur-Yvette (France); Lucchese, R. R. [Department of Chemistry, Texas A& M University, College Station, Texas 77843 (United States); Xu, H.; Pratt, S. T. [Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2015-07-21

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.

MARVEL analysis of the measured high-resolution spectra of 14NH3

International Nuclear Information System (INIS)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-01-01

Accurate, experimental rotational–vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14 NH 3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7–17 000 cm −1 region, with a large gap between 7000 and 15 000 cm −1 . The MARVEL (Measured Active Rotational–Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para- 14 NH 3 , respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14 NH 3 , 8 for ortho- and 22 for para- 14 NH 3 . The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para- 14 NH 3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14 NH 3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14 NH 3 ; these lines are also deposited in the Supporting Information to this paper

MARVEL analysis of the measured high-resolution spectra of 14NH3

Science.gov (United States)

Al Derzi, Afaf R.; Furtenbacher, Tibor; Tennyson, Jonathan; Yurchenko, Sergei N.; Császár, Attila G.

2015-08-01

Accurate, experimental rotational-vibrational energy levels and line positions, with associated labels and uncertainties, are reported for the ground electronic state of the symmetric-top 14NH3 molecule. All levels and lines are based on critically reviewed and validated high-resolution experimental spectra taken from 56 literature sources. The transition data are in the 0.7-17 000 cm-1 region, with a large gap between 7000 and 15 000 cm-1. The MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm is used to determine the energy levels. Out of the 29 450 measured transitions 10 041 and 18 947 belong to ortho- and para-14NH3, respectively. A careful analysis of the related experimental spectroscopic network (SN) allows 28 530 of the measured transitions to be validated, 18 178 of these are unique, while 462 transitions belong to floating components. Despite the large number of spectroscopic measurements published over the last 80 years, the transitions determine only 30 vibrational band origins of 14NH3, 8 for ortho- and 22 for para-14NH3. The highest J value, where J stands for the rotational quantum number, for which an energy level is validated is 31. The number of experimental-quality ortho- and para-14NH3 rovibrational energy levels is 1724 and 3237, respectively. The MARVEL energy levels are checked against ones in the BYTe first-principles database, determined previously. The lists of validated lines and levels for 14NH3 are deposited in the Supporting Information to this paper. Combination of the MARVEL energy levels with first-principles absorption intensities yields a huge number of experimental-quality rovibrational lines, which should prove to be useful for the understanding of future complex high-resolution spectroscopy on 14NH3; these lines are also deposited in the Supporting Information to this paper.

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

Maize MeJA-responsive proteins identified by high-resolution 2-DE PAGE

Directory of Open Access Journals (Sweden)

Yuliang Zhang

2015-12-01

Full Text Available Exogenous methyl jasmonate (MeJA is well-known to induce plant defense mechanisms effective against a wide variety of insect and microbial pests. High-resolution 2-DE gel electrophoresis was used to discover changes in the leaf proteome of maize exposed to MeJA. We sequenced 62 MeJA-responsive proteins by tandem mass spectroscopy, and deposited the mass spectra and identities in the EMBL-EBI PRIDE repository under reference number PXD001793. An analysis and discussion of the identified proteins in relation to maize defense against Asian corn borer is published by Zhang et al. (2015 [1].

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...

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

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.

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

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.

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.

Improved Peak Detection and Deconvolution of Native Electrospray Mass Spectra from Large Protein Complexes.

Science.gov (United States)

Lu, Jonathan; Trnka, Michael J; Roh, Soung-Hun; Robinson, Philip J J; Shiau, Carrie; Fujimori, Danica Galonic; Chiu, Wah; Burlingame, Alma L; Guan, Shenheng

2015-12-01

Native electrospray-ionization mass spectrometry (native MS) measures biomolecules under conditions that preserve most aspects of protein tertiary and quaternary structure, enabling direct characterization of large intact protein assemblies. However, native spectra derived from these assemblies are often partially obscured by low signal-to-noise as well as broad peak shapes because of residual solvation and adduction after the electrospray process. The wide peak widths together with the fact that sequential charge state series from highly charged ions are closely spaced means that native spectra containing multiple species often suffer from high degrees of peak overlap or else contain highly interleaved charge envelopes. This situation presents a challenge for peak detection, correct charge state and charge envelope assignment, and ultimately extraction of the relevant underlying mass values of the noncovalent assemblages being investigated. In this report, we describe a comprehensive algorithm developed for addressing peak detection, peak overlap, and charge state assignment in native mass spectra, called PeakSeeker. Overlapped peaks are detected by examination of the second derivative of the raw mass spectrum. Charge state distributions of the molecular species are determined by fitting linear combinations of charge envelopes to the overall experimental mass spectrum. This software is capable of deconvoluting heterogeneous, complex, and noisy native mass spectra of large protein assemblies as demonstrated by analysis of (1) synthetic mononucleosomes containing severely overlapping peaks, (2) an RNA polymerase II/α-amanitin complex with many closely interleaved ion signals, and (3) human TriC complex containing high levels of background noise. Graphical Abstract ᅟ.

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

Influence of spectral resolution, spectral range and signal-to-noise ratio of Fourier transform infra-red spectra on identification of high explosive substances

Science.gov (United States)

Banas, Krzysztof; Banas, Agnieszka M.; Heussler, Sascha P.; Breese, Mark B. H.

2018-01-01

In the contemporary spectroscopy there is a trend to record spectra with the highest possible spectral resolution. This is clearly justified if the spectral features in the spectrum are very narrow (for example infra-red spectra of gas samples). However there is a plethora of samples (in the liquid and especially in the solid form) where there is a natural spectral peak broadening due to collisions and proximity predominately. Additionally there is a number of portable devices (spectrometers) with inherently restricted spectral resolution, spectral range or both, which are extremely useful in some field applications (archaeology, agriculture, food industry, cultural heritage, forensic science). In this paper the investigation of the influence of spectral resolution, spectral range and signal-to-noise ratio on the identification of high explosive substances by applying multivariate statistical methods on the Fourier transform infra-red spectral data sets is studied. All mathematical procedures on spectral data for dimension reduction, clustering and validation were implemented within R open source environment.

STRAPS v1.0: evaluating a methodology for predicting electron impact ionisation mass spectra for the aerosol mass spectrometer

Directory of Open Access Journals (Sweden)

D. O. Topping

2017-06-01

Full Text Available Our ability to model the chemical and thermodynamic processes that lead to secondary organic aerosol (SOA formation is thought to be hampered by the complexity of the system. While there are fundamental models now available that can simulate the tens of thousands of reactions thought to take place, validation against experiments is highly challenging. Techniques capable of identifying individual molecules such as chromatography are generally only capable of quantifying a subset of the material present, making it unsuitable for a carbon budget analysis. Integrative analytical methods such as the Aerosol Mass Spectrometer (AMS are capable of quantifying all mass, but because of their inability to isolate individual molecules, comparisons have been limited to simple data products such as total organic mass and the O : C ratio. More detailed comparisons could be made if more of the mass spectral information could be used, but because a discrete inversion of AMS data is not possible, this activity requires a system of predicting mass spectra based on molecular composition. In this proof-of-concept study, the ability to train supervised methods to predict electron impact ionisation (EI mass spectra for the AMS is evaluated. Supervised Training Regression for the Arbitrary Prediction of Spectra (STRAPS is not built from first principles. A methodology is constructed whereby the presence of specific mass-to-charge ratio (m∕z channels is fitted as a function of molecular structure before the relative peak height for each channel is similarly fitted using a range of regression methods. The widely used AMS mass spectral database is used as a basis for this, using unit mass resolution spectra of laboratory standards. Key to the fitting process is choice of structural information, or molecular fingerprint. Our approach relies on using supervised methods to automatically optimise the relationship between spectral characteristics and these molecular

STRAPS v1.0: evaluating a methodology for predicting electron impact ionisation mass spectra for the aerosol mass spectrometer

Science.gov (United States)

Topping, David O.; Allan, James; Rami Alfarra, M.; Aumont, Bernard

2017-06-01

Our ability to model the chemical and thermodynamic processes that lead to secondary organic aerosol (SOA) formation is thought to be hampered by the complexity of the system. While there are fundamental models now available that can simulate the tens of thousands of reactions thought to take place, validation against experiments is highly challenging. Techniques capable of identifying individual molecules such as chromatography are generally only capable of quantifying a subset of the material present, making it unsuitable for a carbon budget analysis. Integrative analytical methods such as the Aerosol Mass Spectrometer (AMS) are capable of quantifying all mass, but because of their inability to isolate individual molecules, comparisons have been limited to simple data products such as total organic mass and the O : C ratio. More detailed comparisons could be made if more of the mass spectral information could be used, but because a discrete inversion of AMS data is not possible, this activity requires a system of predicting mass spectra based on molecular composition. In this proof-of-concept study, the ability to train supervised methods to predict electron impact ionisation (EI) mass spectra for the AMS is evaluated. Supervised Training Regression for the Arbitrary Prediction of Spectra (STRAPS) is not built from first principles. A methodology is constructed whereby the presence of specific mass-to-charge ratio (m/z) channels is fitted as a function of molecular structure before the relative peak height for each channel is similarly fitted using a range of regression methods. The widely used AMS mass spectral database is used as a basis for this, using unit mass resolution spectra of laboratory standards. Key to the fitting process is choice of structural information, or molecular fingerprint. Our approach relies on using supervised methods to automatically optimise the relationship between spectral characteristics and these molecular fingerprints. Therefore

The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

Energy Technology Data Exchange (ETDEWEB)

Vasilatou, K.; Michaud, J. M.; Baykusheva, D.; Grassi, G.; Merkt, F. [Laboratorium für Physikalische Chemie, ETH Zürich, CH-8093 Zurich (Switzerland)

2014-08-14

The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra of deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.

Analysis of bovine milk caseins on organic monolithic columns: an integrated capillary liquid chromatography-high resolution mass spectrometry approach for the study of time-dependent casein degradation.

Science.gov (United States)

Pierri, Giuseppe; Kotoni, Dorina; Simone, Patrizia; Villani, Claudio; Pepe, Giacomo; Campiglia, Pietro; Dugo, Paola; Gasparrini, Francesco

2013-10-25

and the contemporary formation of low-molecular-weight proteose-peptones (PP) with exact monoisotopic Mr between 9444.0989 Da and 14098.9861 Da was confirmed through the deconvolution of high resolution mass spectra and literature data. Copyright © 2013 Elsevier B.V. All rights reserved.

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^+.

Decon2LS: An open-source software package for automated processing and visualization of high resolution mass spectrometry data

Directory of Open Access Journals (Sweden)

Anderson Gordon A

2009-03-01

Full Text Available Abstract Background Data generated from liquid chromatography coupled to high-resolution mass spectrometry (LC-MS-based studies of a biological sample can contain large amounts of biologically significant information in the form of proteins, peptides, and metabolites. Interpreting this data involves inferring the masses and abundances of biomolecules injected into the instrument. Because of the inherent complexity of mass spectral patterns produced by these biomolecules, the analysis is significantly enhanced by using visualization capabilities to inspect and confirm results. In this paper we describe Decon2LS, an open-source software package for automated processing and visualization of high-resolution MS data. Drawing extensively on algorithms developed over the last ten years for ICR2LS, Decon2LS packages the algorithms as a rich set of modular, reusable processing classes for performing diverse functions such as reading raw data, routine peak finding, theoretical isotope distribution modelling, and deisotoping. Because the source code is openly available, these functionalities can now be used to build derivative applications in relatively fast manner. In addition, Decon2LS provides an extensive set of visualization tools, such as high performance chart controls. Results With a variety of options that include peak processing, deisotoping, isotope composition, etc, Decon2LS supports processing of multiple raw data formats. Deisotoping can be performed on an individual scan, an individual dataset, or on multiple datasets using batch processing. Other processing options include creating a two dimensional view of mass and liquid chromatography (LC elution time features, generating spectrum files for tandem MS data, creating total intensity chromatograms, and visualizing theoretical peptide profiles. Application of Decon2LS to deisotope different datasets obtained across different instruments yielded a high number of features that can be used to

Adsorbate reactivity and thermal mobility from simple modeling of high-resolution core-level spectra: application to O/Al(111)

International Nuclear Information System (INIS)

Schouborg, Jakob; Raarup, Merete K; Balling, Peter

2009-01-01

A high-resolution core-level spectroscopy investigation of the adsorption of oxygen on Al(111) at variable oxygen exposure demonstrates a low surface reactivity for an intensively cleaned surface. The threshold for oxide formation is as high as ∼200 L (langmuirs), at which point the coverage of the chemisorbed oxygen exceeds half a monolayer. A simple model is presented, using which it is possible to deduce the oxygen coverage from the core-level spectra and determine the initial sticking probability. For our data a value of 0.018 ± 0.004 is obtained. The changes in core-level spectra following low-temperature annealing of low-coverage O/Al(111) reflect the formation of gradually larger islands of oxygen atoms (Ostwald ripening). The island formation is consistent with a random-walk model from which the diffusion barrier can be deduced to be in the range of 0.80-0.90 eV.

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.

High resolution spectroscopy in the microwave and far infrared

Science.gov (United States)

Pickett, Herbert M.

1990-01-01

High resolution rotational spectroscopy has long been central to remote sensing techniques in atmospheric sciences and astronomy. As such, laboratory measurements must supply the required data to make direct interpretation of data for instruments which sense atmospheres using rotational spectra. Spectral measurements in the microwave and far infrared regions are also very powerful tools when combined with infrared measurements for characterizing the rotational structure of vibrational spectra. In the past decade new techniques were developed which have pushed high resolution spectroscopy into the wavelength region between 25 micrometers and 2 mm. Techniques to be described include: (1) harmonic generation of microwave sources, (2) infrared laser difference frequency generation, (3) laser sideband generation, and (4) ultrahigh resolution interferometers.

Infrared emission high spectral resolution atlas of the stratospheric limb

Science.gov (United States)

Maguire, William C.; Kunde, Virgil G.; Herath, Lawrence W.

1989-01-01

An atlas of high resolution infrared emission spectra identifies a number of gaseous atmospheric features significant to stratospheric chemistry in the 770-900/cm and 1100-1360/cm regions at six zenith angles from 86.7 to 95.1 deg. A balloon-borne Michelson interferometer was flown to obtain about 0.03/cm resolution spectra. Two 10/cm extracts are presented here.

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.

α-spectra hyperfine structure resolution by silicon planar detectors

International Nuclear Information System (INIS)

Eremin, V.K.; Verbitskaya, E.M.; Strokan, N.B.; Sukhanov, V.L.; Malyarenko, A.M.

1986-01-01

The lines with 13 keV step from the main one is α-spectra of nuclei with an odd number of nucleons take place. Silicon planar detectors n-Si with the operation surface of 10 mm 2 are developed for resolution of this hyperfine structure. The mechanism of losses in detectors for short-range-path particles is analyzed. The results of measurements from detectors with 10 keV resolution are presented

High resolution X-ray spectra of solar flares. V. interpretation of inner-shell transitions in Fe XX-Fe XXIII

International Nuclear Information System (INIS)

Doschek, G.A.; Feldman, U.; Cowan, R.D.

1981-01-01

We discuss high-resolution solar flare iron line spectra recorded between 1.82 and 1.97 A by a spectrometer flown by the Naval Research Laboratory on an Air Force spacecraft launched on 1979 February 24. The emission line spectrum is due to inner-shell transitions in the ions Fe XX-Fe XXV. Using theoretical spectra and calculations of line intensities obtained by methods discussed by Merts, Cowan, and Magee, we derive electron temperatures as a function for time of two large class X flares. These temperatures are deduced from intensities of lines of Fe XXIII, Fe XXII, and Fe XXIV. Previous measurements by us have involved only lines of Fe XXIV and Fe XXV. We discuss the determination of the differential emission measure between about 12 x 10 6 K and 20 x 10 6 K using these temperatures. The possibility of determining electron densities in flare and tokamak plasmas using the inner-shell spectra of Fe XXI and Fe XX is discussed. We also discuss recent theoretical work by Mewe and Schrijver based on atomic data of Grineva, Safronova, and Urnov

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.

The CARMENES search for exoplanets around M dwarfs. High-resolution optical and near-infrared spectroscopy of 324 survey stars

Science.gov (United States)

Reiners, A.; Zechmeister, M.; Caballero, J. A.; Ribas, I.; Morales, J. C.; Jeffers, S. V.; Schöfer, P.; Tal-Or, L.; Quirrenbach, A.; Amado, P. J.; Kaminski, A.; Seifert, W.; Abril, M.; Aceituno, J.; Alonso-Floriano, F. J.; Ammler-von Eiff, M.; Antona, R.; Anglada-Escudé, G.; Anwand-Heerwart, H.; Arroyo-Torres, B.; Azzaro, M.; Baroch, D.; Barrado, D.; Bauer, F. F.; Becerril, S.; Béjar, V. J. S.; Benítez, D.; Berdinas˜, Z. M.; Bergond, G.; Blümcke, M.; Brinkmöller, M.; del Burgo, C.; Cano, J.; Cárdenas Vázquez, M. C.; Casal, E.; Cifuentes, C.; Claret, A.; Colomé, J.; Cortés-Contreras, M.; Czesla, S.; Díez-Alonso, E.; Dreizler, S.; Feiz, C.; Fernández, M.; Ferro, I. M.; Fuhrmeister, B.; Galadí-Enríquez, D.; Garcia-Piquer, A.; García Vargas, M. L.; Gesa, L.; Galera, V. Gómez; González Hernández, J. I.; González-Peinado, R.; Grözinger, U.; Grohnert, S.; Guàrdia, J.; Guenther, E. W.; Guijarro, A.; Guindos, E. de; Gutiérrez-Soto, J.; Hagen, H.-J.; Hatzes, A. P.; Hauschildt, P. H.; Hedrosa, R. P.; Helmling, J.; Henning, Th.; Hermelo, I.; Hernández Arabí, R.; Hernández Castaño, L.; Hernández Hernando, F.; Herrero, E.; Huber, A.; Huke, P.; Johnson, E. N.; Juan, E. de; Kim, M.; Klein, R.; Klüter, J.; Klutsch, A.; Kürster, M.; Lafarga, M.; Lamert, A.; Lampón, M.; Lara, L. M.; Laun, W.; Lemke, U.; Lenzen, R.; Launhardt, R.; López del Fresno, M.; López-González, J.; López-Puertas, M.; López Salas, J. F.; López-Santiago, J.; Luque, R.; Magán Madinabeitia, H.; Mall, U.; Mancini, L.; Mandel, H.; Marfil, E.; Marín Molina, J. A.; Maroto Fernández, D.; Martín, E. L.; Martín-Ruiz, S.; Marvin, C. J.; Mathar, R. J.; Mirabet, E.; Montes, D.; Moreno-Raya, M. E.; Moya, A.; Mundt, R.; Nagel, E.; Naranjo, V.; Nortmann, L.; Nowak, G.; Ofir, A.; Oreiro, R.; Pallé, E.; Panduro, J.; Pascual, J.; Passegger, V. M.; Pavlov, A.; Pedraz, S.; Pérez-Calpena, A.; Medialdea, D. Pérez; Perger, M.; Perryman, M. A. C.; Pluto, M.; Rabaza, O.; Ramón, A.; Rebolo, R.; Redondo, P.; Reffert, S.; Reinhart, S.; Rhode, P.; Rix, H.-W.; Rodler, F.; Rodríguez, E.; Rodríguez-López, C.; Rodríguez Trinidad, A.; Rohloff, R.-R.; Rosich, A.; Sadegi, S.; Sánchez-Blanco, E.; Sánchez Carrasco, M. A.; Sánchez-López, A.; Sanz-Forcada, J.; Sarkis, P.; Sarmiento, L. F.; Schäfer, S.; Schmitt, J. H. M. M.; Schiller, J.; Schweitzer, A.; Solano, E.; Stahl, O.; Strachan, J. B. P.; Stürmer, J.; Suárez, J. C.; Tabernero, H. M.; Tala, M.; Trifonov, T.; Tulloch, S. M.; Ulbrich, R. G.; Veredas, G.; Vico Linares, J. I.; Vilardell, F.; Wagner, K.; Winkler, J.; Wolthoff, V.; Xu, W.; Yan, F.; Zapatero Osorio, M. R.

2018-04-01

The CARMENES radial velocity (RV) survey is observing 324 M dwarfs to search for any orbiting planets. In this paper, we present the survey sample by publishing one CARMENES spectrum for each M dwarf. These spectra cover the wavelength range 520-1710 nm at a resolution of at least R >80 000, and we measure its RV, Hα emission, and projected rotation velocity. We present an atlas of high-resolution M-dwarf spectra and compare the spectra to atmospheric models. To quantify the RV precision that can be achieved in low-mass stars over the CARMENES wavelength range, we analyze our empirical information on the RV precision from more than 6500 observations. We compare our high-resolution M-dwarf spectra to atmospheric models where we determine the spectroscopic RV information content, Q, and signal-to-noise ratio. We find that for all M-type dwarfs, the highest RV precision can be reached in the wavelength range 700-900 nm. Observations at longer wavelengths are equally precise only at the very latest spectral types (M8 and M9). We demonstrate that in this spectroscopic range, the large amount of absorption features compensates for the intrinsic faintness of an M7 star. To reach an RV precision of 1 m s-1 in very low mass M dwarfs at longer wavelengths likely requires the use of a 10 m class telescope. For spectral types M6 and earlier, the combination of a red visual and a near-infrared spectrograph is ideal to search for low-mass planets and to distinguish between planets and stellar variability. At a 4 m class telescope, an instrument like CARMENES has the potential to push the RV precision well below the typical jitter level of 3-4 m s-1.

High-cadence, High-resolution Spectroscopic Observations of Herbig Stars HD 98922 and V1295 Aquila

Energy Technology Data Exchange (ETDEWEB)

Aarnio, Alicia N.; Monnier, John D.; Calvet, Nuria; Che, Xiao [Department of Astronomy, University of Michigan, 311 West Hall, 1085 S. University Avenue, Ann Arbor, MI 48109 (United States); Harries, Tim J.; Kraus, Stefan; Acreman, David [Department of Physics and Astronomy, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)

2017-10-10

Recent observational work has indicated that mechanisms for accretion and outflow in Herbig Ae/Be star–disk systems may differ from magnetospheric accretion (MA) as it is thought to occur in T Tauri star–disk systems. In this work, we assess the temporal evolution of spectral lines probing accretion and mass loss in Herbig Ae/Be systems and test for consistency with the MA paradigm. For two Herbig Ae/Be stars, HD 98922 (B9e) and V1295 Aql (A2e), we have gathered multi-epoch (∼years) and high-cadence (∼minutes) high-resolution optical spectra to probe a wide range of kinematic processes. Employing a line equivalent width evolution correlation metric introduced here, we identify species co-evolving (indicative of common line origin) via novel visualization. We interferometrically constrain often problematically degenerate parameters, inclination and inner-disk radius, allowing us to focus on the structure of the wind, magnetosphere, and inner gaseous disk in radiative transfer models. Over all timescales sampled, the strongest variability occurs within the blueshifted absorption components of the Balmer series lines; the strength of variability increases with the cadence of the observations. Finally, high-resolution spectra allow us to probe substructure within the Balmer series’ blueshifted absorption components: we observe static, low-velocity features and time-evolving features at higher velocities. Overall, we find the observed line morphologies and variability are inconsistent with a scaled-up T Tauri MA scenario. We suggest that as magnetic field structure and strength change dramatically with increasing stellar mass from T Tauri to Herbig Ae/Be stars, so too may accretion and outflow processes.

High-cadence, High-resolution Spectroscopic Observations of Herbig Stars HD 98922 and V1295 Aquila

International Nuclear Information System (INIS)

Aarnio, Alicia N.; Monnier, John D.; Calvet, Nuria; Che, Xiao; Harries, Tim J.; Kraus, Stefan; Acreman, David

2017-01-01

Recent observational work has indicated that mechanisms for accretion and outflow in Herbig Ae/Be star–disk systems may differ from magnetospheric accretion (MA) as it is thought to occur in T Tauri star–disk systems. In this work, we assess the temporal evolution of spectral lines probing accretion and mass loss in Herbig Ae/Be systems and test for consistency with the MA paradigm. For two Herbig Ae/Be stars, HD 98922 (B9e) and V1295 Aql (A2e), we have gathered multi-epoch (∼years) and high-cadence (∼minutes) high-resolution optical spectra to probe a wide range of kinematic processes. Employing a line equivalent width evolution correlation metric introduced here, we identify species co-evolving (indicative of common line origin) via novel visualization. We interferometrically constrain often problematically degenerate parameters, inclination and inner-disk radius, allowing us to focus on the structure of the wind, magnetosphere, and inner gaseous disk in radiative transfer models. Over all timescales sampled, the strongest variability occurs within the blueshifted absorption components of the Balmer series lines; the strength of variability increases with the cadence of the observations. Finally, high-resolution spectra allow us to probe substructure within the Balmer series’ blueshifted absorption components: we observe static, low-velocity features and time-evolving features at higher velocities. Overall, we find the observed line morphologies and variability are inconsistent with a scaled-up T Tauri MA scenario. We suggest that as magnetic field structure and strength change dramatically with increasing stellar mass from T Tauri to Herbig Ae/Be stars, so too may accretion and outflow processes.

Skew Projection of Echo-Detected EPR Spectra for Increased Sensitivity and Resolution

Science.gov (United States)

Bowman, Michael K.; Krzyaniak, Matthew D.; Cruce, Alex A.; Weber, Ralph T.

2013-01-01

The measurement of EPR spectra during pulsed EPR experiments is commonly accomplished by recording the integral of the electron spin echo as the applied magnetic field is stepped through the spectrum. This approach to echo-detected EPR spectral measurement (ED-EPR) limits sensitivity and spectral resolution and can cause gross distortions in the resulting spectra because some of the information present in the electron spin echo is discarded in such measurements. However, Fourier Transformation of echo shapes measured at a series of magnetic field values followed by skew projection onto either a magnetic field or resonance frequency axis can increase both spectral resolution and sensitivity without the need to trade one against the other. Examples of skew-projected spectra with single crystals, glasses and powders show resolution improvements as large as a factor of seven with sensitivity increases of as much as a factor of five. PMID:23644351

An Investigation of the Complexity of Maillard Reaction Product Profiles from the Thermal Reaction of Amino Acids with Sucrose Using High Resolution Mass Spectrometry

Directory of Open Access Journals (Sweden)

Agnieszka Golon

2014-08-01

Full Text Available Thermal treatment of food changes its chemical composition drastically with the formation of “so-called” Maillard reaction products, being responsible for the sensory properties of food, along with detrimental and beneficial health effects. In this contribution, we will describe the reactivity of several amino acids, including arginine, lysine, aspartic acid, tyrosine, serine and cysteine, with carbohydrates. The analytical strategy employed involves high and ultra-high resolution mass spectrometry followed by chemometric-type data analysis. The different reactivity of amino acids towards carbohydrates has been observed with cysteine and serine, resulting in complex MS spectra with thousands of detectable reaction products. Several compounds have been tentatively identified, including caramelization reaction products, adducts of amino acids with carbohydrates, their dehydration and hydration products, disproportionation products and aromatic compounds based on molecular formula considerations.

Quantification of aluminium-27 NMR spectra of high-surface-area oxides

International Nuclear Information System (INIS)

Pearson, R.M.; Schramm, C.M.

1990-01-01

This paper discusses the quantitation of 27 Al NMR spectra. It is showns that the so called 'invisible' aluminium atoms seen by recent workers are completely consistent with known continuous wave NMR studies of the 27 Al NMR spectra of high surface area aluminium oxides. The use of pulsed NMR techniques further complicate the quantitative measurement of 27 Al NMR spectra, especially when high resolution NMR spectrometers are used for this purpose. Methods are described which allow both the estimation of aluminium not seen by continuous wave techniques and the amounts of the NMR spectra lost in pulsed work. (author). 24 refs.; 6 figs.; 1 tab

High resolution NMR spectroscopy of nanocrystalline proteins at ultra-high magnetic field

International Nuclear Information System (INIS)

Sperling, Lindsay J.; Nieuwkoop, Andrew J.; Lipton, Andrew S.; Berthold, Deborah A.; Rienstra, Chad M.

2010-01-01

Magic-angle spinning (MAS) solid-state NMR (SSNMR) spectroscopy of uniformly- 13 C, 15 N labeled protein samples provides insight into atomic-resolution chemistry and structure. Data collection efficiency has advanced remarkably in the last decade; however, the study of larger proteins is still challenged by relatively low resolution in comparison to solution NMR. In this study, we present a systematic analysis of SSNMR protein spectra acquired at 11.7, 17.6 and 21.1 Tesla ( 1 H frequencies of 500, 750, and 900 MHz). For two protein systems-GB1, a 6 kDa nanocrystalline protein and DsbA, a 21 kDa nanocrystalline protein-line narrowing is demonstrated in all spectral regions with increasing field. Resolution enhancement is greatest in the aliphatic region, including methine, methylene and methyl sites. The resolution for GB1 increases markedly as a function of field, and for DsbA, resolution in the C-C region increases by 42%, according to the number of peaks that can be uniquely picked and integrated in the 900 MHz spectra when compared to the 500 MHz spectra. Additionally, chemical exchange is uniquely observed in the highest field spectra for at least two isoleucine Cδ1 sites in DsbA. These results further illustrate the benefits of high-field MAS SSNMR spectroscopy for protein structural studies.

Clustering and Filtering Tandem Mass Spectra Acquired in Data-Independent Mode

Science.gov (United States)

Pak, Huisong; Nikitin, Frederic; Gluck, Florent; Lisacek, Frederique; Scherl, Alexander; Muller, Markus

2013-12-01

Data-independent mass spectrometry activates all ion species isolated within a given mass-to-charge window ( m/z) regardless of their abundance. This acquisition strategy overcomes the traditional data-dependent ion selection boosting data reproducibility and sensitivity. However, several tandem mass (MS/MS) spectra of the same precursor ion are acquired during chromatographic elution resulting in large data redundancy. Also, the significant number of chimeric spectra and the absence of accurate precursor ion masses hamper peptide identification. Here, we describe an algorithm to preprocess data-independent MS/MS spectra by filtering out noise peaks and clustering the spectra according to both the chromatographic elution profiles and the spectral similarity. In addition, we developed an approach to estimate the m/z value of precursor ions from clustered MS/MS spectra in order to improve database search performance. Data acquired using a small 3 m/z units precursor mass window and multiple injections to cover a m/z range of 400-1400 was processed with our algorithm. It showed an improvement in the number of both peptide and protein identifications by 8 % while reducing the number of submitted spectra by 18 % and the number of peaks by 55 %. We conclude that our clustering method is a valid approach for data analysis of these data-independent fragmentation spectra. The software including the source code is available for the scientific community.

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.

Mass spectra of liquid crystals. III.Phenylpyrimidine derivatives

NARCIS (Netherlands)

Leclercq, P.A.; Bogaert, van den H.M.

1991-01-01

The 70 eV electron impact mass spectra of 34 1-phenyl-2,5-pyrimidine derivatives are presented. Based on the observed mass shifts by the various substituents, the nature of the main fragment ions is rationalized.

High resolution neutron spectroscopy for helium isotopes

International Nuclear Information System (INIS)

Abdel-Wahab, M.S.; Klages, H.O.; Schmalz, G.; Haesner, B.H.; Kecskemeti, J.; Schwarz, P.; Wilczynski, J.

1992-01-01

A high resolution fast neutron time-of-flight spectrometer is described, neutron time-of-flight spectra are taken using a specially designed TDC in connection to an on-line computer. The high time-of-flight resolution of 5 ps/m enabled the study of the total cross section of 4 He for neutrons near the 3/2 + resonance in the 5 He nucleus. The resonance parameters were determined by a single level Breit-Winger fit to the data. (orig.)

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)

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.

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....

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

High-Resolution X-Ray Spectra of the Symbiotic Star SS73 17

Science.gov (United States)

Eze, R. N. C.; Luna, G. J. M.; Smith, R. K.

2010-01-01

SS73 17 was an innocuous Mira-type symbiotic star until the International Gamma-Ray Astrophysics Laboratory and Swift discovered its bright hard X-ray emission, adding it to the small class of "hard X-ray emitting symbiotics." Suzaku observations in 2006 then showed it emits three bright iron lines as well, with little to no emission in the 0.3-2.0 keV bandpass. We present here follow-up observations with the Chandra High Energy Transmission Grating and Suzaku that confirm the earlier detection of strong emission lines of Fe K(alpha) fluorescence, Fe XXV and Fe XXVI but also show significantly more soft X-ray emission. The high-resolution spectrum also shows emission lines of other highly ionized ions as Si xiv and possibly S XVI. In addition, a re-analysis of the 2006 Suzaku data using the latest calibration shows that the hard (15-50 keV) X-ray emission is brighter than previously thought and remains constant in both the 2006 and 2008 data. The G ratio calculated from the Fe xxv lines shows that these lines are thermal, not photoionized, in origin.With the exception of the hard X-ray emission, the spectra from both epochs can be fit using thermal radiation assuming a differential emission measure based on a cooling-flow model combined with a full and partial absorber. We show that acceptable fits can be obtained for all the data in the 1-10 keV band varying only the partial absorber. Based on the temperature and accretion rate, the thermal emission appears to be arising from the boundary layer between the accreting white dwarf and the accretion disk.

HIGH-RESOLUTION X-RAY SPECTRA OF THE SYMBIOTIC STAR SS73 17

International Nuclear Information System (INIS)

Eze, R. N. C.; Luna, G. J. M.; Smith, R. K.

2010-01-01

SS73 17 was an innocuous Mira-type symbiotic star until the International Gamma-Ray Astrophysics Laboratory and Swift discovered its bright hard X-ray emission, adding it to the small class of 'hard X-ray emitting symbiotics'. Suzaku observations in 2006 then showed it emits three bright iron lines as well, with little to no emission in the 0.3-2.0 keV bandpass. We present here follow-up observations with the Chandra High Energy Transmission Grating and Suzaku that confirm the earlier detection of strong emission lines of Fe Kα fluorescence, Fe XXV and Fe XXVI but also show significantly more soft X-ray emission. The high-resolution spectrum also shows emission lines of other highly ionized ions as Si XIV and possibly S XVI. In addition, a re-analysis of the 2006 Suzaku data using the latest calibration shows that the hard (15-50 keV) X-ray emission is brighter than previously thought and remains constant in both the 2006 and 2008 data. The G ratio calculated from the Fe XXV lines shows that these lines are thermal, not photoionized, in origin. With the exception of the hard X-ray emission, the spectra from both epochs can be fit using thermal radiation assuming a differential emission measure based on a cooling-flow model combined with a full and partial absorber. We show that acceptable fits can be obtained for all the data in the 1-10 keV band varying only the partial absorber. Based on the temperature and accretion rate, the thermal emission appears to be arising from the boundary layer between the accreting white dwarf and the accretion disk.

A scale space approach for unsupervised feature selection in mass spectra classification for ovarian cancer detection.

Science.gov (United States)

Ceccarelli, Michele; d'Acierno, Antonio; Facchiano, Angelo

2009-10-15

Mass spectrometry spectra, widely used in proteomics studies as a screening tool for protein profiling and to detect discriminatory signals, are high dimensional data. A large number of local maxima (a.k.a. peaks) have to be analyzed as part of computational pipelines aimed at the realization of efficient predictive and screening protocols. With this kind of data dimensions and samples size the risk of over-fitting and selection bias is pervasive. Therefore the development of bio-informatics methods based on unsupervised feature extraction can lead to general tools which can be applied to several fields of predictive proteomics. We propose a method for feature selection and extraction grounded on the theory of multi-scale spaces for high resolution spectra derived from analysis of serum. Then we use support vector machines for classification. In particular we use a database containing 216 samples spectra divided in 115 cancer and 91 control samples. The overall accuracy averaged over a large cross validation study is 98.18. The area under the ROC curve of the best selected model is 0.9962. We improved previous known results on the problem on the same data, with the advantage that the proposed method has an unsupervised feature selection phase. All the developed code, as MATLAB scripts, can be downloaded from http://medeaserver.isa.cnr.it/dacierno/spectracode.htm.

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.)

High Resolution Thz and FIR Spectroscopy of SOCl_2

Science.gov (United States)

Martin-Drumel, M. A.; Cuisset, A.; Sadovskii, D. A.; Mouret, G.; Hindle, F.; Pirali, O.

2013-06-01

Thionyl chloride (SOCl_2) is an extremely powerful oxidant widely used in industrial processes and playing a role in the chemistry of the atmosphere. In addition, it has a molecular configuration similar to that of phosgene (COCl_2), and is therefore of particular interest for security and defense applications. Low resolution vibrational spectra of gas phase SOCl_2 as well as high resolution pure rotational transitions up to 25 GHz have previously been investigated. To date no high resolution data are reported at frequencies higher than 25 GHz. We have investigated the THz absorption spectrum of SOCl_2 in the spectral region 70-650 GHz using a frequency multiplier chain coupled to a 1 m long single path cell containing a pressure of about 15 μbar. At the time of the writing, about 8000 pure rotational transitions of SO^{35}Cl_2 with highest J and K_a values of 110 and 50 respectively have been assigned on the spectrum. We have also recorded the high resolution FIR spectra of SOCl_2 in the spectral range 50-700 wn using synchrotron radiation at the AILES beamline of SOLEIL facility. A White-type cell aligned with an absorption path length of 150 m has been used to record, at a resolution of 0.001 wn, two spectra at pressures of 5 and 56 μbar of SOCl_2. On these spectra all FIR modes of SOCl_2 are observed (ν_2 to ν_6) and present a resolved rotational structure. Their analysis is in progress. T. J. Johnson et al., J. Phys. Chem. A 107, 6183 (2003) D. E. Martz and R. T. Lagemann, J. Chem. Phys. 22,1193 (1954) H. S. P. Müller and M. C. L. Gerry, J. Chem. Soc. Faraday Trans. 90, 3473 (1994)

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

Studies on the microbial biotransformation of the novel psychoactive substance methylenedioxypyrovalerone (MDPV) in wastewater by means of liquid chromatography-high resolution mass spectrometry/mass spectrometry.

Science.gov (United States)

Mardal, Marie; Meyer, Markus R

2014-09-15

Sewage profiling as a mean to estimate consumption of drugs of abuse is gaining increasing attention. However, only scarce data are available so far on the impact of microbial biotransformation on the presence and hence detectability of drugs of abuse and their metabolites in wastewater (WW) samples. The aim of this work was therefore to study the biotransformation pathways of the novel psychoactive substance 3,4-methylenedioxypyrovalerone (MPDV) in WW by incubating it, based on the OECD guideline 314 A. MDPV was incubated (100 μg/L) for 10d at 22 °C in WW from a local WW treatment plant. Furthermore, urine and feces collected from rats administered 20mg MDPV/kg BW were incubated correspondingly. Samples were worked-up either by centrifugation/filtration and solid-phase (HCX) extraction or QuEChERS. High resolution (HR) mass spectra (MS) were recorded using an Orbitrap mass spectrometer. All products were identified via their HR-MS(2) spectra and chromatographic properties. The observed biotransformations in WW were: demethylenation and subsequent O-methylation, hydroxylation at the phenyl part, hydroxylation at the pyrrolidine part with subsequent methylation or oxidation, N-demethylation, and hydroxylation at the alkyl part as well as combination of them. In total, 12 biotransformation products were identified after 10 days of incubation. Three of these biotransformation products were previously reported to be also rat and human metabolites. No additional MDPV biotransformation products could be found after incubating the rat urine and feces samples. Instead, the urinary phase II glucuronides were nearly completely cleaved after one day of WW incubation. The presented study indicates that demethylenyl-methyl MDPV, the most abundant metabolite in human urine, should be the best indicator in WW to estimate its use. Copyright © 2014 Elsevier B.V. All rights reserved.

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS: THE REALM OF ANHARMONICITY

Energy Technology Data Exchange (ETDEWEB)

Maltseva, Elena; Buma, Wybren Jan [University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Tielens, Alexander G. G. M. [Leiden Observatory, Niels Bohrweg 2, 2333 CA Leiden (Netherlands); Huang, Xinchuan; Lee, Timothy J. [SETI Institute, 189 Bernardo Avenue, Suite 100, Mountain View, CA 94043 (United States); Oomens, Jos, E-mail: w.j.buma@uva.nl, E-mail: petrignani@strw.leidenuniv.nl [Radboud University, Toernooiveld 7, 6525 ED Nijmegen (Netherlands)

2015-11-20

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3-μm CH stretching region of polycyclic aromatic hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (∼4 K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main bands that fall within 0.5% of the experimental frequencies. The implications for the aromatic infrared bands, specifically the 3-μm band, are discussed.

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

Science.gov (United States)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-01-01

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

Interpretation of Tandem Mass Spectrometry (MSMS) Spectra for Peptide Analysis

DEFF Research Database (Denmark)

Hjernø, Karin; Højrup, Peter

2015-01-01

The aim of this chapter is to give a short introduction to peptide analysis by mass spectrometry (MS) and interpretation of fragment mass spectra. Through examples and guidelines we demonstrate how to understand and validate search results and how to perform de novo sequencing based on the often...... very complex fragmentation pattern obtained by tandem mass spectrometry (also referred to as MSMS). The focus is on simple rules for interpretation of MSMS spectra of tryptic as well as non-tryptic peptides....

Deriving temperature, mass, and age of evolved stars from high-resolution spectra. Application to field stars and the open cluster IC 4651

Science.gov (United States)

Biazzo, K.; Pasquini, L.; Girardi, L.; Frasca, A.; da Silva, L.; Setiawan, J.; Marilli, E.; Hatzes, A. P.; Catalano, S.

2007-12-01

Aims:We test our capability of deriving stellar physical parameters of giant stars by analysing a sample of field stars and the well studied open cluster IC 4651 with different spectroscopic methods. Methods: The use of a technique based on line-depth ratios (LDRs) allows us to determine with high precision the effective temperature of the stars and to compare the results with those obtained with a classical LTE abundance analysis. Results: (i) For the field stars we find that the temperatures derived by means of the LDR method are in excellent agreement with those found by the spectral synthesis. This result is extremely encouraging because it shows that spectra can be used to firmly derive population characteristics (e.g., mass and age) of the observed stars. (ii) For the IC 4651 stars we use the determined effective temperature to derive the following results. a) The reddening E(B-V) of the cluster is 0.12±0.02, largely independent of the color-temperature calibration used. b) The age of the cluster is 1.2±0.2 Gyr. c) The typical mass of the analysed giant stars is 2.0±0.2~M⊙. Moreover, we find a systematic difference of about 0.2 dex in log g between spectroscopic and evolutionary values. Conclusions: We conclude that, in spite of known limitations, a classical spectroscopic analysis of giant stars may indeed result in very reliable stellar parameters. We caution that the quality of the agreement, on the other hand, depends on the details of the adopted spectroscopic analysis. Based on observations collected at the ESO telescopes at the Paranal and La Silla Observatories, Chile.

Quantitative analysis of multiple high-resolution mass spectrometry images using chemometric methods: quantitation of chlordecone in mouse liver.

Science.gov (United States)

Mohammadi, Saeedeh; Parastar, Hadi

2018-05-15

In this work, a chemometrics-based strategy is developed for quantitative mass spectrometry imaging (MSI). In this regard, quantification of chlordecone as a carcinogenic organochlorinated pesticide (C10Cll0O) in mouse liver using the matrix-assisted laser desorption ionization MSI (MALDI-MSI) method is used as a case study. The MSI datasets corresponded to 1, 5 and 10 days of mouse exposure to the standard chlordecone in the quantity range of 0 to 450 μg g-1. The binning approach in the m/z direction is used to group high resolution m/z values and to reduce the big data size. To consider the effect of bin size on the quality of results, three different bin sizes of 0.25, 0.5 and 1.0 were chosen. Afterwards, three-way MSI data arrays (two spatial and one m/z dimensions) for seven standards and four unknown samples were column-wise augmented with m/z values as the common mode. Then, these datasets were analyzed using multivariate curve resolution-alternating least squares (MCR-ALS) using proper constraints. The resolved mass spectra were used for identification of chlordecone in the presence of a complex background and interference. Additionally, the augmented spatial profiles were post-processed and 2D images for each component were obtained in calibration and unknown samples. The sum of these profiles was utilized to set the calibration curve and to obtain the analytical figures of merit (AFOMs). Inspection of the results showed that the lower bin size (i.e., 0.25) provides more accurate results. Finally, the obtained results by MCR for three datasets were compared with those of gas chromatography-mass spectrometry (GC-MS) and MALDI-MSI. The results showed that the MCR-assisted method gives a higher amount of chlordecone than MALDI-MSI and a lower amount than GC-MS. It is concluded that a combination of chemometric methods with MSI can be considered as an alternative way for MSI quantification.

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.).

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

ELM: an Algorithm to Estimate the Alpha Abundance from Low-resolution Spectra

Science.gov (United States)

Bu, Yude; Zhao, Gang; Pan, Jingchang; Bharat Kumar, Yerra

2016-01-01

We have investigated a novel methodology using the extreme learning machine (ELM) algorithm to determine the α abundance of stars. Applying two methods based on the ELM algorithm—ELM+spectra and ELM+Lick indices—to the stellar spectra from the ELODIE database, we measured the α abundance with a precision better than 0.065 dex. By applying these two methods to the spectra with different signal-to-noise ratios (S/Ns) and different resolutions, we found that ELM+spectra is more robust against degraded resolution and ELM+Lick indices is more robust against variation in S/N. To further validate the performance of ELM, we applied ELM+spectra and ELM+Lick indices to SDSS spectra and estimated α abundances with a precision around 0.10 dex, which is comparable to the results given by the SEGUE Stellar Parameter Pipeline. We further applied ELM to the spectra of stars in Galactic globular clusters (M15, M13, M71) and open clusters (NGC 2420, M67, NGC 6791), and results show good agreement with previous studies (within 1σ). A comparison of the ELM with other widely used methods including support vector machine, Gaussian process regression, artificial neural networks, and linear least-squares regression shows that ELM is efficient with computational resources and more accurate than other methods.

ELM: AN ALGORITHM TO ESTIMATE THE ALPHA ABUNDANCE FROM LOW-RESOLUTION SPECTRA

International Nuclear Information System (INIS)

Bu, Yude; Zhao, Gang; Kumar, Yerra Bharat; Pan, Jingchang

2016-01-01

We have investigated a novel methodology using the extreme learning machine (ELM) algorithm to determine the α abundance of stars. Applying two methods based on the ELM algorithm—ELM+spectra and ELM+Lick indices—to the stellar spectra from the ELODIE database, we measured the α abundance with a precision better than 0.065 dex. By applying these two methods to the spectra with different signal-to-noise ratios (S/Ns) and different resolutions, we found that ELM+spectra is more robust against degraded resolution and ELM+Lick indices is more robust against variation in S/N. To further validate the performance of ELM, we applied ELM+spectra and ELM+Lick indices to SDSS spectra and estimated α abundances with a precision around 0.10 dex, which is comparable to the results given by the SEGUE Stellar Parameter Pipeline. We further applied ELM to the spectra of stars in Galactic globular clusters (M15, M13, M71) and open clusters (NGC 2420, M67, NGC 6791), and results show good agreement with previous studies (within 1σ). A comparison of the ELM with other widely used methods including support vector machine, Gaussian process regression, artificial neural networks, and linear least-squares regression shows that ELM is efficient with computational resources and more accurate than other methods

ELM: AN ALGORITHM TO ESTIMATE THE ALPHA ABUNDANCE FROM LOW-RESOLUTION SPECTRA

Energy Technology Data Exchange (ETDEWEB)

Bu, Yude [School of Mathematics and Statistics, Shandong University, Weihai, 264209, Shandong (China); Zhao, Gang; Kumar, Yerra Bharat [Key Laboratory for Optical Astronomy, National Astronomical Observatories, Chinese Academy of Sciences, Beijing, 100012 (China); Pan, Jingchang, E-mail: ydbu@bao.ac.cn, E-mail: gzhao@nao.cas.cn [School of Mechanical, Electrical and Information Engineering, Shandong University, Weihai, 264209, Shandong (China)

2016-01-20

We have investigated a novel methodology using the extreme learning machine (ELM) algorithm to determine the α abundance of stars. Applying two methods based on the ELM algorithm—ELM+spectra and ELM+Lick indices—to the stellar spectra from the ELODIE database, we measured the α abundance with a precision better than 0.065 dex. By applying these two methods to the spectra with different signal-to-noise ratios (S/Ns) and different resolutions, we found that ELM+spectra is more robust against degraded resolution and ELM+Lick indices is more robust against variation in S/N. To further validate the performance of ELM, we applied ELM+spectra and ELM+Lick indices to SDSS spectra and estimated α abundances with a precision around 0.10 dex, which is comparable to the results given by the SEGUE Stellar Parameter Pipeline. We further applied ELM to the spectra of stars in Galactic globular clusters (M15, M13, M71) and open clusters (NGC 2420, M67, NGC 6791), and results show good agreement with previous studies (within 1σ). A comparison of the ELM with other widely used methods including support vector machine, Gaussian process regression, artificial neural networks, and linear least-squares regression shows that ELM is efficient with computational resources and more accurate than other methods.

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.

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...

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.

cap alpha. -spectra hyperfine structure resolution by silicon planar detectors

Energy Technology Data Exchange (ETDEWEB)

Eremin, V K; Verbitskaya, E M; Strokan, N B; Sukhanov, V L; Malyarenko, A M

1986-10-01

The lines with 13 keV step from the main one is ..cap alpha..-spectra of nuclei with an odd number of nucleons take place. Silicon planar detectors n-Si with the operation surface of 10 mm/sup 2/ are developed for resolution of this hyperfine structure. The mechanism of losses in detectors for short-range-path particles is analyzed. The results of measurements from detectors with 10 keV resolution are presented.

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.

Deconvolution of mixture spectra and increased throughput of Peptide identification by utilization of intensified complementary ions formed in tandem mass spectrometry

DEFF Research Database (Denmark)

Kryuchkov, Fedor; Verano-Braga, Thiago; Hansen, Thomas Aarup

2013-01-01

-resolution orbitrap mass spectrometry, an increase in the number of peptide identifications was obtained relative to the original CAD MS/MS spectra when intensified golden complementary (+18.6%) and CAD complementary pairs (+17.2%) were submitted to the Mascot search engine. This also exceeded the results obtained...

Evidence for mass loss at moderate to high velocity in Be stars

International Nuclear Information System (INIS)

Snow, T.P. Jr.; Marlborough, J.M.

1976-01-01

Ultraviolet spectra of intermediate resolution have been obtained with Copernicus of 12 objects classified as Be or shell stars, and 19 additional early B dwarfs. Some of these spectra show marked asymmetries in certain resonance lines, especially the Si iv doublet at 1400 A, indicating the presence in some cases of outflowing material with maximum velocities of nearly 1000 km s -1 . Direct evidence for mass loss at these velocities is seen for the first time in dwarf stars as late as B1.5; the only objects later than B0.5 which show this effect are Be or shell stars. Among the stars considered there is a correlation between the presence of mass-loss effects and projected rotational velocity, suggesting that the ultraviolet flux from B1-B2 dwarfs is sufficient to drive high-velocity stellar winds only if rotation effects reduce the effective gravity near the equator. The mass loss rate for one of the most active Be stars, 59 Cyg, is crudely estimated to be 10 -10 --10 -9 M/sub sun/ yr -1 . The data are suggestive that the extended atmospheres associated with Be star phenomena may be formed by mass ejection

CHEMICAL ABUNDANCES IN FIELD RED GIANTS FROM HIGH-RESOLUTION H-BAND SPECTRA USING THE APOGEE SPECTRAL LINELIST

International Nuclear Information System (INIS)

Smith, Verne V.; Cunha, Katia; Shetrone, Matthew D.; Meszaros, Szabolcs; Allende Prieto, Carlos; Bizyaev, Dmitry; Garcìa Pèrez, Ana; Majewski, Steven R.; Schiavon, Ricardo; Holtzman, Jon; Johnson, Jennifer A.

2013-01-01

High-resolution H-band spectra of five bright field K, M, and MS giants, obtained from the archives of the Kitt Peak National Observatory Fourier transform spectrometer, are analyzed to determine chemical abundances of 16 elements. The abundances were derived via spectrum synthesis using the detailed linelist prepared for the Sloan Digital Sky Survey III Apache Point Galactic Evolution Experiment (APOGEE), which is a high-resolution near-infrared spectroscopic survey to derive detailed chemical abundance distributions and precise radial velocities for 100,000 red giants sampling all Galactic stellar populations. The red giant sample studied here was chosen to probe which chemical elements can be derived reliably from the H-band APOGEE spectral region. These red giants consist of two K-giants (α Boo and μ Leo), two M-giants (β And and δ Oph), and one thermally pulsing asymptotic giant branch (TP-AGB) star of spectral type MS (HD 199799). Measured chemical abundances include the cosmochemically important isotopes 12 C, 13 C, 14 N, and 16 O, along with Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. The K and M giants exhibit the abundance signature of the first dredge-up of CN-cycle material, while the TP-AGB star shows clear evidence of the addition of 12 C synthesized during 4 He-burning thermal pulses and subsequent third dredge-up. A comparison of the abundances derived here with published values for these stars reveals consistent results to ∼0.1 dex. The APOGEE spectral region and linelist is thus well suited for probing both Galactic chemical evolution, as well as internal nucleosynthesis and mixing in populations of red giants via high-resolution spectroscopy.

CHEMICAL ABUNDANCES IN FIELD RED GIANTS FROM HIGH-RESOLUTION H-BAND SPECTRA USING THE APOGEE SPECTRAL LINELIST

Energy Technology Data Exchange (ETDEWEB)

Smith, Verne V.; Cunha, Katia [National Optical Astronomy Observatories, Tucson, AZ 85719 (United States); Shetrone, Matthew D. [Department of Astronomy and McDonald Observatory, University of Texas, Austin, TX 78712 (United States); Meszaros, Szabolcs; Allende Prieto, Carlos [Instituto d' Astrofisica de Canarias, E-38205, La Laguna, Tenerife (Spain); Bizyaev, Dmitry [Apache Point Observatory, Sunspot, NM 88349 (United States); Garcia Perez, Ana; Majewski, Steven R. [Department of Astronomy, University of Virginia, Charlottesville, VA 22904 (United States); Schiavon, Ricardo [Astrophysics Research Institute, Liverpool John Moores University, Liverpool L3 5UX (United Kingdom); Holtzman, Jon [Department of Astronomy, New Mexico State University, Las Cruces, NM 88003 (United States); Johnson, Jennifer A., E-mail: vsmith@noao.edu [Department of Astronomy, Ohio State University, Columbus, OH 43210 (United States)

2013-03-01

High-resolution H-band spectra of five bright field K, M, and MS giants, obtained from the archives of the Kitt Peak National Observatory Fourier transform spectrometer, are analyzed to determine chemical abundances of 16 elements. The abundances were derived via spectrum synthesis using the detailed linelist prepared for the Sloan Digital Sky Survey III Apache Point Galactic Evolution Experiment (APOGEE), which is a high-resolution near-infrared spectroscopic survey to derive detailed chemical abundance distributions and precise radial velocities for 100,000 red giants sampling all Galactic stellar populations. The red giant sample studied here was chosen to probe which chemical elements can be derived reliably from the H-band APOGEE spectral region. These red giants consist of two K-giants ({alpha} Boo and {mu} Leo), two M-giants ({beta} And and {delta} Oph), and one thermally pulsing asymptotic giant branch (TP-AGB) star of spectral type MS (HD 199799). Measured chemical abundances include the cosmochemically important isotopes {sup 12}C, {sup 13}C, {sup 14}N, and {sup 16}O, along with Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. The K and M giants exhibit the abundance signature of the first dredge-up of CN-cycle material, while the TP-AGB star shows clear evidence of the addition of {sup 12}C synthesized during {sup 4}He-burning thermal pulses and subsequent third dredge-up. A comparison of the abundances derived here with published values for these stars reveals consistent results to {approx}0.1 dex. The APOGEE spectral region and linelist is thus well suited for probing both Galactic chemical evolution, as well as internal nucleosynthesis and mixing in populations of red giants via high-resolution spectroscopy.

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.

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.

INTRAMOLECULAR ISOTOPE EFFECTS IN HYDROCARBON MASS SPECTRA

Energy Technology Data Exchange (ETDEWEB)

Stevenson, D. P.; Schachtschneider, J. H.

1963-07-15

Approximate calculations based on the quasi-equilibrium rate theory of the origin of mass spectra are shown to lead to an approximately correct magnitude for the intramolecular ( pi /sup -/) isotope effect on C--H bond dissociation probabilities of various deuterohydrocarbons. (auth)

A method for analyzing low statistics high resolution spectra from 210Pb in underground coal miners from Brazil

International Nuclear Information System (INIS)

Dantas, A.L.A.; Dantas, B.M.; Lipsztein, J.L.; Spitz, H.B.

2006-01-01

A survey conducted by the IRD-CNEN determined that some workers from an underground coal mine in the south of Brazil were exposed to elevated airborne concentrations of 222 Rn. Because inhalation of high airborne concentrations of 222 Rn can lead to an increase of 210 Pb in bone, in vivo measurements of 210 Pb in the skeleton were performed in selected underground workers from this mine. Measurements were performed using an array of high-resolution germanium detectors positioned around the head and knee to detect the low abundant 46.5 keV photon emitted by 210 Pb. The gamma-ray spectra were analyzed using a moving median smoothing function to detect the presence of a photopeak at 46.5 keV. The minimum detectable activity of 210 Pb in the skeleton using this methodology was 50 Bq. (author)

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.

High resolution transmission spectroscopy as a diagnostic for Jovian exoplanet atmospheres: constraints from theoretical models

Energy Technology Data Exchange (ETDEWEB)

Kempton, Eliza M.-R. [Department of Physics, Grinnell College, Grinnell, IA 50112 (United States); Perna, Rosalba [Department of Physics and Astronomy, Stony Brook University, Stony Brook, NY 11794 (United States); Heng, Kevin, E-mail: kemptone@grinnell.edu [University of Bern, Center for Space and Habitability, Sidlerstrasse 5, CH-3012 Bern (Switzerland)

2014-11-01

We present high resolution transmission spectra of giant planet atmospheres from a coupled three-dimensional (3D) atmospheric dynamics and transmission spectrum model that includes Doppler shifts which arise from winds and planetary motion. We model Jovian planets covering more than two orders of magnitude in incident flux, corresponding to planets with 0.9-55 day orbital periods around solar-type stars. The results of our 3D dynamical models reveal certain aspects of high resolution transmission spectra that are not present in simple one-dimensional (1D) models. We find that the hottest planets experience strong substellar to anti-stellar (SSAS) winds, resulting in transmission spectra with net blueshifts of up to 3 km s{sup –1}, whereas less irradiated planets show almost no net Doppler shifts. We find only minor differences between transmission spectra for atmospheres with temperature inversions and those without. Compared to 1D models, peak line strengths are significantly reduced for the hottest atmospheres owing to Doppler broadening from a combination of rotation (which is faster for close-in planets under the assumption of tidal locking) and atmospheric winds. Finally, high resolution transmission spectra may be useful in studying the atmospheres of exoplanets with optically thick clouds since line cores for very strong transitions should remain optically thick to very high altitude. High resolution transmission spectra are an excellent observational test for the validity of 3D atmospheric dynamics models, because they provide a direct probe of wind structures and heat circulation. Ground-based exoplanet spectroscopy is currently on the verge of being able to verify some of our modeling predictions, most notably the dependence of SSAS winds on insolation. We caution that interpretation of high resolution transmission spectra based on 1D atmospheric models may be inadequate, as 3D atmospheric motions can produce a noticeable effect on the absorption

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...

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.)

High resolution X-ray spectroscopy of laser generated plasmas

International Nuclear Information System (INIS)

Faenov, A.Ya.; Skobelev, I.Yu.; Rosmej, F.B.

1999-01-01

The application of recently developed spectroscopic instruments in laser produced plasmas with simultaneous high spectral and spatial resolution combined with high luminosity discovered new types of X-ray spectra. These new types are characterised by the disappearance of the resonance lines and the strong emission of dielectronic satellite spectra. Several types of transitions of highly charged ions are discovered which are unknown from usual sources employed in atomic physics. New theoretical models are developed and successfully applied for the interpretation and for plasma diagnostics. (orig.)

High resolution X-ray spectroscopy of laser generated plasmas

Energy Technology Data Exchange (ETDEWEB)

Faenov, A.Ya.; Skobelev, I.Yu. [Multicharged Ions Spectra Data Center of VNIIFTRI, Mendeleevo (Russian Federation); Rosmej, F.B. [Technische Hochschule Darmstadt (Germany). Inst. fuer Kernphysik

1999-11-01

The application of recently developed spectroscopic instruments in laser produced plasmas with simultaneous high spectral and spatial resolution combined with high luminosity discovered new types of X-ray spectra. These new types are characterised by the disappearance of the resonance lines and the strong emission of dielectronic satellite spectra. Several types of transitions of highly charged ions are discovered which are unknown from usual sources employed in atomic physics. New theoretical models are developed and successfully applied for the interpretation and for plasma diagnostics. (orig.) 28 refs.

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

Evidence for mass loss at moderate to high velocity in Be stars

Science.gov (United States)

Snow, T. P., Jr.; Marlborough, J. M.

1976-01-01

Ultraviolet spectra of intermediate resolution have been obtained with Copernicus for 12 objects classified as Be or shell stars and for 19 additional early B dwarfs. Some of these spectra show marked asymmetries in certain resonance lines, especially the Si IV doublet at 1400 A, indicating the presence in some cases of outflowing material with maximum velocities of nearly 1000 km/s. Direct evidence for mass loss at these velocities is seen for the first time in dwarf stars as late as B1.5; the only objects later than B0.5 which show this effect are Be or shell stars. Among the stars considered, there is a correlation between the presence of mass-loss effects and projected rotational velocity, suggesting that the ultraviolet flux from B1-B2 dwarfs is sufficient to drive high-velocity stellar winds only if rotational effects reduce the effective gravity near the equator. The mass-loss rate for one of the most active Be stars, 59 Cyg, is crudely estimated to be one billionth or one ten-billionth of a solar mass per year. The data suggest that the extended atmospheres associated with Be-star phenomena may be formed by mass ejection.

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.

Screening of Chlamydomonas reinhardtii Populations with Single-Cell Resolution by Using a High-Throughput Microscale Sample Preparation for Matrix-Assisted Laser Desorption Ionization Mass Spectrometry.

Science.gov (United States)

Krismer, Jasmin; Sobek, Jens; Steinhoff, Robert F; Fagerer, Stephan R; Pabst, Martin; Zenobi, Renato

2015-08-15

The consequences of cellular heterogeneity, such as biocide persistence, can only be tackled by studying each individual in a cell population. Fluorescent tags provide tools for the high-throughput analysis of genomes, RNA transcripts, or proteins on the single-cell level. However, the analysis of lower-molecular-weight compounds that elude tagging is still a great challenge. Here, we describe a novel high-throughput microscale sample preparation technique for single cells that allows a mass spectrum to be obtained for each individual cell within a microbial population. The approach presented includes spotting Chlamydomonas reinhardtii cells, using a noncontact microarrayer, onto a specialized slide and controlled lysis of cells separated on the slide. Throughout the sample preparation, analytes were traced and individual steps optimized using autofluorescence detection of chlorophyll. The lysates of isolated cells are subjected to a direct, label-free analysis using matrix-assisted laser desorption ionization mass spectrometry. Thus, we were able to differentiate individual cells of two Chlamydomonas reinhardtii strains based on single-cell mass spectra. Furthermore, we showed that only population profiles with real single-cell resolution render a nondistorted picture of the phenotypes contained in a population. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

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

A Search for Water in a Super-Earth Atmosphere: High-resolution Optical Spectroscopy of 55Cancri e

Energy Technology Data Exchange (ETDEWEB)

Esteves, Lisa J. [Astronomy and Astrophysics, University of Toronto, 50 St. George Street, Toronto, Ontario M5S 3H4 (Canada); De Mooij, Ernst J. W.; Watson, Chris [Astrophysics Research Centre, School of Mathematics and Physics, Queens University, Belfast (United Kingdom); Jayawardhana, Ray [Physics and Astronomy, York University, Toronto, Ontario L3T 3R1 (Canada); De Kok, Remco, E-mail: esteves@astro.utoronto.ca, E-mail: ernst.demooij@dcu.ie, E-mail: c.a.watson@qub.ac.uk, E-mail: rayjay@yorku.ca, E-mail: r.j.de.kok@sron.nl [Leiden Observatory, Leiden University, Postbus 9513, 2300 RA, Leiden (Netherlands)

2017-06-01

We present the analysis of high-resolution optical spectra of four transits of 55Cnc e, a low-density super-Earth that orbits a nearby Sun-like star in under 18 hr. The inferred bulk density of the planet implies a substantial envelope, which, according to mass–radius relationships, could be either a low-mass extended or a high-mass compact atmosphere. Our observations investigate the latter scenario, with water as the dominant species. We take advantage of the Doppler cross-correlation technique, high-spectral resolution, and the large wavelength coverage of our observations to search for the signature of thousands of optical water absorption lines. Using our observations with HDS on the Subaru telescope and ESPaDOnS on the Canada–France–Hawaii Telescope, we are able to place a 3 σ lower limit of 10 g mol{sup −1} on the mean-molecular weight of 55Cnc e’s water-rich (volume mixing ratio >10%), optically thin atmosphere, which corresponds to an atmospheric scale-height of ∼80 km. Our study marks the first high-spectral resolution search for water in a super-Earth atmosphere, and demonstrates that it is possible to recover known water-vapor absorption signals in a nearby super-Earth atmosphere, using high-resolution transit spectroscopy with current ground-based instruments.

Low resolution spectroscopy of selected Algol systems

Science.gov (United States)

Devarapalli, Shanti Priya; Jagirdar, Rukmini; Parthasarathy, M.; Sahu, D. K.; Mohan, Vijay; Bhatt, B. C.; Thomas, Vineet S.

2018-04-01

The analysis of spectroscopic data for 30 Algol-type binaries is presented. All these systems are short period Algols having primaries with spectral types B and A. Dominant spectral lines were identified for the spectra collected and their equivalent widths were calculated. All the spectra were examined to understand presence of mass transfer, a disk or circumstellar matter and chromospheric emission. We also present first spectroscopic and period study for few Algols and conclude that high resolution spectra within and outside the primary minimum are needed for better understanding of these Algol type close binaries.

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

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.

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

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

Peptide de novo sequencing of mixture tandem mass spectra

DEFF Research Database (Denmark)

Gorshkov, Vladimir; Hotta, Stéphanie Yuki Kolbeck; Braga, Thiago Verano

2016-01-01

they decrease the identification performance using database search engines. De novo sequencing approaches are expected to be even more sensitive to the reduction in mass spectrum quality resulting from peptide precursor co-isolation and thus prone to false identifications. The deconvolution approach matched...... complementary b-, y-ions to each precursor peptide mass, which allowed the creation of virtual spectra containing sequence specific fragment ions of each co-isolated peptide. Deconvolution processing resulted in equally efficient identification rates but increased the absolute number of correctly sequenced...... peptides. The improvement was in the range of 20–35% additional peptide identifications for a HeLa lysate sample. Some correct sequences were identified only using unprocessed spectra; however, the number of these was lower than those where improvement was obtained by mass spectral deconvolution. Tight...

High resolution SETI: Experiences and prospects

Science.gov (United States)

Horowitz, Paul; Clubok, Ken

Megachannel spectroscopy with sub-Hertz resolution constitutes an attractive strategy for a microwave search for extraterrestrial intelligence (SETI), assuming the transmission of a narrowband radiofrequency beacon. Such resolution matches the properties of the interstellar medium, and the necessary Doppler corrections provide a high degree of interference rejection. We have constructed a frequency-agile receiver with an FFT-based 8 megachannel digital spectrum analyzer, on-line signal recognition, and multithreshold archiving. We are using it to conduct a meridian transit search of the northern sky at the Harvard-Smithsonian 26-m antenna, with a second identical system scheduled to begin observations in Argentina this month. Successive 400 kHz spectra, at 0.05 Hz resolution, are searched for features characteristic of an intentional narrowband beacon transmission. These spectra are centered on guessable frequencies (such as λ21 cm), referenced successively to the local standard of rest, the galactic barycenter, and the cosmic blackbody rest frame. This search has rejected interference admirably, but is greatly limited both in total frequency coverage and sensitivity to signals other than carriers. We summarize five years of high resolution SETI at Harvard, in the context of answering the questions "How useful is narrowband SETI, how serious are its limitations, what can be done to circumvent them, and in what direction should SETI evolve?" Increasingly powerful signal processing hardware, combined with ever-higher memory densities, are particularly relevant, permitting the construction of compact and affordable gigachannel spectrum analyzers covering hundreds of megahertz of instantaneous bandwidth.

Burn-Up Determination by High Resolution Gamma Spectrometry: Spectra from Slightly-Irradiated Uranium and Plutonium between 400-830 keV

International Nuclear Information System (INIS)

Forsyth, R.S.; Ronqvist, N.

1966-08-01

Previously published studies of the short-cooled fission product spectra of irradiated uranium have been severely restricted by the poor energy resolution of the sodium iodide detectors used. In this report are presented fission product spectra of irradiated uranium and plutonium obtained by means of a lithium-drifted germanium detector. The resolved gamma peaks have been assigned to various fission products by correlation of measured energy and half-life values with published data. By simultaneous study of the spectra of two irradiated mixtures of plutonium and uranium, the possibility of using the activities of Ru-103 and Ru-106 as a measure of the relative fission rate in U-235 and Pu-239 has been briefly examined

Burn-Up Determination by High Resolution Gamma Spectrometry: Spectra from Slightly-Irradiated Uranium and Plutonium between 400-830 keV

Energy Technology Data Exchange (ETDEWEB)

Forsyth, R S; Ronqvist, N

1966-08-15

Previously published studies of the short-cooled fission product spectra of irradiated uranium have been severely restricted by the poor energy resolution of the sodium iodide detectors used. In this report are presented fission product spectra of irradiated uranium and plutonium obtained by means of a lithium-drifted germanium detector. The resolved gamma peaks have been assigned to various fission products by correlation of measured energy and half-life values with published data. By simultaneous study of the spectra of two irradiated mixtures of plutonium and uranium, the possibility of using the activities of Ru-103 and Ru-106 as a measure of the relative fission rate in U-235 and Pu-239 has been briefly examined.

Prepared for the thirtieth annual conference on bioassay analytical and environmental chemistry. Reliable analysis of high resolution gamma spectra

International Nuclear Information System (INIS)

Spitz, H.B.; Buschbom, R.; Rieksts, G.A.; Palmer, H.E.

1985-01-01

A new method has been developed to reliably analyze pulse height-energy spectra obtained from measurements employing high resolution germanium detectors. The method employs a simple data transformation and smoothing function to calculate background and identify photopeaks and isotopic analysis. This technique is elegant in its simplicity because it avoids dependence upon complex spectrum deconvolution, stripping, or other least-square-fitting techniques which complicate the assessment of measurement reliability. A moving median was chosen for data smoothing because, unlike moving averages, medians are not dominated by extreme data points. Finally, peaks are identified whenever the difference between the background spectrum and the transformed spectrum exceeds a pre-determined number of standard deviations

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

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.

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

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

Jet mass spectra in Higgs+one jet at NNLL

International Nuclear Information System (INIS)

Jouttenus, Teppo T.; Stewart, Iain W.; Waalewijn, Wouter J.

2013-02-01

The invariant mass of a jet is a benchmark variable describing the structure of jets at the LHC. We calculate the jet mass spectrum for Higgs plus one jet at the LHC at next-to-next-to-leading logarithmic (NNLL) order using a factorization formula. At this order, the cross section becomes sensitive to perturbation theory at the soft m 2 jet /p jet T scale. Our calculation is exclusive and uses the 1-jettiness global event shape to implement a veto on additional jets. The dominant dependence on the jet veto is removed by normalizing the spectrum, leaving residual dependence from non-global logarithms depending on the ratio of the jet mass and jet veto variables. For our exclusive jet cross section these non-global logarithms are parametrically smaller than in the inclusive case, allowing us to obtain a complete NNLL result. Results for the dependence of the jet mass spectrum on the kinematics, jet algorithm, and jet size R are given. Using individual partonic channels we illustrate the difference between the jet mass spectra for quark and gluon jets. We also study the effect of hadronization and underlying event on the jet mass in Pythia. To highlight the similarity of inclusive and exclusive jet mass spectra, a comparison to LHC data is presented.

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.)

In silico fragmentation for computer assisted identification of metabolite mass spectra

Directory of Open Access Journals (Sweden)

Müller-Hannemann Matthias

2010-03-01

Full Text Available Abstract Background Mass spectrometry has become the analytical method of choice in metabolomics research. The identification of unknown compounds is the main bottleneck. In addition to the precursor mass, tandem MS spectra carry informative fragment peaks, but the coverage of spectral libraries of measured reference compounds are far from covering the complete chemical space. Compound libraries such as PubChem or KEGG describe a larger number of compounds, which can be used to compare their in silico fragmentation with spectra of unknown metabolites. Results We created the MetFrag suite to obtain a candidate list from compound libraries based on the precursor mass, subsequently ranked by the agreement between measured and in silico fragments. In the evaluation MetFrag was able to rank most of the correct compounds within the top 3 candidates returned by an exact mass query in KEGG. Compared to a previously published study, MetFrag obtained better results than the commercial MassFrontier software. Especially for large compound libraries, the candidates with a good score show a high structural similarity or just different stereochemistry, a subsequent clustering based on chemical distances reduces this redundancy. The in silico fragmentation requires less than a second to process a molecule, and MetFrag performs a search in KEGG or PubChem on average within 30 to 300 seconds, respectively, on an average desktop PC. Conclusions We presented a method that is able to identify small molecules from tandem MS measurements, even without spectral reference data or a large set of fragmentation rules. With today's massive general purpose compound libraries we obtain dozens of very similar candidates, which still allows a confident estimate of the correct compound class. Our tool MetFrag improves the identification of unknown substances from tandem MS spectra and delivers better results than comparable commercial software. MetFrag is available through a web

High resolution γ-ray spectroscopy: The first 85 years

International Nuclear Information System (INIS)

Deslattes, R.D.

2000-01-01

This opening review attempts to follow the main trends in crystal diffraction spectrometry of nuclear γ rays from its 1914 beginning in Rutherford's laboratory to the ultra-high resolution instrumentation realized in the current generation of spectrometers at the Institute Laue Langeven (ILL). The authors perspective is that of an instrumentalist hoping to convey a sense of intellectual debt to a number of predecessors, each of whom realized a certain elegance in making the tools that have enabled much good science, including that to which the remainder of this workshop is dedicated. This overview follows some of the main ideas along a trajectory toward higher resolution at higher energies, thereby enabling not only the disentangling of dense spectra, but also allowing detailed study of aspects of spectral profiles sensitive to excited state lifetimes and interatomic potentials. The parallel evolution toward increasing efficiency while preserving needed resolution is also an interesting story of artful compromise that should not be neglected. Finally, it is the robustness of the measurement chain connecting γ-ray wavelengths with optical wave-lengths associated with the Rydberg constant that only recently has allowed γ-ray data to contribute to determine of particle masses and fundamental constants, as will be described in more detail in other papers from this workshop

Programme in Basic-Applesoft language for microcomputer to analyse pulse spectra from a high-resolution gamma ray system

International Nuclear Information System (INIS)

Nascimento Filho, V.F. do; Marques, D.A.; Pessenda, L.C.R.; Barros Ferraz, E.S. de; Nadai, E.A. de; Sao Paulo Univ., Piracicaba

1988-01-01

A programme in BASIC-Applesoft language has been developed for low cost microcomputer to analyze spectra from a high-resolution gamma-ray system (high-purity germanium and 4096 channels analyzer). Data is received by the microcomputer directly from analyzer (4 min) or keyboard and shown on video (4 min) or printed (9,7 min). Graphics of parts of the spectrum can be either shown on video (a cursor is used to identify peaks) or printed. The peak search, centroid, energy, net photopeak area, standard deviation and relative standard deviation are included in the programme (5 min), besides filing of data in flexible disk (1,3 min). The programme was used on a 12 h real-time detection in Marinelli beaker of 1265 g sandy soil sample (Ref-Yellow Latosol, 0-3 cm layer). Thirty-one peaks from U-238 and Th-232 daughters were analyzed (rsd less than 20%), besides natural K-40 and artificial Cs-137, from fallout. (author) [pt

Resolution and Assignment of Differential Ion Mobility Spectra of Sarcosine and Isomers

Science.gov (United States)

Berthias, Francis; Maatoug, Belkis; Glish, Gary L.; Moussa, Fathi; Maitre, Philippe

2018-02-01

Due to their central role in biochemical processes, fast separation and identification of amino acids (AA) is of importance in many areas of the biomedical field including the diagnosis and monitoring of inborn errors of metabolism and biomarker discovery. Due to the large number of AA together with their isomers and isobars, common methods of AA analysis are tedious and time-consuming because they include a chromatographic separation step requiring pre- or post-column derivatization. Here, we propose a rapid method of separation and identification of sarcosine, a biomarker candidate of prostate cancer, from isomers using differential ion mobility spectrometry (DIMS) interfaced with a tandem mass spectrometer (MS/MS) instrument. Baseline separation of protonated sarcosine from α- and β-alanine isomers can be easily achieved. Identification of DIMS peak is performed using an isomer-specific activation mode where DIMS- and mass-selected ions are irradiated at selected wavenumbers allowing for the specific fragmentation via an infrared multiple photon dissociation (IRMPD) process. Two orthogonal methods to MS/MS are thus added, where the MS/MS(IRMPD) is nothing but an isomer-specific multiple reaction monitoring (MRM) method. The identification relies on the comparison of DIMS-MS/MS(IRMPD) chromatograms recorded at different wavenumbers. Based on the comparison of IR spectra of the three isomers, it is shown that specific depletion of the two protonated α- and β-alanine can be achieved, thus allowing for clear identification of the sarcosine peak. It is also demonstrated that DIMS-MS/MS(IRMPD) spectra in the carboxylic C=O stretching region allow for the resolution of overlapping DIMS peaks. [Figure not available: see fulltext.

A high resolution x-ray fluorescence spectrometer for near edge absorption studies

International Nuclear Information System (INIS)

Stojanoff, V.; Hamalainen, K.; Siddons, D.P.; Hastings, J.B.; Berman, L.E.; Cramer, S.; Smith, G.

1991-01-01

A high resolution fluorescence spectrometer using a Johann geometry in a back scattering arrangement was developed. The spectrometer, with a resolution of 0.3 eV at 6.5 keV, combined with an incident beam, with a resolution of 0.7 eV, form the basis of a high resolution instrument for measuring x-ray absorption spectra. The advantages of the instrument are illustrated with the near edge absorption spectrum of dysprosium nitrate. 10 refs., 4 figs

High Resolution Temperature Measurement of Liquid Stainless Steel Using Hyperspectral Imaging

Directory of Open Access Journals (Sweden)

Wim Devesse

2017-01-01

Full Text Available A contactless temperature measurement system is presented based on a hyperspectral line camera that captures the spectra in the visible and near infrared (VNIR region of a large set of closely spaced points. The measured spectra are used in a nonlinear least squares optimization routine to calculate a one-dimensional temperature profile with high spatial resolution. Measurements of a liquid melt pool of AISI 316L stainless steel show that the system is able to determine the absolute temperatures with an accuracy of 10%. The measurements are made with a spatial resolution of 12 µm/pixel, justifying its use in applications where high temperature measurements with high spatial detail are desired, such as in the laser material processing and additive manufacturing fields.

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.

Spectra of fluorinated rare earth β-diketonates with added ligands

International Nuclear Information System (INIS)

Khomenko, V.S.; Lozinskij, M.O.; Fialkov, Yu.A.; Rasshinina, T.A.; Krasovskaya, L.I.; AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

1984-01-01

Different-ligand rare earth complexes are synthesized. Fluorated β-diketones, triethylphosphine oxide and trifluoracetic acid are used as active ligands. Mass-spectra of low and high resolution are taken at the energy of ionizing electrons of 70 eV, as well as luminescence spectra of complexes. Fragmentation ways of complexes decomposition under electron shock are studied. A series of changing the bound strength of additional ligands with europium in mixed complexes is determined. It is shown that the introduction of additional ligands can purposefully change physical and chemical properties of complexes

Spectra of fluorinated rare earth. beta. -diketonates with added ligands

Energy Technology Data Exchange (ETDEWEB)

Khomenko, V.S.; Lozinskij, M.O.; Fialkov, Yu.A.; Rasshinina, T.A.; Krasovskaya, L.I. (AN Belorusskoj SSR, Minsk. Inst. Fiziki; AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

1984-01-01

Different-ligand rare earth complexes are synthesized. Fluorated ..beta..-diketones, triethylphosphine oxide and trifluoracetic acid are used as active ligands. Mass-spectra of low and high resolution are taken at the energy of ionizing electrons of 70 eV, as well as luminescence spectra of complexes. Fragmentation ways of complexes decomposition under electron shock are studied. A series of changing the bound strength of additional ligands with europium in mixed complexes is determined. It is shown that the introduction of additional ligands can purposefully change physical and chemical properties of complexes.

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.

High-resolution 3-μm spectra of Jupiter: Latitudinal spectral variations influenced by molecules, clouds, and haze

Science.gov (United States)

Kim, Sang J.; Geballe, T. R.; Kim, J. H.; Jung, A.; Seo, H. J.; Minh, Y. C.

2010-08-01

We present latitudinally-resolved high-resolution ( R = 37,000) pole-to-pole spectra of Jupiter in various narrow longitudinal ranges, in spectral intervals covering roughly half of the spectral range 2.86-3.53 μm. We have analyzed the data with the aid of synthetic spectra generated from a model jovian atmosphere that included lines of CH 4, CH 3D, NH 3, C 2H 2, C 2H 6, PH 3, and HCN, as well as clouds and haze. Numerous spectral features of many of these molecular species are present and are individually identified for the first time, as are many lines of H3+ and a few unidentified spectral features. In both polar regions the 2.86-3.10-μm continuum is more than 10 times weaker than in spectra at lower latitudes, implying that in this wavelength range the single-scattering albedos of polar haze particles are very low. In contrast, the 3.24-3.53 μm the weak polar and equatorial continua are of comparable intensity. We derive vertical distributions of NH 3, C 2H 2 and C 2H 6, and find that the mixing ratios of NH 3 and C 2H 6 show little variation between equatorial and polar regions. However, the mixing ratios of C 2H 2 in the northern and southern polar regions are ˜6 and ˜3 times, respectively, less than those in the equatorial regions. The derived mixing ratio curves of C 2H 2 and C 2H 6 extend up to the 10 -6 bar level, a significantly higher altitude than most previous results in the literature. Further ground-based observations covering other longitudes are needed to test if these mixing ratios are representative values for the equatorial and polar regions.

High-resolution Al L2,3-edge x-ray absorption near edge structure spectra of Al-containing crystals and glasses: coordination number and bonding information from edge components

International Nuclear Information System (INIS)

Weigel, C; Calas, G; Cormier, L; Galoisy, L; Henderson, G S

2008-01-01

High-resolution Al L 2,3 -edge x-ray absorption near edge structure (XANES) spectra have been measured in selected materials containing aluminium in 4-, 5- and 6-coordination. A shift of 1.5 eV is observed between the onset of [4] Al and [6] Al L 2,3 -edge XANES, in agreement with the magnitude of the shift observed at the Al K-edge. The differences in the position and shape of low-energy components of Al L 2,3 -edge XANES spectra provide a unique fingerprint of the geometry of the Al site and of the nature of Al-O chemical bond. The high resolution allows the calculation of electronic parameters such as the spin-orbit coupling and exchange energy using intermediate coupling theory. The electron-hole exchange energy decreases in tetrahedral as compared to octahedral symmetry, in relation with the increased screening of the core hole in the former. Al L 2,3 -edge XANES spectra confirm a major structural difference between glassy and crystalline NaAlSi 2 O 6 , with Al in 4- and 6-coordination, respectively, Al coordination remaining unchanged in NaAl 1-x Fe x Si 2 O 6 glasses, as Fe is substituted for Al

Jet mass spectra in Higgs+one jet at NNLL

Energy Technology Data Exchange (ETDEWEB)

Jouttenus, Teppo T.; Stewart, Iain W. [Massachusetts Institute of Technology, Cambridge, MA (United States). Center for Theoretical Physics; Tackmann, Frank J. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Waalewijn, Wouter J. [California Univ., San Diego, La Jolla, CA (United States). Dept. of Physics

2013-02-15

The invariant mass of a jet is a benchmark variable describing the structure of jets at the LHC. We calculate the jet mass spectrum for Higgs plus one jet at the LHC at next-to-next-to-leading logarithmic (NNLL) order using a factorization formula. At this order, the cross section becomes sensitive to perturbation theory at the soft m{sup 2}{sub jet}/p{sup jet}{sub T} scale. Our calculation is exclusive and uses the 1-jettiness global event shape to implement a veto on additional jets. The dominant dependence on the jet veto is removed by normalizing the spectrum, leaving residual dependence from non-global logarithms depending on the ratio of the jet mass and jet veto variables. For our exclusive jet cross section these non-global logarithms are parametrically smaller than in the inclusive case, allowing us to obtain a complete NNLL result. Results for the dependence of the jet mass spectrum on the kinematics, jet algorithm, and jet size R are given. Using individual partonic channels we illustrate the difference between the jet mass spectra for quark and gluon jets. We also study the effect of hadronization and underlying event on the jet mass in Pythia. To highlight the similarity of inclusive and exclusive jet mass spectra, a comparison to LHC data is presented.

Toward high-resolution NMR spectroscopy of microscopic liquid samples

Energy Technology Data Exchange (ETDEWEB)

Butler, Mark C.; Mehta, Hardeep S.; Chen, Ying; Reardon, Patrick N.; Renslow, Ryan S.; Khbeis, Michael; Irish, Duane; Mueller, Karl T.

2017-01-01

A longstanding limitation of high-resolution NMR spectroscopy is the requirement for samples to have macroscopic dimensions. Commercial probes, for example, are designed for volumes of at least 5 mL, in spite of decades of work directed toward the goal of miniaturization. Progress in miniaturizing inductive detectors has been limited by a perceived need to meet two technical requirements: (1) minimal separation between the sample and the detector, which is essential for sensitivity, and (2) near-perfect magnetic-field homogeneity at the sample, which is typically needed for spectral resolution. The first of these requirements is real, but the second can be relaxed, as we demonstrate here. By using pulse sequences that yield high-resolution spectra in an inhomogeneous field, we eliminate the need for near-perfect field homogeneity and the accompanying requirement for susceptibility matching of microfabricated detector components. With this requirement removed, typical imperfections in microfabricated components can be tolerated, and detector dimensions can be matched to those of the sample, even for samples of volume << 5 uL. Pulse sequences that are robust to field inhomogeneity thus enable small-volume detection with optimal sensitivity. We illustrate the potential of this approach to miniaturization by presenting spectra acquired with a flat-wire detector that can easily be scaled to subnanoliter volumes. In particular, we report high-resolution NMR spectroscopy of an alanine sample of volume 500 pL.

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.

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

Maximum entropy decomposition of quadrupole mass spectra

International Nuclear Information System (INIS)

Toussaint, U. von; Dose, V.; Golan, A.

2004-01-01

We present an information-theoretic method called generalized maximum entropy (GME) for decomposing mass spectra of gas mixtures from noisy measurements. In this GME approach to the noisy, underdetermined inverse problem, the joint entropies of concentration, cracking, and noise probabilities are maximized subject to the measured data. This provides a robust estimation for the unknown cracking patterns and the concentrations of the contributing molecules. The method is applied to mass spectroscopic data of hydrocarbons, and the estimates are compared with those received from a Bayesian approach. We show that the GME method is efficient and is computationally fast

Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

Directory of Open Access Journals (Sweden)

Y.-L. Sun

2011-02-01

Full Text Available Submicron aerosol particles (PM₁ were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY. Organic aerosol (OA and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM₁ mass. The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (D_va and an accumulation mode (~550 nm that is internally mixed with sulfate, nitrate, and ammonium. The diurnal cycles of both sulfate and OA peak between 01:00–02:00 p.m. EST due to photochemical production. The average (±σ oxygen-to-carbon (O/C, hydrogen-to-carbon (H/C, and nitrogen-to-carbon (N/C ratios of OA in NYC are 0.36 (±0.09, 1.49 (±0.08, and 0.012 (±0.005, respectively, corresponding to an average organic mass-to-carbon (OM/OC ratio of 1.62 (±0.11. Positive matrix factorization (PMF of the high resolution mass spectra identified two primary OA (POA sources, traffic and cooking, and three secondary OA (SOA components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 0.63, a less oxidized, semi-volatile SV-OOA (O/C = 0.38 and a unique nitrogen-enriched OA (NOA; N/C = 0.053 characterized with prominent C_xH_{2x + 2}N⁺ peaks likely from amino compounds. Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study. The OA composition is dominated by secondary species, especially during high PM events. SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass. The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA. Detailed

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.

Moessbauer spectroscopy with a high velocity resolution: advances in biomedical, pharmaceutical, cosmochemical and nano technological research

International Nuclear Information System (INIS)

Oshtrakha, M.I.; Semionkina, V.A.

2011-01-01

Full text: Velocity resolution is a term denoted the smallest velocity step (2V/2 n ) in velocity driving system of Moessbauer spectrometer and velocity step for the one point in Moessbauer spectrum. Velocity resolution coefficient 1/2 n in velocity driving system is constant and velocity resolution value depends on velocity range (2V) only while velocity resolution in Moessbauer spectrum may be the same or less. Moessbauer spectroscopy with a high velocity resolution is a new method to measure precision high quality spectra. It is well known that one of the main parts of Moessbauer spectrometer is velocity driving system. Usual spectrometers are used sinusoidal or triangular velocity reference signal and 256 or 512 channels to form velocity signal. Such velocity driving system provides spectra measurement with a low velocity resolution (2 n =256 or 512 channels) with possibility to decrease measurement time and reach needed signal/noise ratio by spectra folding on the direct and reverse motion. However, these driving systems do not provide a low systematic error for velocity signal while folding increases integral velocity error due to different velocity errors on the direct and reverse motions. These problems can be neglected if a high precision is not required for spectra measurement. Nevertheless, further development of Moessbauer spectroscopy may be related to increase in precision and quality of spectra measurement with less instrumental (systematic) velocity error and to increase in velocity resolution for both spectrometer and spectrum. A new velocity driving system was developed for Moessbauer spectrometer SM- 2201. This system uses saw-tooth shape velocity reference signal and 2 n =4096 channels to form velocity signal. On the basis of SM-2201 and liquid nitrogen cryostat with moving absorber and temperature variation in the range of 295-85 K a new automated precision Moessbauer spectrometric system with a high velocity resolution was created

Optimization of search algorithms for a mass spectra library

International Nuclear Information System (INIS)

Domokos, L.; Henneberg, D.; Weimann, B.

1983-01-01

The SISCOM mass spectra library search is mainly an interpretative system producing a ''hit list'' of similar spectra based on six comparison factors. This paper deals with extension of the system; the aim is exact identification (retrieval) of those reference spectra in the SISCOM hit list that correspond to the unknown compounds or components of the mixture. Thus, instead of a similarity measure, a decision (retrieval) function is needed to establish the identity of reference and unknown compounds by comparison of their spectra. To facilitate estimation of the weightings of the different variables in the retrieval function, pattern recognition algorithms were applied. Numerous statistical evaluations of three different library collections were made to check the quality of data bases and to derive appropriate variables for the retrieval function. (Auth.)

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...

High resolution γ spectra of 40-44 MeV γ photon activation products: Part 3 - a summary of γ rays, radionuclides and nuclear interferences observed

International Nuclear Information System (INIS)

Williams, D.R.; Hislop, J.S.

1980-09-01

A table of γ rays observed in the high resolution γ ray spectra of 40 to 44 MeV γ photon activation products is presented. This table is arranged in order of increasing γ ray energy and the parent isotopes, their half-lives and their inactive precursors are identified. Nuclear interferences caused by production of an active isotope from different parent elements have been identified and evaluated quantitatively. These are also tabulated. (author)

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.

Mass Spectra Analyses of Amides and Amide Dimers of Steviol, Isosteviol, and Steviolbioside

Directory of Open Access Journals (Sweden)

Lin-Wen Lee

2012-01-01

Full Text Available The mass spectra of a series of stevioside analogues including the amide and dimer compounds of steviol, isosteviol, and steviolbioside were examined. Positive ion mass spectral fragmentation of new steviol, isosteviol, and steviolbioside amides and the amide dimers are reported and discussed. The techniques included their synthesis procedures, fast-atom bombardment (FAB, and LC/MS/MS mass spectra. Intense [M+H]+ and [M+Na]+ ion peaks were observed on the FAB and ESI spectra. LC/MS/MS also yielded ES+ and ES− ion peaks that fairly agreed with the results of the FAB and ESI studies. Mass spectral analysis of compounds 4p-q, 5a-g, 6, and 7 revealed the different cleavage pathway patterns that can help in identifying the structures of steviolbioside and its amide derivatives.

IN-SYNC I: Homogeneous stellar parameters from high-resolution apogee spectra for thousands of pre-main sequence stars

International Nuclear Information System (INIS)

Cottaar, Michiel; Meyer, Michael R.; Covey, Kevin R.; Nidever, David L.; Stassun, Keivan G.; Foster, Jonathan B.; Tan, Jonathan C.; Da Rio, Nicola; Chojnowski, S. Drew; Skrutskie, Michael; Majewski, Steven R.; Wilson, John C.; Zasowski, Gail; Flaherty, Kevin M.; Frinchaboy, Peter M.

2014-01-01

Over two years, 8859 high-resolution H-band spectra of 3493 young (1-10 Myr) stars were gathered by the multi-object spectrograph of the APOGEE project as part of the IN-SYNC ancillary program of the SDSS-III survey. Here we present the forward modeling approach used to derive effective temperatures, surface gravities, radial velocities, rotational velocities, and H-band veiling from these near-infrared spectra. We discuss in detail the statistical and systematic uncertainties in these stellar parameters. In addition, we present accurate extinctions by measuring the E(J – H) of these young stars with respect to the single-star photometric locus in the Pleiades. Finally, we identify an intrinsic stellar radius spread of about 25% for late-type stars in IC 348 using three (nearly) independent measures of stellar radius, namely, the extinction-corrected J-band magnitude, the surface gravity, and the Rsin i from the rotational velocities and literature rotation periods. We exclude that this spread is caused by uncertainties in the stellar parameters by showing that the three estimators of stellar radius are correlated, so that brighter stars tend to have lower surface gravities and larger Rsin i than fainter stars at the same effective temperature. Tables providing the spectral and photometric parameters for the Pleiades and IC 348 have been provided online.

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

Yeast-expressed human membrane protein aquaporin-1 yields excellent resolution of solid-state MAS NMR spectra

International Nuclear Information System (INIS)

Emami, Sanaz; Fan Ying; Munro, Rachel; Ladizhansky, Vladimir; Brown, Leonid S.

2013-01-01

One of the biggest challenges in solid-state NMR studies of membrane proteins is to obtain a homogeneous natively folded sample giving high spectral resolution sufficient for structural studies. Eukaryotic membrane proteins are especially difficult and expensive targets in this respect. Methylotrophic yeast Pichia pastoris is a reliable producer of eukaryotic membrane proteins for crystallography and a promising economical source of isotopically labeled proteins for NMR. We show that eukaryotic membrane protein human aquaporin 1 can be doubly ( 13 C/ 15 N) isotopically labeled in this system and functionally reconstituted into phospholipids, giving excellent resolution of solid-state magic angle spinning NMR spectra.

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 μm region: role of hydrogenation and alkylation

Science.gov (United States)

Maltseva, Elena; Mackie, Cameron J.; Candian, Alessandra; Petrignani, Annemieke; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2018-03-01

Aim. We aim to elucidate the spectral changes in the 3 μm region that result from chemical changes in the molecular periphery of polycyclic aromatic hydrocarbons (PAHs) with extra hydrogens (H-PAHs) and methyl groups (Me-PAHs). Methods: Advanced laser spectroscopic techniques combined with mass spectrometry were applied on supersonically cooled 1,2,3,4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 1,2,3,6,7,8-hexahydropyrene, 9-methylanthracene, and 9,10-dimethylanthracene, allowing us to record mass-selective and conformationally selective absorption spectra of the aromatic, aliphatic, and alkyl CH-stretches in the 3.175 - 3.636 µm region with laser-limited resolution. We compared the experimental absorption spectra with standard harmonic calculations and with second-order vibrational perturbation theory anharmonic calculations that use the SPECTRO program for treating resonances. Results: We show that anharmonicity plays an important if not dominant role, affecting not only aromatic, but also aliphatic and alkyl CH-stretch vibrations. The experimental high-resolution data lead to the conclusion that the variation in Me- and H-PAHs composition might well account for the observed variations in the 3 μm emission spectra of carbon-rich and star-forming regions. Our laboratory studies also suggest that heavily hydrogenated PAHs form a significant fraction of the carriers of IR emission in regions in which an anomalously strong 3 μm plateau is observed.

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

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.

THE SEGUE STELLAR PARAMETER PIPELINE. V. ESTIMATION OF ALPHA-ELEMENT ABUNDANCE RATIOS FROM LOW-RESOLUTION SDSS/SEGUE STELLAR SPECTRA

International Nuclear Information System (INIS)

Lee, Young Sun; Beers, Timothy C.; Prieto, Carlos Allende; Lai, David K.; Rockosi, Constance M.; Morrison, Heather L.; Johnson, Jennifer A.; An, Deokkeun; Sivarani, Thirupathi; Yanny, Brian

2011-01-01

We present a method for the determination of [α/Fe] ratios from low-resolution (R = 2000) SDSS/SEGUE stellar spectra. By means of a star-by-star comparison with degraded spectra from the ELODIE spectral library and with a set of moderately high-resolution (R = 15, 000) and medium-resolution (R = 6000) spectra of SDSS/SEGUE stars, we demonstrate that we are able to measure [α/Fe] from SDSS/SEGUE spectra (with S/N>20/1) to a precision of better than 0.1 dex, for stars with atmospheric parameters in the range T eff = [4500, 7000] K, log g = [1.5, 5.0], and [Fe/H] = [-1.4, +0.3], over the range [α/Fe] = [-0.1, +0.6]. For stars with [Fe/H] 25/1). Over the full temperature range considered, the lowest metallicity star for which a confident estimate of [α/Fe] can be obtained from our approach is [Fe/H] ∼-2.5; preliminary tests indicate that a metallicity limit as low as [Fe/H] ∼-3.0 may apply to cooler stars. As a further validation of this approach, weighted averages of [α/Fe] obtained for SEGUE spectra of likely member stars of Galactic globular clusters (M15, M13, and M71) and open clusters (NGC 2420, M67, and NGC 6791) exhibit good agreement with the values of [α/Fe] from previous studies. The results of the comparison with NGC 6791 imply that the metallicity range for the method may extend to ∼+0.5.

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.

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.

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.

High Resolution Optical Spectroscopy of the Classical Nova V5668 Sgr Showing the Presence of Lithium

Science.gov (United States)

Wagner, R. Mark; Woodward, Charles E.; Starrfield, Sumner; Ilyin, Ilya; Strassmeier, Klaus

2018-01-01

The classical nova (CN) V5668 Sgr was discovered on 2015 March 15.634 and initial optical spectra implied it was an Fe II-class CN. We obtained high resolution optical spectroscopy on 30 nights between 2015 April 3 and 2016 June 5 with the 2 x 8.4 m Large Binocular Telescope (LBT) and the 1.8 m Vatican Advanced Technology Telescope (VATT) using the Potsdam Echelle Polarimetric Spectroscopic Instrument (PEPSI). The spectra cover all or part of the 3830-9065 Å spectral region at a spectral resolution of up to 270,000 (1 km/s); the highest resolution currently available on any 8-10 m class telescope. The early spectra are dominated by emission lines of the Balmer and Paschen series of hydrogen, Fe II, Ca II, and Na I with P Cyg-type line profiles as well as emission lines of [O I]. Numerous interstellar lines and bands are readily apparent at high spectral resolution. The permitted line profiles show complex and dramatic variations in the multi-component P Cyg-type line profiles with time. We detect a weak blue-shifted absorption line at a velocity consistent with Li I 6708 Å when compared with the line profiles of Hβ, Fe II 5169 Å, and Na I D. This line is present in spectra obtained on 7 of 8 consecutive nights up to day 21 of the outburst; but absent on day 42 when it is evident that the ionization of the ejecta has significantly increased. The equivalent width of the line converted to a column density, and the resulting mass fraction, imply a significant enrichment of 7Li in the ejecta. 7Li is produced by the decay of unstable 7Be created during the thermonuclear runaway. The discovery of the resonance lines of 7Be II in the optical spectra of the recent CNe V339 Del, V2944 Oph, and V5668 Sgr by Tajitsu et al. (2016) and its subsequent decay to 7Li (half life of 53 days) suggests a significant enrichment of 7Li in the Galaxy from CNe is possible. Our observations of the Li I 6708 Å line in the early optical spectra of V5668 Sgr mark the second direct

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

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.

High-resolution spectroscopic probes of collisions and half-collisions

Energy Technology Data Exchange (ETDEWEB)

Hall, G.E. [Brookhaven National Laboratory, Upton, NY (United States)

1993-12-01

Research in this program explores the dynamics of gas phase collisions and photodissociation by high-resolution laser spectroscopy. Simultaneous state and velocity detection frequently permits a determination of scalar or vector correlations among products. The correlated product distributions are always more informative, and often easier to interpret than the uncorrelated product state distributions. The authors have recently built an apparatus to record transient absorption spectra with 50 nS time resolution and 20 MHz frequency resolution using a single frequency Ti:sapphire laser. The photodissociation of NCCN and C{sub 2}H{sub 5}SCN at 193 nm is discussed.

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.

Heavy meson mass spectra by general relativistic methods

International Nuclear Information System (INIS)

Italiano, A.; Lattuada, M.; Maccarrone, G.D.; Recami, E.; Riggi, F.; Vinciguerra, D.

1984-01-01

By applying the classical methods of general relativity to elementary particles one can get, in a natural way, the observed confinement of their constituents, avoiding any recourse to phenome-nological models such as bag model and allowing the deduction of the heavy meson (i.e. charmonium (J/psi) and bottomium (UPSILON)) mass spectra

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

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

Concept of dual-resolution light field imaging using an organic photoelectric conversion film for high-resolution light field photography.

Science.gov (United States)

Sugimura, Daisuke; Kobayashi, Suguru; Hamamoto, Takayuki

2017-11-01

Light field imaging is an emerging technique that is employed to realize various applications such as multi-viewpoint imaging, focal-point changing, and depth estimation. In this paper, we propose a concept of a dual-resolution light field imaging system to synthesize super-resolved multi-viewpoint images. The key novelty of this study is the use of an organic photoelectric conversion film (OPCF), which is a device that converts spectra information of incoming light within a certain wavelength range into an electrical signal (pixel value), for light field imaging. In our imaging system, we place the OPCF having the green spectral sensitivity onto the micro-lens array of the conventional light field camera. The OPCF allows us to acquire the green spectra information only at the center viewpoint with the full resolution of the image sensor. In contrast, the optical system of the light field camera in our imaging system captures the other spectra information (red and blue) at multiple viewpoints (sub-aperture images) but with low resolution. Thus, our dual-resolution light field imaging system enables us to simultaneously capture information about the target scene at a high spatial resolution as well as the direction information of the incoming light. By exploiting these advantages of our imaging system, our proposed method enables the synthesis of full-resolution multi-viewpoint images. We perform experiments using synthetic images, and the results demonstrate that our method outperforms other previous methods.

Prospects for Measuring Abundances of >20 Elements with Low-resolution Stellar Spectra

Energy Technology Data Exchange (ETDEWEB)

Ting Yuan-Sen; Conroy, Charlie; Cargile, Phillip [Harvard–Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Rix, Hans-Walter [Max Planck Institute for Astronomy, Königstuhl 17, D-69117 Heidelberg (Germany)

2017-07-01

Understanding the evolution of the Milky Way calls for the precise abundance determination of many elements in many stars. A common perception is that deriving more than a few elemental abundances ([Fe/H], [ α /Fe], perhaps [C/H], [N/H]) requires medium-to-high spectral resolution, R ≳ 10,000, mostly to overcome the effects of line blending. In a recent work, we presented an efficient and practical way to model the full stellar spectrum, even when fitting a large number of stellar labels simultaneously. In this paper, we quantify to what precision the abundances of many different elements can be recovered, as a function of spectroscopic resolution and wavelength range. In the limit of perfect spectral models and spectral normalization, we show that the precision of elemental abundances is nearly independent of resolution, for a fixed exposure time and number of detector pixels; low-resolution spectra simply afford much higher S/N per pixel and generally larger wavelength range in a single setting. We also show that estimates of most stellar labels are not strongly correlated with one another once R ≳ 1000. Modest errors in the line-spread function, as well as small radial velocity errors, do not affect these conclusions, and data-driven models indicate that spectral (continuum) normalization can be achieved well enough in practice. These results, to be confirmed with an analysis of observed low-resolution data, open up new possibilities for the design of large spectroscopic stellar surveys and for the reanalysis of archival low-resolution data sets.

[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.

Montecarlo simulation for a new high resolution elemental analysis methodology

Energy Technology Data Exchange (ETDEWEB)

Figueroa S, Rodolfo; Brusa, Daniel; Riveros, Alberto [Universidad de La Frontera, Temuco (Chile). Facultad de Ingenieria y Administracion

1996-12-31

Full text. Spectra generated by binary, ternary and multielement matrixes when irradiated by a variable energy photon beam are simulated by means of a Monte Carlo code. Significative jumps in the counting rate are shown when the photon energy is just over the edge associated to each element, because of the emission of characteristic X rays. For a given associated energy, the net height of these jumps depends mainly on the concentration and of the sample absorption coefficient. The spectra were obtained by a monochromatic energy scan considering all the emitted radiation by the sample in a 2{pi} solid angle, associating a single multichannel spectrometer channel to each incident energy (Multichannel Scaling (MCS) mode). The simulated spectra were made with Monte Carlo simulation software adaptation of the package called PENELOPE (Penetration and Energy Loss of Positrons and Electrons in matter). The results show that it is possible to implement a new high resolution spectroscopy methodology, where a synchrotron would be an ideal source, due to the high intensity and ability to control the energy of the incident beam. The high energy resolution would be determined by the monochromating system and not by the detection system and not by the detection system, which would basicalbe a photon counter. (author)

Montecarlo simulation for a new high resolution elemental analysis methodology

International Nuclear Information System (INIS)

Figueroa S, Rodolfo; Brusa, Daniel; Riveros, Alberto

1996-01-01

Full text. Spectra generated by binary, ternary and multielement matrixes when irradiated by a variable energy photon beam are simulated by means of a Monte Carlo code. Significative jumps in the counting rate are shown when the photon energy is just over the edge associated to each element, because of the emission of characteristic X rays. For a given associated energy, the net height of these jumps depends mainly on the concentration and of the sample absorption coefficient. The spectra were obtained by a monochromatic energy scan considering all the emitted radiation by the sample in a 2π solid angle, associating a single multichannel spectrometer channel to each incident energy (Multichannel Scaling (MCS) mode). The simulated spectra were made with Monte Carlo simulation software adaptation of the package called PENELOPE (Penetration and Energy Loss of Positrons and Electrons in matter). The results show that it is possible to implement a new high resolution spectroscopy methodology, where a synchrotron would be an ideal source, due to the high intensity and ability to control the energy of the incident beam. The high energy resolution would be determined by the monochromating system and not by the detection system and not by the detection system, which would basicalbe a photon counter. (author)

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

Characterization of polyesters by matrix-assisted laser desorption/ionization and Fourier transform mass spectrometry.

Science.gov (United States)

Mize, Todd H; Simonsick, William J; Amster, I Jonathan

2003-01-01

Two homopolyesters, poly(neopentyl glycol-alt-isophthalic acid) and poly(hexanediol-alt-azelaic acid), and two copolyesters, poly(dipropoxylated bisphenol-A-alt-(isophthalic acid-co-adipic acid)) and poly(neopentyl glycol-alt-(adipic acid-co-isophthalic acid)) were analyzed by internal source matrix assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS). The high resolution and high mass accuracy provided by FTMS greatly facilitate the characterization of the polyester and copolyester samples. Isobaric resolution allows the ion abundances of overlapping isotopic envelopes to be assessed. Repeat units were confirmed and end functionality assigned. Single shot mass spectra of the entire polymeric distribution demonstrate that the dynamic range of this internal MALDI source instrument and the analyzer cell exceeds performance of those previously reported for higher field instruments. Corrections of space charge mass shift effects are demonstrated for the analytes using an external calibrant and (subsequent to confirmation of structure) via internal calibration which removes ambiguity due to space charge differences in calibrant and analyte spectra. Capillary gel permeation chromatography was used to prepare low polydispersity samples from a high polydispersity polyester, improving the measurement of molecular weight distribution two-fold while retaining the benefits of high resolution mass spectrometry for elucidation of oligomer identity.

MS2Analyzer: A Software for Small Molecule Substructure Annotations from Accurate Tandem Mass Spectra

Science.gov (United States)

2015-01-01

Systematic analysis and interpretation of the large number of tandem mass spectra (MS/MS) obtained in metabolomics experiments is a bottleneck in discovery-driven research. MS/MS mass spectral libraries are small compared to all known small molecule structures and are often not freely available. MS2Analyzer was therefore developed to enable user-defined searches of thousands of spectra for mass spectral features such as neutral losses, m/z differences, and product and precursor ions from MS/MS spectra in MSP/MGF files. The software is freely available at http://fiehnlab.ucdavis.edu/projects/MS2Analyzer/. As the reference query set, 147 literature-reported neutral losses and their corresponding substructures were collected. This set was tested for accuracy of linking neutral loss analysis to substructure annotations using 19 329 accurate mass tandem mass spectra of structurally known compounds from the NIST11 MS/MS library. Validation studies showed that 92.1 ± 6.4% of 13 typical neutral losses such as acetylations, cysteine conjugates, or glycosylations are correct annotating the associated substructures, while the absence of mass spectra features does not necessarily imply the absence of such substructures. Use of this tool has been successfully demonstrated for complex lipids in microalgae. PMID:25263576

High-resolution transmission measurements of CO2 at high temperatures for industrial applications

DEFF Research Database (Denmark)

Evseev, Vadim; Fateev, Alexander; Clausen, Sønnik

2012-01-01

. The spectra have been recorded in a high-temperature flow gas cell and using a Fourier transform infrared (FTIR) spectrometer at a nominal resolution of 0.125 cm-1. The volume fractions of CO2 in the measurements were 1,10 and 100%. The measurements have been validated by comparison with medium...

Application of Spectra Accuracy for Analysis of Organic Explosive: 2,4,6-trinitrotoluene by AccuTOF-DART

Directory of Open Access Journals (Sweden)

Zhanfang Liu

2016-01-01

Full Text Available This paper, through mass spectrometric (MS analysis for nitro compound explosives on a direct analysis in a real-time time-of-flight MS, indicates that even on a high-resolution MS with accurate mass measurement capabilities, there is no guarantee to obtain the unique molecular formula of a compound. By calculating spectra accuracy, highly accurate isotope pattern matching can be conducted to significantly improve performance of compound confirmation or identification.

NEUTRINO-DRIVEN CONVECTION IN CORE-COLLAPSE SUPERNOVAE: HIGH-RESOLUTION SIMULATIONS

Energy Technology Data Exchange (ETDEWEB)

Radice, David; Ott, Christian D. [TAPIR, Walter Burke Institute for Theoretical Physics, Mailcode 350-17, California Institute of Technology, Pasadena, CA 91125 (United States); Abdikamalov, Ernazar [Department of Physics, School of Science and Technology, Nazarbayev University, Astana 010000 (Kazakhstan); Couch, Sean M. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Haas, Roland [Max-Planck-Institut für Gravitationsphysik, Albert-Einstein-Institut, D-14476 Golm (Germany); Schnetter, Erik, E-mail: dradice@caltech.edu [Perimeter Institute for Theoretical Physics, Waterloo, ON (Canada)

2016-03-20

We present results from high-resolution semiglobal simulations of neutrino-driven convection in core-collapse supernovae. We employ an idealized setup with parameterized neutrino heating/cooling and nuclear dissociation at the shock front. We study the internal dynamics of neutrino-driven convection and its role in redistributing energy and momentum through the gain region. We find that even if buoyant plumes are able to locally transfer heat up to the shock, convection is not able to create a net positive energy flux and overcome the downward transport of energy from the accretion flow. Turbulent convection does, however, provide a significant effective pressure support to the accretion flow as it favors the accumulation of energy, mass, and momentum in the gain region. We derive an approximate equation that is able to explain and predict the shock evolution in terms of integrals of quantities such as the turbulent pressure in the gain region or the effects of nonradial motion of the fluid. We use this relation as a way to quantify the role of turbulence in the dynamics of the accretion shock. Finally, we investigate the effects of grid resolution, which we change by a factor of 20 between the lowest and highest resolution. Our results show that the shallow slopes of the turbulent kinetic energy spectra reported in previous studies are a numerical artifact. Kolmogorov scaling is progressively recovered as the resolution is increased.

NEUTRINO-DRIVEN CONVECTION IN CORE-COLLAPSE SUPERNOVAE: HIGH-RESOLUTION SIMULATIONS

International Nuclear Information System (INIS)

Radice, David; Ott, Christian D.; Abdikamalov, Ernazar; Couch, Sean M.; Haas, Roland; Schnetter, Erik

2016-01-01

We present results from high-resolution semiglobal simulations of neutrino-driven convection in core-collapse supernovae. We employ an idealized setup with parameterized neutrino heating/cooling and nuclear dissociation at the shock front. We study the internal dynamics of neutrino-driven convection and its role in redistributing energy and momentum through the gain region. We find that even if buoyant plumes are able to locally transfer heat up to the shock, convection is not able to create a net positive energy flux and overcome the downward transport of energy from the accretion flow. Turbulent convection does, however, provide a significant effective pressure support to the accretion flow as it favors the accumulation of energy, mass, and momentum in the gain region. We derive an approximate equation that is able to explain and predict the shock evolution in terms of integrals of quantities such as the turbulent pressure in the gain region or the effects of nonradial motion of the fluid. We use this relation as a way to quantify the role of turbulence in the dynamics of the accretion shock. Finally, we investigate the effects of grid resolution, which we change by a factor of 20 between the lowest and highest resolution. Our results show that the shallow slopes of the turbulent kinetic energy spectra reported in previous studies are a numerical artifact. Kolmogorov scaling is progressively recovered as the resolution is increased

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)

High resolution measurements of Cyg X-1 from rockets

International Nuclear Information System (INIS)

Rothschild, R.E.; Boldt, E.A.; Holt, S.S.; Serlemitsos, P.J.

1976-01-01

Cyg X-1 was observed on two occasions (Oct. 4, 1973 and Oct. 3, 1974) by the Goddard x-ray rocket payload. This payload consisted of two gas proportional counters (xenon--methane with 710 cm 2 and argon--methane with 610 cm 2 ) using the same 128 channel pulse height analyzer and having 320 μs temporal resolution on the 1973 flight and 160 μs resolution on the 1974 flight. During both flights bursts of 1 ms duration were observed with very high statistical certainty. To date all 13 of these bursts have been analyzed for spectral and temporal character, and the results of this analysis are presented. The spectra of overall x-ray emission from both flights are also presented. In a source known for its variability it is remarkable that the spectra taken one year apart are virtually identical

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.

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.

High Time Resolution Astrophysics

CERN Document Server

Phelan, Don; Shearer, Andrew

2008-01-01

High Time Resolution Astrophysics (HTRA) is an important new window to the universe and a vital tool in understanding a range of phenomena from diverse objects and radiative processes. This importance is demonstrated in this volume with the description of a number of topics in astrophysics, including quantum optics, cataclysmic variables, pulsars, X-ray binaries and stellar pulsations to name a few. Underlining this science foundation, technological developments in both instrumentation and detectors are described. These instruments and detectors combined cover a wide range of timescales and can measure fluxes, spectra and polarisation. These advances make it possible for HTRA to make a big contribution to our understanding of the Universe in the next decade.

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

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.

Using data-independent, high-resolution mass spectrometry in protein biomarker research: perspectives and clinical applications.

Science.gov (United States)

Sajic, Tatjana; Liu, Yansheng; Aebersold, Ruedi

2015-04-01

In medicine, there is an urgent need for protein biomarkers in a range of applications that includes diagnostics, disease stratification, and therapeutic decisions. One of the main technologies to address this need is MS, used for protein biomarker discovery and, increasingly, also for protein biomarker validation. Currently, data-dependent analysis (also referred to as shotgun proteomics) and targeted MS, exemplified by SRM, are the most frequently used mass spectrometric methods. Recently developed data-independent acquisition techniques combine the strength of shotgun and targeted proteomics, while avoiding some of the limitations of the respective methods. They provide high-throughput, accurate quantification, and reproducible measurements within a single experimental setup. Here, we describe and review data-independent acquisition strategies and their recent use in clinically oriented studies. In addition, we also provide a detailed guide for the implementation of SWATH-MS (where SWATH is sequential window acquisition of all theoretical mass spectra)-one of the data-independent strategies that have gained wide application of late. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Characterisation of nanoparticles by means of high-resolution SEM/EDS in transmission mode

International Nuclear Information System (INIS)

Hodoroaba, V-D; Rades, S; Mielke, J; Ortel, E; Salge, T; Schmidt, R

2016-01-01

Advances in scanning electron microscopy (SEM) enable the high-resolution imaging of single nanoparticles (NPs) with sizes well below 10 nm. The SEM analysis in transmission mode (T-SEM) of NPs on thin film supports has many benefits when compared to the analysis of NPs on bulk substrates. The enhanced material (mass - thickness) contrast of the T-SEM imaging mode is well suited for in-depth and, particularly valuable, to very accurate, traceable, lateral dimensional measurements of NPs. Compared to samples prepared on bulk substrates, T-SEM with energy dispersive X-ray spectroscopy (EDS) achieves a drastically improved spatial resolution of the emitted X-rays. The poor signal-to-noise ratio of the X-ray spectra emitted by a single nanoparticle (NP) can be improved by the use of high-sensitivity (high collection solid angle) silicon drift (SDD), energy-dispersive X-ray spectrometers (EDS). The EDS spectral imaging of a single NP with a spatial resolution below 10 nm has become possible. This is demonstrated by means of various examples of nanostructures. Advanced data processing of T-SEM/EDS results sets the stage for the automated classification of NPs by feature analysis. This method combines the detection of morphological structures of interest by image processing of T-SEM micrographs with the chemical classification by EDS. (paper)

New Measurements of s-Process Enrichments in Planetary Nebulae from High-Resolution Near-Infrared Spectra

Science.gov (United States)

Dinerstein, Harriet L.; Karakas, Amanda; Sterling, Nicholas C.; Kaplan, Kyle

2017-06-01

We present preliminary results from a high-spectral resolution survey of near-infrared emission lines of neutron-capture elements in planetary nebulae using the Immersion Grating Infrared Spectrometer, IGRINS (Park et al. 2014, SPIE. 9147, 1), which spans the H- and K-bands at spectral resolving power R ≈ 45,000. Both the [Kr III] and [Se IV] lines identified by Dinerstein (2001, ApJL, 550, L223) are seen in nearly all of an initial sample of ≈ 15 nebulae, with improved accuracy over earlier studies based on lower-resolution data (Sterling & Dinerstein 2008, ApJS, 174, 158; Sterling, Porter, & Dinerstein 2015, ApJS, 218, 25). Several new detections of the [Rb IV], [Cd IV], and [Ge VI] lines identified by Sterling et al. (2016, ApJL, 819, 9), as well as a [Br V] line, were made. About half the objects in this sample descend from stars with [Fe/H] = -0.7 ± 0.2 dex, while the remainder have -0.3 ≤ [Fe/H] ≤ 0. We compare the measured enhancements of Se, Kr, Rb, and Cd with predictions of their production by slow-neutron captures (the s-process) during the AGB from theoretical evolutionary models for the corresponding metallicities and various initial masses. New nucleosynthesis calculations were carried out for [Fe/H] = -0.7 for initial masses between 1.1 and 3 M⊙ using the Monash stellar evolution and post-processing codes described in Karakas & Lugaro (2016, ApJ, 825, 26), which provides the nucleosynthesis predictions for the metal-rich end of our sample. The Monash models predict enrichments larger by factors of two or more than those from FRUITY (Cristallo et al. 2015, ApJS, 219, 40) and NuGRID (Pignatari et al. 2016, ApJS, 225, 24) models for the same masses and metallicities. We find that the Monash models are in substantially better agreement than the others with the abundances derived from the IGRINS observations.This work is based on data taken at the McDonald Observatory of the University of Texas at Austin. IGRINS was developed with support from

Synthesis and Electrospray Ionization Mass Spectra of N-(1,3,2-Dioxaphosphorinan-2-ylmethyl)thiophosphoramidates

Institute of Scientific and Technical Information of China (English)

MIAO,Zhi-Wei; FU,Cui-Rong; WANG,Bin; CUI,Zhan-Wei; ZHANG,Jian-Feng; CHEN,Ru-Yu

2007-01-01

N-(1,3,2-Dioxaphosphorinan-2-ylmethyl) thiophosphoramidates were synthesized and determined by NMR spectra and positive ion electrospray ionization mass spectrometry (ESI-MS) in conjunction with tandem mass spectrometry (MS/MS). The fragmentation pathways were investigated. The results show that these characteristic ions in ESI mass spectra are useful in the structural determination of N-(1,3,2-dioxaphosphorinan-2-ylmethyl)thiophosphoramidates.

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

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

High-resolution spectroscopy of gases for industrial applications

OpenAIRE

Fateev, Alexander; Clausen, Sønnik

2012-01-01

High-resolution spectroscopy of gases is a powerful technique which has various fundamental and practical applications: in situ simultaneous measurements of gas temperature and gas composition, radiative transfer modeling, validation of existing and developing of new databases and etc. Existing databases (e.g. HITRAN, HITEMP or CDSD) can normally be used for absorption spectra calculations at limited temperature/pressure ranges. Therefore experimental measurements of absorption/transmission s...

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.

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

Multivariate curve resolution using a combination of mid-infrared and near-infrared spectra for the analysis of isothermal epoxy curing reaction

Science.gov (United States)

Yamasaki, Hideki; Morita, Shigeaki

2018-05-01

Multivariate curve resolution (MCR) was applied to a hetero-spectrally combined dataset consisting of mid-infrared (MIR) and near-infrared (NIR) spectra collected during the isothermal curing reaction of an epoxy resin. An epoxy monomer, bisphenol A diglycidyl ether (BADGE), and a hardening agent, 4,4‧-diaminodiphenyl methane (DDM), were used for the reaction. The fundamental modes of the Nsbnd H and Osbnd H stretches were highly overlapped in the MIR region, while their first overtones could be independently identified in the NIR region. The concentration profiles obtained by MCR using the hetero-spectral combination showed good agreement with the results of calculations based on the Beer-Lambert law and the mass balance. The band assignments and absorption sites estimated by the analysis also showed good agreement with the results using two-dimensional (2D) hetero-correlation spectroscopy.

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.

Design and construction of a high-stability, low-noise power supply for use with high-resolution electron energy loss spectrometers

International Nuclear Information System (INIS)

Katz, J.E.; Davies, P.W.; Crowell, J.E.; Somorjai, G.A.

1982-01-01

The design and construction of a high-stability, low-noise power supply which provides potentials for the lens and analyzer elements of a 127 0 Ehrhardt-type high-resolution electron energy loss spectrometer (HREELS) is described. The supply incorporates a filament emission-control circuit and facilities for measuring electron beam current at each spectrometer element, thus facilitating optimal tuning of the spectrometer. Spectra obtained using this supply are shown to have a four-fold improvement in signal-to-noise ratio and a higher resolution of the vibrational loss features when compared with spectra taken using a previously existing supply based on passive potential divider networks

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.

MEASURING DETAILED CHEMICAL ABUNDANCES FROM CO-ADDED MEDIUM-RESOLUTION SPECTRA. I. TESTS USING MILKY WAY DWARF SPHEROIDAL GALAXIES AND GLOBULAR CLUSTERS

International Nuclear Information System (INIS)

Yang Lei; Peng, Eric W.; Kirby, Evan N.; Guhathakurta, Puragra; Cheng, Lucy

2013-01-01

The ability to measure metallicities and α-element abundances in individual red giant branch (RGB) stars using medium-resolution spectra (R ≈ 6000) is a valuable tool for deciphering the nature of Milky Way dwarf satellites and the history of the Galactic halo. Extending such studies to more distant systems like Andromeda is beyond the ability of the current generation of telescopes, but by co-adding the spectra of similar stars, we can attain the necessary signal-to-noise ratio (S/N) to make detailed abundance measurements. In this paper, we present a method to determine metallicities and α-element abundances using the co-addition of medium-resolution spectra. We test the method of spectral co-addition using high-S/N spectra of more than 1300 RGB stars from Milky Way globular clusters and dwarf spheroidal galaxies obtained with the Keck II telescope/DEIMOS spectrograph. We group similar stars using photometric criteria and compare the weighted ensemble average abundances ([Fe/H], [Mg/Fe], [Si/Fe], [Ca/Fe], and [Ti/Fe]) of individual stars in each group with the measurements made on the corresponding co-added spectrum. We find a high level of agreement between the two methods, which permits us to apply this co-added spectra technique to more distant RGB stars, like stars in the M31 satellite galaxies. This paper outlines our spectral co-addition and abundance measurement methodology and describes the potential biases in making these measurements.

Mass spectra of alicylic compounds Pt. 8

International Nuclear Information System (INIS)

Remane, H.; Haufe, G.

1980-01-01

Mass spectrometric fragmentation of C 5 -C 8 as well as C 12 ring systems of tBHC and tBMC is discussed and compared to the fragmentation of Br-, hydroxy- and methoxy cycloalkanes of similar ring sizes. The dominant processes are the splitting of the functional groups yielding M-H 2 O 1+ , M-HOCH 3 1+ and M-Br 1+ fragments, and the disintegration of the rings producing C 3 H 4 X 1+ fragments (X=Br, OH, OCH 3 ). Intensities of the more important fragments correspond to the size of the ring. The isomers can be distinguished by their mass spectra due to the inequality of the intensities of the trans- and cis-forms of BHC and BMC. Functional groups influence mass spectrometric fragmentation as it is indicated by the correlation of the fragments of the bis-functional tBHC and tBMC and the fragments of monofractional compounds. (Sz.J.)

Comparison of Australasian tertiary coals based on resolution- enhanced solid-state /sup 13/C NMR spectra

Energy Technology Data Exchange (ETDEWEB)

Newman, R H; Davenport, S J

1986-04-01

/sup 13/C solid-state nuclear magnetic resonance spectroscopy was used to characterize 32 low-rank coals from New Zealand and Australia. A combination of high magnetic field (4.7 T) and resolution enhancement was used to extract spectral details beyond those seen in published spectra of coals of similar rank. Signal heights were used to characterize organic functional distributions. The spectra showed close similarities between Australian brown coals and low-rank New Zealand subbituminous coals, particularly those mined in the North Island. The spectra of New Zealand lignites all showed stronger signals from cellulose, methoxyl groups and phenols. Almost all of the New Zealand coals showed a relatively strong signal from polymethylene chains, compared with the Australian brown coals. This led to a prediction of higher alkene yields from pyrolysis of the New Zealand coals. Variations in phenolic substitution patterns were attributed to variations in the relative proportions of tannins and lignins in the depositional environments.

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

Searches for Supersymmetry with compressed mass spectra using monojet events with the CMS detector at the LHC

CERN Document Server

Lucas, Robyn Elizabeth; Worm, Steve

2015-01-01

A novel search for supersymmetric particles in events with one high transverse momentum jet and large missing transverse energy is performed using an integrated luminosity of 19.7 fb$^{-1}$ of pp collision data collected using the CMS detector at the Large Hadron Collider. By using events with an energetic radiated jet, sensitivity to supersymmetric models with compressed mass spectra is gained where the decay products have very low energy. Standard Model background estimates are evaluated with the use of data control samples. No excess over Standard Model expectations is observed, and limits are placed on third generation squark production at the 95% confidence level using supersymmetric simplified models. The development of a Level 1 trigger algorithm to reconstruct jets in the Phase 1 Upgrade of the CMS detector is presented. Utilising the full granularity of the CMS calorimeter and time-multiplexed-trigger technology, a new algorithm with increased flexibility and resolution is presented. It is possible t...

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.

Photoionization of Ar2 at high resolution

International Nuclear Information System (INIS)

Dehmer, P.M.

1982-01-01

The relative photoionization cross section of Ar 2 was determined at a resolution of 0.07 A in the wavelength region from 800 to 850 A using a new photoionization mass spectrometer that combines a high intensity helium continuum lamp with a free supersonic molecular beam source. In the region studied, the photoionization cross section is dominated by autoionization of molecular Rydberg states, and the structure is diffuse owing to the combined effects of autoionization and predissociation. The molecular photoionization spectrum is extremely complex and shows little resemblence either to the corresponding atomic spectrum (indicating that the spectrum of the dimer is not simply a perturbed atomic spectrum) or to the molecular absorption spectrum at longer wavelengths. The regular vibrational progressions seen at longer wavelengths are absent above the first ionization potential. Detailed spectroscopic analysis is possible for only a small fraction of the observed features; however, vibrational intervals of 50--100 cm -1 suggest that some of the Rydberg states have B 2 Pi/sub 3/2g/ ionic cores. A comparison of the absorption and photoionization spectra shows that, at wavelengths shorter than approx.835 A, many of the excited states decay via mechanisms other than autoionization

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

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...

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...

Localization and mass spectra of various matter fields on Weyl thin brane

Energy Technology Data Exchange (ETDEWEB)

Sui, Tao-Tao; Zhao, Li; Zhang, Yu-Peng [Lanzhou University, Institute of Theoretical Physics, Lanzhou (China); Xie, Qun-Ying [Lanzhou University, School of Information Science and Engineering, Lanzhou (China)

2017-06-15

It has been shown that the thin brane model in a five-dimensional Weyl gravity can deal with the wrong-signed Friedmann-like equation in the Randall-Sundrum-1 (RS1) model. In the Weyl brane model, there are also two branes with opposite brane tensions, but the four-dimensional graviton (the gravity zero mode) is localized near the negative tension brane, while our four-dimensional universe is localized on the positive tension brane. In this paper, we consider the mass spectra of various bulk matter fields (i.e., scalar, vector, and fermion fields) on the Weyl brane. It is shown that the zero modes of those matter fields can be localized on the positive tension brane under some conditions. The mass spectra of the bulk matter fields are equidistant for the higher excited states, and relatively sparse for the lower excited states. The size of the extra dimension determines the gap of the mass spectra. We also consider the correction to the Newtonian potential in this model and it is proportional to 1/r{sup 3}. (orig.)

HIGH-RESOLUTION INFRARED IMAGING AND SPECTROSCOPY OF THE Z CANIS MAJORIS SYSTEM DURING QUIESCENCE AND OUTBURST

Energy Technology Data Exchange (ETDEWEB)

Hinkley, Sasha; Hillenbrand, Lynne; Crepp, Justin R. [Department of Astronomy, California Institute of Technology, 1200 E. California Blvd, MC 249-17, Pasadena, CA 91125 (United States); Oppenheimer, Ben R.; Zimmerman, Neil; Brenner, Douglas [Astrophysics Department, American Museum of Natural History, Central Park West at 79th Street, New York, NY 10024 (United States); Rice, Emily L. [Department of Engineering Science and Physics, College of Staten Island, City University of New York, 2800 Victory Bvld, Staten Island, NY 10314 (United States); Pueyo, Laurent [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Vasisht, Gautam; Roberts, Jennifer E.; Roberts, Lewis C. Jr.; Burruss, Rick; Wallace, J. Kent; Cady, Eric; Zhai, Chengxing [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Dr., Pasadena, CA 91109 (United States); Kraus, Adam L. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA, 02138 (United States); Ireland, Michael J. [Department of Physics and Astronomy, Macquarie University, New South Wales, NSW 2109 (Australia); Beichman, Charles [NASA Exoplanet Science Institute, California Institute of Technology, Pasadena, CA 91125 (United States); Dekany, Richard [Caltech Optical Observatories, California Institute of Technology, Pasadena, CA 91125 (United States); Parry, Ian R. [Institute of Astronomy, University of Cambridge, Madingley Road, Cambridge CB3 0HA (United Kingdom); and others

2013-01-20

We present adaptive optics photometry and spectra in the JHKL bands along with high spectral resolution K-band spectroscopy for each component of the Z Canis Majoris system. Our high angular resolution photometry of this very young ({approx}<1 Myr) binary, comprised of an FU Ori object and a Herbig Ae/Be star, was gathered shortly after the 2008 outburst while our high-resolution spectroscopy was gathered during a quiescent phase. Our photometry conclusively determines that the outburst was due solely to the embedded Herbig Ae/Be member, supporting results from earlier works, and that the optically visible FU Ori component decreased slightly ({approx}30%) in luminosity during the same period, consistent with previous works on the variability of FU Ori type systems. Further, our high-resolution K-band spectra definitively demonstrate that the 2.294 {mu}m CO absorption feature seen in composite spectra of the system is due solely to the FU Ori component, while a prominent CO emission feature at the same wavelength, long suspected to be associated with the innermost regions of a circumstellar accretion disk, can be assigned to the Herbig Ae/Be member. These findings clarify previous analyses of the origin of the CO emission in this complex system.

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.

Optical spectra of radio planetary nebulae in the large Magellanic Cloud

Directory of Open Access Journals (Sweden)

Payne J.L.

2008-01-01

Full Text Available We present 11 spectra from 12 candidate radio sources co-identified with known planetary nebulae (PNe in the Large Magellanic Cloud (LMC. Originally found in Australia Telescope Compact Array (ATCA LMC surveys at 1.4, 4.8 and 8.64 GHz and confirmed by new high resolution ATCA images at 6 and 3 cm (4' /2' , these complement data recently presented for candidate radio PNe in the Small Magellanic Cloud (SMC. Their spectra were obtained using the Radcliff 1.9-meter telescope in Sutherland (South Africa. All of the optical PNe and radio candidates are within 2' and may represent a population of selected radio bright sample only. Nebular ionized masses of these objects are estimated to be as high as 1.8 Mfi, supporting the idea that massive PNe progenitor central stars lose much of their mass in the asymptotic giant branch (AGB phase or prior. We also identify a sub-population (33% of radio PNe candidates with prominent ionized iron emission lines.

Nonnegative constraint quadratic program technique to enhance the resolution of γ spectra

Science.gov (United States)

Li, Jinglun; Xiao, Wuyun; Ai, Xianyun; Chen, Ye

2018-04-01

Two concepts of the nonnegative least squares problem (NNLS) and the linear complementarity problem (LCP) are introduced for the resolution enhancement of the γ spectra. The respective algorithms such as the active set method and the primal-dual interior point method are applied to solve the above two problems. In mathematics, the nonnegative constraint results in the sparsity of the optimal solution of the deconvolution, and it is this sparsity that enhances the resolution. Finally, a comparison in the peak position accuracy and the computation time is made between these two methods and the boosted L_R and Gold methods.

Comparative analysis of native and permethylated human milk oligosaccharides by liquid chromatography coupled to high resolution mass spectrometry.

Science.gov (United States)

Oursel, Stéphanie; Cholet, Sophie; Junot, Christophe; Fenaille, François

2017-12-15

Human milk oligosaccharides (HMOs) represent the third most abundant components of milk after lactose and lipids. HMOs are indigestible by the suckling infant but can act as prebiotics and have significant biological functions regarding the organism defense against pathogens (such as bacteria or viruses) by preventing interactions with their receptors. Although constituted of only five distinct monosaccharide building blocks, HMOs are highly structurally diverse compounds with many co-existing structural isomers. Here we report the development and comparison of two distinct glycomic platforms based on liquid chromatography coupled to high resolution mass spectrometry (LC-MS) for analyzing HMOs. We have implemented and thoroughly compared the LC-MS of permethylated and native HMOs on reversed phase (RP) and porous graphitic carbon (PGC) columns for their ability to resolve the natural heterogeneity of milk oligosaccharides at the highest sensitivity. Our data essentially underlines the usefulness of analyzing HMOs as permethylated derivatives especially for getting more precise structural information at high sensitivity. For instance, permethylation annihilates gas-phase fucose migration during MS/MS experiments, thus facilitating spectra interpretation and giving access to relevant information regarding oligosaccharide branching and isomer distinction. At the opposite, LC-MS profiling of native HMOs (using PGC) in milk performed best in terms of detected species, while also being much faster in terms of sample preparation. Although less efficient than PGC chromatography, RPLC proved successful for separating pairs of permethylated isomeric HMOs. A key advantage of RP over PGC liquid chromatography is that retention times can be correlated to molecular weights, which can greatly facilitate further HMO identification using retention time prediction. Altogether these data lead us to think that LC-MS analysis of native HMOs (using PGC) can be used as first

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.

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...

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.

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.

Quantifying K, U and Th contents of marine sediments using shipboard natural gamma radiation spectra measured on DV JOIDES Resolution

Science.gov (United States)

De Vleeschouwer, David; Dunlea, Ann G.; Auer, Gerald; Anderson, Chloe H.; Brumsack, Hans; de Loach, Aaron; Gurnis, Michael C.; Huh, Youngsook; Ishiwa, Takeshige; Jang, Kwangchul; Kominz, Michelle A.; März, Christian; Schnetger, Bernhard; Murray, Richard W.; Pälike, Heiko; Expedition 356 shipboard scientists, IODP

2017-04-01

During International Ocean Discovery Program (IODP) expeditions, shipboard-generated data provide the first insights into the cored sequences. The natural gamma radiation (NGR) of the recovered material, for example, is routinely measured on the ocean drilling research vessel DV JOIDES Resolution. At present, only total NGR counts are readily available as shipboard data, although full NGR spectra (counts as a function of gamma-ray energy level) are produced and archived. These spectra contain unexploited information, as one can estimate the sedimentary contents of potassium (K), thorium (Th), and uranium (U) from the characteristic gamma-ray energies of isotopes in the 40K, 232Th, and 238U radioactive decay series. Dunlea et al. [2013] quantified K, Th and U contents in sediment from the South Pacific Gyre by integrating counts over specific energy levels of the NGR spectrum. However, the algorithm used in their study is unavailable to the wider scientific community due to commercial proprietary reasons. Here, we present a new MATLAB algorithm for the quantification of NGR spectra that is transparent and accessible to future NGR users. We demonstrate the algorithm's performance by comparing its results to shore-based inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-emission spectrometry (ICP-ES), and quantitative wavelength-dispersive X-ray fluorescence (XRF) analyses. Samples for these comparisons come from eleven sites (U1341, U1343, U1366-U1369, U1414, U1428-U1430, U1463) cored in two oceans during five expeditions. In short, our algorithm rapidly produces detailed high-quality information on sediment properties during IODP expeditions at no extra cost. Dunlea, A. G., R. W. Murray, R. N. Harris, M. A. Vasiliev, H. Evans, A. J. Spivack, and S. D'Hondt (2013), Assessment and use of NGR instrumentation on the JOIDES Resolution to quantify U, Th, and K concentrations in marine sediment, Scientific Drilling, 15, 57-63.

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.

High-resolution solution-state NMR of unfractionated plant cell walls

Science.gov (United States)

John Ralph; Fachuang Lu; Hoon Kim; Dino Ress; Daniel J. Yelle; Kenneth E. Hammel; Sally A. Ralph; Bernadette Nanayakkara; Armin Wagner; Takuya Akiyama; Paul F. Schatz; Shawn D. Mansfield; Noritsugu Terashima; Wout Boerjan; Bjorn Sundberg; Mattias Hedenstrom

2009-01-01

Detailed structural studies on the plant cell wall have traditionally been difficult. NMR is one of the preeminent structural tools, but obtaining high-resolution solution-state spectra has typically required fractionation and isolation of components of interest. With recent methods for dissolution of, admittedly, finely divided plant cell wall material, the wall can...

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)

Formularity: Software for Automated Formula Assignment of Natural and Other Organic Matter from Ultrahigh-Resolution Mass Spectra.

Science.gov (United States)

Tolić, Nikola; Liu, Yina; Liyu, Andrey; Shen, Yufeng; Tfaily, Malak M; Kujawinski, Elizabeth B; Longnecker, Krista; Kuo, Li-Jung; Robinson, Errol W; Paša-Tolić, Ljiljana; Hess, Nancy J

2017-12-05

Ultrahigh resolution mass spectrometry, such as Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), can resolve thousands of molecular ions in complex organic matrices. A Compound Identification Algorithm (CIA) was previously developed for automated elemental formula assignment for natural organic matter (NOM). In this work, we describe software Formularity with a user-friendly interface for CIA function and newly developed search function Isotopic Pattern Algorithm (IPA). While CIA assigns elemental formulas for compounds containing C, H, O, N, S, and P, IPA is capable of assigning formulas for compounds containing other elements. We used halogenated organic compounds (HOC), a chemical class that is ubiquitous in nature as well as anthropogenic systems, as an example to demonstrate the capability of Formularity with IPA. A HOC standard mix was used to evaluate the identification confidence of IPA. Tap water and HOC spike in Suwannee River NOM were used to assess HOC identification in complex environmental samples. Strategies for reconciliation of CIA and IPA assignments were discussed. Software and sample databases with documentation are freely available.

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)

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

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.

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.

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.

Re-hardening of hadron transverse mass spectra in relativistic heavy-ion collisions

International Nuclear Information System (INIS)

Ohnishi, A.; Otuka, N.; Sahu, P.K.; Isse, M.; Nara, Y.

2001-01-01

We analyze the spectra of pions and protons in heavy-ion collisions at relativistic energies from 2 A GeV to 65 + 65 A GeV by using a jet-implemented hadron-string cascade model. In this energy region, hadron transverse mass spectra first show softening until SPS energies, and re-hardening may emerge at RHIC energies. Since hadronic matter is expected to show only softening at higher energy densities, this re-hardening of spectra can be interpreted as a good signature of the quark-gluon plasma formation. (author)

Bayesian model comparison using Gauss approximation on multicomponent mass spectra from CH4 plasma

International Nuclear Information System (INIS)

Kang, H.D.; Dose, V.

2004-01-01

We performed Bayesian model comparison on mass spectra from CH4 rf process plasmas to detect radicals produced in the plasma. The key ingredient for its implementation is the high-dimensional evidence integral. We apply Gauss approximation to evaluate the evidence. The results were compared with those calculated by the thermodynamic integration method using Markov Chain Monte Carlo technique. In spite of very large difference in the computation time between two methods a very good agreement was obtained. Alternatively, a Monte Carlo integration method based on the approximated Gaussian posterior density is presented. Its applicability to the problem of mass spectrometry is discussed

Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

Energy Technology Data Exchange (ETDEWEB)

UC Davis; Cappa, Christopher D.; Wilson, Kevin R.

2010-10-28

Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the alpha-pinene + O3 reaction (alphaP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the alphaP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the alphaP spectra suggest that the evaporation of alphaP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from the alphaP particles existing as in a glassy state instead of having the expected liquid-like behavior. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

Measurement and Simulation of Spontaneous Raman Scattering Spectra in High-Pressure, Fuel-Rich H2-Air Flames

Science.gov (United States)

Kojima, Jun; Nguyen, Quang-Viet

2003-01-01

Rotational vibrational spontaneous Raman spectra (SRS) of H2, N2, and H2O have been measured in H2-air flames at pressures up to 30 atm as a first stem towards establishing a comprehensive Raman spectral database for temperatures and species in high-pressure combustion. A newly developed high-pressure burner facility provides steady, reproducible flames with a high degree of flow precision. We have obtained an initial set of measurements that indicate the spectra are of sufficient quality in terms of spectral resolution, wavelength coverage, and signal-to-noise ratio for use in future reference standards. The fully resolved Stokes and anti-Stokes shifted SRS spectra were collected in the visible wavelength range (400-700 nm) using pulse-stretched 532 nm excitation and a non-intensified CCD spectrograph with a high-speed shutter. Reasonable temperatures were determined via the intensity distribution of rotational H2 lines at stoichiometry and fuel-rich conditions. Theoretical Raman spectra of H2 were computed using a semi-classical harmonic-oscillator model with recent pressure broadening data and were compared with experimental results. The data and simulation indicated that high-J rotational lines of H2 might interfere with the N2 vibrational Q-branch lines, and this could lead to errors in N2-Raman thermometry based on the line-fitting method. From a comparison of N2 Q-branch spectra in lean H2 low-pressure (1.2 atm) and high-pressure (30 atm) flames, we found no significant line-narrowing or -broadening effects at the current spectrometer resolution of 0.04 nm.

Principles of high resolution NMR in solids

CERN Document Server

Mehring, Michael

1983-01-01

The field of Nuclear Magnetic Resonance (NMR) has developed at a fascinating pace during the last decade. It always has been an extremely valuable tool to the organic chemist by supplying molecular "finger print" spectra at the atomic level. Unfortunately the high resolution achievable in liquid solutions could not be obtained in solids and physicists and physical chemists had to live with unresolved lines open to a wealth of curve fitting procedures and a vast amount of speculations. High resolution NMR in solids seemed to be a paradoxon. Broad structure­ less lines are usually encountered when dealing with NMR in solids. Only with the recent advent of mUltiple pulse, magic angle, cross-polarization, two-dimen­ sional and multiple-quantum spectroscopy and other techniques during the last decade it became possible to resolve finer details of nuclear spin interactions in solids. I have felt that graduate students, researchers and others beginning to get involved with these techniques needed a book which trea...

Ultra-high resolution spectroscopy of the He doubly excited states

International Nuclear Information System (INIS)

Bozek, J.D.; Schlachter, A.S.; Kaindl, G.; Schulz, K.

1995-11-01

Photoionization spectra of the doubly-excited states of He were measured using beamline 9.0.1 at the Advanced Light Source. The beamline utilizes a 4.5 m long 8 cm period undulator as its source together with a spherical grating monochromator to provide an extremely bright source of photons in the range of 20 - 300 eV. A resolving power (E/ΔE) of 64,000 was obtained from the 1 MeV FWEM (2p,3d) doubly excited state resonance of He at 64.12 eV. The high brightness of the source and the very high quality optical elements of the beamline were all essential for achieving such a high resolution. The beamline components and operation are described and spectra of the double excitation resonances of He presented

High spatial resolution observations of the T Tau system - II. Interferometry in the mid-infrared

International Nuclear Information System (INIS)

Ratzka, Thorsten

2008-01-01

Each time the resolution was improved, observations of the young low-mass star T Tau led to new insights. Initially classified as the prototype of low-mass pre-main-sequence stars, measurements with high resolution techniques in the near-infrared revealed the existence of a deeply embedded companion only 0.7 arcsec to the south. Later on, this companion itself has been resolved into two sources with a separation of only about 50 mas. We investigated both the optically bright northern component and the embedded southern binary with the MID-infrared Interferometric instrument (MIDI). The resulting visibilities of the northern component decrease with wavelength, independent of the baseline's position angle. This is a clear sign of the large face-on circumstellar disc. With a simultaneous fit of a radiative transfer model to both the interferometric results and the spectral energy distribution, the properties of this disc can be determined without the high degeneracy of fits to the spectral energy distribution alone. Since the visibilities of the southern binary are clearly dominated by the typical sinusoidal binary signal, we could for the first time in the mid-infrared derive separate spectra for both components together with a very precise relative position. This position is in excellent agreement with the orbit found from a fit to the near-infrared adaptive optics measurements. The orbit with its small periastron distance indicates tidally truncated discs, which are consistent with the interferometric measurements. The peculiar properties of the infrared companion can be explained by the model of an intermediate mass star extincted by an almost edge-on disc.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS.

Science.gov (United States)

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-11-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation. Graphical Abstract ᅟ.

[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.

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

Mass spectra features of biomass burning boiler and coal burning boiler emitted particles by single particle aerosol mass spectrometer.

Science.gov (United States)

Xu, Jiao; Li, Mei; Shi, Guoliang; Wang, Haiting; Ma, Xian; Wu, Jianhui; Shi, Xurong; Feng, Yinchang

2017-11-15

In this study, single particle mass spectra signatures of both coal burning boiler and biomass burning boiler emitted particles were studied. Particle samples were suspended in clean Resuspension Chamber, and analyzed by ELPI and SPAMS simultaneously. The size distribution of BBB (biomass burning boiler sample) and CBB (coal burning boiler sample) are different, as BBB peaks at smaller size, and CBB peaks at larger size. Mass spectra signatures of two samples were studied by analyzing the average mass spectrum of each particle cluster extracted by ART-2a in different size ranges. In conclusion, BBB sample mostly consists of OC and EC containing particles, and a small fraction of K-rich particles in the size range of 0.2-0.5μm. In 0.5-1.0μm, BBB sample consists of EC, OC, K-rich and Al_Silicate containing particles; CBB sample consists of EC, ECOC containing particles, while Al_Silicate (including Al_Ca_Ti_Silicate, Al_Ti_Silicate, Al_Silicate) containing particles got higher fractions as size increase. The similarity of single particle mass spectrum signatures between two samples were studied by analyzing the dot product, results indicated that part of the single particle mass spectra of two samples in the same size range are similar, which bring challenge to the future source apportionment activity by using single particle aerosol mass spectrometer. Results of this study will provide physicochemical information of important sources which contribute to particle pollution, and will support source apportionment activities. Copyright © 2017. Published by Elsevier B.V.

A high-resolution atlas of the infrared spectrum of the Sun and the Earth atmosphere from space: A compilation of ATMOS spectra of the region from 650 to 4800 cm (2.3 to 16 micron). Volume 1: The Sun

Science.gov (United States)

Farmer, Crofton B.; Norton, Robert H.

1989-01-01

During the period April 29 through May 2, 1985, the Atmospheric Trace Molecular Spectroscopy experiment was operated as part of the Spacelab-3 payload of the shuttle Challenger. The instrument, a modified Michelson Interferometer covering the frequency range from 600 to 5000/cm, at a spectral resolution of 0.01/cm, recorded infrared spectra of the Sun and of the Earth's atmosphere at times close to entry into and exit from occultation by the Earth's limb as seen from the shuttle orbit of 360 km. Spectra were obtained that are free from absorptions due to constituents of the atmosphere (i.e., solar pure spectra), as well as spectra of the atmosphere itself, covering line-of-sight tangent altitudes that span the range from the lower thermosphere to the bottom of the troposphere. This atlas, believed to be the first record of observations of the continuous high resolution infrared spectrum of the Sun and the Earth's atmosphere from space, provides a compilation of these spectra arranged in a hardcopy format suitable for quick-look reference purposes; the data are also available in digital form.

Formularity: Software for Automated Formula Assignment of Natural and Other Organic Matter from Ultrahigh-Resolution Mass Spectra

Energy Technology Data Exchange (ETDEWEB)

Tolic, Nikola; Liu, Yina; Liyu, Andrey V.; Shen, Yufeng; Tfaily, Malak M.; Kujawinski, Elizabeth B.; Longnecker, Krista; Kuo, Li-Jung; Robinson, Errol W.; Pasa Tolic, Ljiljana; Hess, Nancy J.

2017-11-13

Ultrahigh-resolution mass spectrometry, such as Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS), can resolve thousands of molecular ions in complex organic matrices. A Compound Identification Algorithm (CIA) was previously developed for automated elemental formula assignment for natural organic matter (NOM). In this work we describe a user friendly interface for CIA, titled Formularity, which includes an additional functionality to perform search of formulas based on an Isotopic Pattern Algorithm (IPA). While CIA assigns elemental formulas for compounds containing C, H, O, N, S, and P, IPA is capable of assigning formulas for compounds containing other elements. We used halogenated organic compounds (HOC), a chemical class that is ubiquitous in nature as well as anthropogenic systems, as an example to demonstrate the capability of Formularity with IPA. A HOC standard mix was used to evaluate the identification confidence of IPA. The HOC spike in NOM and tap water were used to assess HOC identification in natural and anthropogenic matrices. Strategies for reconciliation of CIA and IPA assignments are discussed. Software and sample databases with documentation are freely available from the PNNL OMICS software repository https://omics.pnl.gov/software/formularity.

Determination of polycyclic aromatic hydrocarbons and their nitrated derivatives in Diesel soot by gas chromatography and high resolution mass spectrometry

International Nuclear Information System (INIS)

Remberg, G.

1998-11-01

Periodical monitoring of the exposure levels towards chemical hazards is an important issue of occupational safety and health. Some constituents of diesel exhaust emissions, like polycyclic aromatic hydrocarbons and their nitrated derivatives, have attracted special attention due to their carcinogenic and partly mutagenic properties. Therefore, the present work focused on the development of new methodical aspects for the determination of these substances in diesel particulate matter. In the first stage of this study the essential gas chromatographic and mass spectrometric characteristics of 51 authentic PAH and NPAH single standards have been investigated. A retention index system on DB-5 type capillary columns has been established in order to facilitate the identification of these target compounds in complex matrices. Before choosing proper MID quantification ions the full scan (+)EI- and ECNCI-mass spectra of all standards were acquired. The GC-(+)EI-MS detection limits of three NPAH were determined with different mass spectrometric modes (i.e. LR/full scan, LR/MID and HR/MID), being in the range of a few picograms in the latter mode. The use of large volume injection in conjunction with a PTV for PAH/NPAH trace analysis was studied and optimized for an injection volume of up to nine microliters. Extraction of diesel soot with dichloromethane was performed in accordance with US EPA method 3545 by means of accelerated solvent extraction, which takes significantly less than one hour. Gas chromatographic investigations on such extracts with various detectors of different selectivity (i.e. FID, LRMS and HRMS) showed the exclusive capability of high mass spectral resolution (about R ∼10000) to differentiate between analytes and matrix components. On the basis of these preliminary results an operating procedure was proposed. Its key-elements are accelerated solvent extraction of the sample and analysis of the resulting solution by means of GC-(+)EI-HRMS followed by

Development of high resolution vacuum ultraviolet beam line at Indus-1 synchrotron source

International Nuclear Information System (INIS)

Shukla, R.P.; Das, N.C.; Udupa, D.V.; Saraswathy, P.; Sunanda, K.; Jha, S.N.; Shastri, Aparna; Singh, Paramjeet; Mallick, Manika; Mishra, A.P.; Sahoo, N.K.; Sinha, A.K.; Bhatt, S.; Sahni, V.C.

2005-07-01

High resolution vacuum ultraviolet beamline at Indus-1 450 MeV synchrotron source has been developed for carrying out absorption spectral studies of atoms and molecules. The beamline consists of three major parts i.e. a focusing optical system, an absorption cell and a high resolution 6.65 m vacuum ultraviolet spectrometer in Eagle mount. The wavelength range of the spectrometer is from 700 A to 2000 A and the resolution of the spectrometer is 0.01 A. Using the synchrotron source Indus-1, the absorption spectra of oxygen, ammonia and carbon disulphide have been recorded at the wavelength band of 1750 A, 1881 A and 3100 A respectively. Details of different aspects of design and development of the high resolution VUV beamline are described in this report. (author)

Comprehensive Two-dimensional Liquid Chromatography coupled to High Resolution Time of Flight Mass Spectrometry for Chemical Characterization of Sewage Treatment Plant Effluents

NARCIS (Netherlands)

Ouyang, X.; Leonards, P.E.G.; Legler, J.; van der Oost, R.; de Boer, J.; Lamoree, M.H.

2015-01-01

For the first time a comprehensive two-dimensional liquid chromatography (LC. ×. LC) system coupled with a high resolution time-of-flight mass spectrometer (HR-ToF MS) was developed and applied for analysis of emerging toxicants in wastewater effluent. The system was optimized and validated using

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.