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Sample records for thermal ionization mass

  1. Effect of microstructure of graphite on the nonreductive thermal ion emission in thermal ionization mass spectrometry.

    Science.gov (United States)

    Wei, H Z; Jiang, S Y; Xiao, Y K

    2010-02-25

    The emission behavior of polyatomic ions in the ionization source of thermal ionization mass spectrometry (TIMS) was investigated. The results suggest that the presence of a graphite promoter plays a key role for the formation and stable emission of polyatomic ions, such as M(2)X(+), M(2)BO(2)(+), Cs(2)NO(2)(+), and Cs(2)CNO(+). Our data further implied that the intensity of M(2)X(+) and M(2)BO(2)(+) increases and the emission temperature decreases with increasing cationic and anionic radius. During the boron isotopic measurement using the Cs(2)BO(2)(+)-graphite-PTIMS method, the isobaric interference ion Cs(2)CNO(+) cannot be transformed from nitrate or organic compounds containing an amide group but can be induced by the existence of trace amounts of boron because of its special electron-deficiency property (B(3+)). Characterization on the planar crystalline structure of various graphite samples with SEM, TEM, and Raman spectroscopy confirmed the relationship of the emission capacity of polyatomic ions and the crystal microstructure of graphite and provides direct evidence that graphite with a perfect parallel and equidistant layer orientation shows a beneficial effect on the emission of polyatomic ions in TIMS. The mechanism study on the formation of polyatomic ions opens the possibility to establish high precision methods for isotopic composition analysis of more nonmetal elements with the TIMS technique.

  2. GoAmazon 2014/15 Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, JN [Univ. of California, Irvine, CA (United States)

    2016-04-01

    The Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) deployment to the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility T3 site in Manacapuru, Brazil, was motivated by two main scientific objectives of the Green Ocean Amazon (GoAmazon) 2014/15 field campaign. 1) Study the interactions between anthropogenic and biogenic emissions by determining important molecular species in ambient nanoparticles. To address this, TDCIMS data will be combined with coincident measurements such as gas-phase sulfuric acid to determine the contribution of sulfuric acid condensation to nucleation and growth. We can then compare that result to TDCIMS-derived nanoparticle composition to determine the fraction of growth that can be attributed to the uptake of organic compounds. The molecular composition of sampled particles will also be used to attribute specific chemical species and mechanisms to growth, such as the condensation of low-volatility species or the oligomerization of α-dicarbonyl compounds. 2) Determine the source of new ambient nanoparticles in the Amazon. The hypothesis prior to measurements was that potassium salts formed from the evaporation of primary particles emitted by fungal spores can provide a unique and important pathway for new particle production in the Amazon basin. To explore this hypothesis, the TDCIMS recorded the mass spectra of sampled ambient particles using a protonated water cluster Chemical Ionization Mass Spectrometer (CIMS). Laboratory tests performed using potassium salts show that the TDCIMS can detect potassium with high sensitivity with this technique.

  3. Separation Techniques for Uranium and Plutonium at Trace Levels for the Thermal Ionization Mass Spectrometric Determination

    Energy Technology Data Exchange (ETDEWEB)

    Suh, M. Y.; Han, S. H.; Kim, J. G.; Park, Y. J.; Kim, W. H

    2005-12-15

    This report describes the state of the art and the progress of the chemical separation and purification techniques required for the thermal ionization mass spectrometric determination of uranium and plutonium in environmental samples at trace or ultratrace levels. Various techniques, such as precipitation, solvent extraction, extraction chromatography, and ion exchange chromatography, for separation of uranium and plutonium were evaluated. Sample preparation methods and dissolution techniques for environmental samples were also discussed. Especially, both extraction chromatographic and anion exchange chromatographic procedures for uranium and plutonium in environmental samples, such as soil, sediment, plant, seawater, urine, and bone ash were reviewed in detail in order to propose some suitable methods for the separation and purification of uranium and plutonium from the safeguards environmental or swipe samples. A survey of the IAEA strengthened safeguards system, the clean room facility of IAEA's NWAL(Network of Analytical Laboratories), and the analytical techniques for safeguards environmental samples was also discussed here.

  4. [Real-time analysis of polyvinyl chloride thermal decomposition/combustion products with single photon ionization/photoelectron ionization online mass spectrometer].

    Science.gov (United States)

    Chen, Wen-Dong; Hou, Ke-Yong; Chen, Ping; Li, Fang-Long; Zhao, Wu-Duo; Cui, Hua-Peng; Hua, Lei; Xie, Yuan-Yuan; Li, Hai-Yang

    2013-01-01

    With the features of a broad range of ionizable compounds, reduced fragments and simple mass spectrum, a homemade magnetic field enhanced photoelectron ionization (MEPEI) source combined with single photon ionization (SPI) for time-of-flight mass spectrometer was built and applied to analyze thermal decomposition/combustion products of polyvinyl chloride (PVC). The combined ion source can be switched very fast between SPI mode and SPI-MEPEI mode for detecting different targeted compounds, and only adjusting the voltage of the electrode in the ionization region to trigger the switch. Among the PVC thermal decomposition/combustion products, HCl and CO2, which ionization energies (12.74 eV, 13.77 eV respectively) were higher than the energy of photon (10.60 eV), were ionized by MEPEI, while alkenes, dichloroethylene, benzene and its homologs, monochlorobenzene, styrene, indane, naphthalene and its homologs were ionized by SPI and MEPEI simultaneously. Spectra of interested products as a function of temperatures indicated that products are formed via two main mechanisms: (1) dechlorination and intramolecular cyclization can lead to the formation of HCl, benzene and naphthalene at 250-370 degrees C; (2) intermolecular crosslinking leads to the formation of alkyl aromatics such as toluene and xylene/ethylbenzene at 380-510 degrees C. The experimental results show that the combined ion source of SPI/ SPI-MEPEI for TOF-MS has broad application prospects in the online analysis field.

  5. Separation and Analysis of Boron Isotope in High Plant by Thermal Ionization Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Qingcai Xu

    2015-01-01

    Full Text Available Knowledge of boron and its isotope in plants is useful to better understand the transposition and translocation of boron within plant, the geochemical behavior in the interface between soil and plant, and the biogeochemical cycle of boron. It is critical to develop a useful method to separate boron from the plant for the geochemical application of boron and its isotope. A method was developed for the extraction of boron in plant sample, whose isotope was determined by thermal ionization mass spectrometry. The results indicated that this method of dry ashing coupled with two-step ion-exchange chromatography is powerful for the separation of boron in plant sample with large amounts of organic matters completely. The ratios of boron isotope composition in those plant tissue samples ranged from -19.45‰ to +28.13‰ (total range: 47.58‰ with a mean value of 2.61±11.76‰ SD. The stem and root isotopic compositions were lower than those in flower and leaf. The molecular mechanism of boron isotope may be responsible for the observed variation of boron isotopic composition and are considered as a useful tool for the better understanding of boron cycling process in the environment and for the signature of living systems.

  6. Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

    Science.gov (United States)

    Fantle, M.S.; Bullen, T.D.

    2009-01-01

    The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a

  7. High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry.

    Science.gov (United States)

    Paul, Maxence; Bridgestock, Luke; Rehkämper, Mark; van DeFlierdt, Tina; Weiss, Dominik

    2015-03-10

    A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a (207)Pb-(204)Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28±21 pg (1sd) and typical Pb recoveries of 40-60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12±4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700-1500 ppm and 1000-2000 ppm were achieved for (207)Pb/(206)Pb, (208)Pb/(206)Pb and (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor (204)Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the (206)Pb/(204)Pb ratios are well correlated

  8. Ambient ionization mass spectrometry

    Science.gov (United States)

    Lebedev, A. T.

    2015-07-01

    Ambient ionization mass spectrometry emerged as a new scientific discipline only about ten years ago. A considerable body of information has been reported since that time. Keeping the sensitivity, performance and informativity of classical mass spectrometry methods, the new approach made it possible to eliminate laborious sample preparation procedures and triggered the development of miniaturized instruments to work directly in the field. The review concerns the theoretical foundations and design of ambient ionization methods. Their advantages and drawbacks, as well as prospects for application in chemistry, biology, medicine, environmetal analysis, etc., are discussed. The bibliography includes 194 references.

  9. Direct analysis of anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption-dielectric barrier discharge ionization mass spectrometry.

    Science.gov (United States)

    Saha, Subhrakanti; Mandal, Mridul Kanti; Nonami, Hiroshi; Hiraoka, Kenzo

    2014-08-11

    Rapid detection of trace level anabolic steroids in urine is highly desirable to monitor the consumption of performance enhancing anabolic steroids by athletes. The present article describes a novel strategy for identifying the trace anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption (LPTD) coupled to dielectric barrier discharge (DBD) ionization mass spectrometry. Using this method the steroid molecules are enriched within a liquid droplet during the thermal desorption process and desorbed all-together at the last moment of droplet evaporation in a short time domain. The desorbed molecules were ionized using a dielectric barrier discharge ion-source in front of the mass spectrometer inlet at open atmosphere. This process facilitates the sensitivity enhancement with several orders of magnitude compared to the thermal desorption at a lower temperature. The limits of detection (LODs) of various steroid molecules were found to be in the range of 0.05-0.1 ng mL(-1) for standard solutions and around two orders of magnitude higher for synthetic urine samples. The detection limits of urinary anabolic steroids could be lowered by using a simple and rapid dichloromethane extraction technique. The analytical figures of merit of this technique were evaluated at open atmosphere using suitable internal standards. The technique is simple and rapid for high sensitivity and high throughput screening of anabolic steroids in urine. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Rapid characterization of chemical compounds in liquid and solid states using thermal desorption electrospray ionization mass spectrometry.

    Science.gov (United States)

    Huang, Min-Zong; Zhou, Chi-Chang; Liu, De-Lin; Jhang, Siou-Sian; Cheng, Sy-Chyi; Shiea, Jentaie

    2013-10-01

    Rapid characterization of thermally stable chemical compounds in solid or liquid states is achieved through thermal desorption electrospray ionization mass spectrometry (TD-ESI/MS). A feature of this technique is that sampling, desorption, ionization, and mass spectrometric detection are four separate events with respect to time and location. A metal probe was used to sample analytes in their solid or liquid states. The probe was then inserted in a preheated oven to thermally desorb the analytes on the probe. The desorbed analytes were carried by a nitrogen gas stream into an ESI plume, where analyte ions were formed via interactions with charged solvent species generated in the ESI plume. The analyte ions were subsequently detected by a mass analyzer attached to the TD-ESI source. Quantification of acetaminophen in aqueous solutions using TD-ESI/MS was also performed in which a linear response for acetaminophen was obtained between 25 and 500 ppb (R(2) = 0.9978). The standard deviation for a reproducibility test for ten liquid samples was 9.6%. Since sample preparation for TD-ESI/MS is unnecessary, a typical analysis can be completed in less than 10 s. Analytes such as the active ingredients in over-the-counter drugs were rapidly characterized regardless of the different physical properties of said drugs, which included liquid eye drops, viscous cold syrup solution, ointment cream, and a drug tablet. This approach was also used to detect trace chemical compounds in illicit drugs and explosives, in which samples were obtained from the surfaces of a cell phone, piece of luggage made from hard plastic, business card, and wooden desk.

  11. Thermal ionization mass spectrometry U-series dating of a hominid site near Nanjing, China

    Science.gov (United States)

    Zhao, Jian-Xin; Hu, Kai; Collerson, Kenneth D.; Xu, Han-Kui

    2001-01-01

    Mass spectrometric U-series dating of speleothems from Tangshan Cave, combined with ecological and paleoclimatic evidence, indicates that Nanjing Man, a typical Homo erectus morphologically correlated with Peking Man at Zhoukoudian, should be at least 580 k.y. old, or more likely lived during the glacial oxygen isotope stage 16 (˜620 ka). Such an age estimate, which is ˜270 ka older than previous electron spin resonance and alpha-counting U-series dates, has significant implications for the evolution of Asian H. erectus. Dentine and enamel samples from the coexisting fossil layer yield significantly younger apparent ages, that of the enamel sample being only less than one-fourth of the minimum age of Nanjing Man. This suggests that U uptake history is far more complex than existing models can handle. As a result, great care must be taken in the interpretation of electron spin resonance and U-series dates of fossil teeth.

  12. Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

    Science.gov (United States)

    Yamakawa, Akane; Yamashita, Katsuyuki; Makishima, Akio; Nakamura, Eizo

    2009-12-01

    A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

  13. Emission mechanism of polyatomic ions Cs2Cl+ and Cs2BO2(+) in thermal ionization mass spectrometry with various carbon materials.

    Science.gov (United States)

    Wei, Hai-Zhen; Jiang, Shao-Yong; Hemming, Gary N; Yang, Jing-Hong; Xiao, Ying-Kai; Yang, Tao; Yan, Xiong; Yan, Yan

    2011-12-29

    The emission behavior of polyatomic ions Cs(2)Cl(+) and Cs(2)BO(2)(+) in the presence of various carbon materials (Graphite, Carbon, SWNTs, and Fullerenes) in the ionization source of thermal ionization mass spectrometry (TIMS) has been investigated. The emission capacity of various carbon materials are remarkably different as evidenced by the obvious discrepancy in signal intensity of polyatomic ions and accuracy/precision of boron and chlorine isotopic composition determined using Cs(2)Cl(+)-graphite-PTIMS/Cs(2)BO(2)(+)-graphite-PTIMS methods. Combined with morphology and microstructure properties of four selected carbon materials, it could be concluded that the emission behavior of the polyatomic ions strongly depends on the microstructure of the carbon materials used. A surface-induced collision mechanism for formation of such kinds of polyatomic ions in the ionization source of TIMS has been proposed based on the optimized configuration of Cs(2)BO(2)(+) and Cs(2)Cl(+) ions in the gas phase using a molecular dynamics method. The combination of the geometry of the selected carbon materials with the configuration of two polyatomic ions explains the structure effect of carbon materials on the emission behavior of polyatomic ions, where graphite samples with perfect parallels and equidistant layers ensure the capacity of emission to the maximum extent, and fullerenes worsen the emission of polyatomic ions by blocking their pathway. © 2011 American Chemical Society

  14. Ambient ionization mass spectrometry: A tutorial

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Min-Zong; Cheng, Sy-Chi; Cho, Yi-Tzu [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Shiea, Jentaie, E-mail: jetea@fac.nsysu.edu.tw [Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Cancer Center, Kaohsiung Medical University, Kaohsiung, Taiwan (China)

    2011-09-19

    Highlights: {yields} Ambient ionization technique allows the direct analysis of sample surfaces with little or no sample pretreatment. {yields} We sort ambient ionization techniques into three main analytical strategies, direct ionization, direct desorption/ionization, and two-step ionization. {yields} The underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques are described and compared. - Abstract: Ambient ionization is a set of mass spectrometric ionization techniques performed under ambient conditions that allows the direct analysis of sample surfaces with little or no sample pretreatment. Using combinations of different types of sample introduction systems and ionization methods, several novel techniques have been developed over the last few years with many applications (e.g., food safety screening; detection of pharmaceuticals and drug abuse; monitoring of environmental pollutants; detection of explosives for antiterrorism and forensics; characterization of biological compounds for proteomics and metabolomics; molecular imaging analysis; and monitoring chemical and biochemical reactions). Electrospray ionization and atmospheric pressure chemical ionization are the two main ionization principles most commonly used in ambient ionization mass spectrometry. This tutorial paper provides a review of the publications related to ambient ionization techniques. We describe and compare the underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques.

  15. Graphene-based filament material for thermal ionization

    Energy Technology Data Exchange (ETDEWEB)

    Hewitt, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Shick, C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Siegfried, M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-19

    The use of graphene oxide materials for thermal ionization mass spectrometry analysis of plutonium and uranium has been investigated. Filament made from graphene oxide slurries have been 3-D printed. A method for attaching these filaments to commercial thermal ionization post assemblies has been devised. Resistive heating of the graphene based filaments under high vacuum showed stable operation in excess of 4 hours. Plutonium ion production has been observed in an initial set of filaments spiked with the Pu 128 Certified Reference Material.

  16. Ion chromatography electrospray ionization mass spectrometry method development and investigation of lithium hexafluorophosphate-based organic electrolytes and their thermal decomposition products.

    Science.gov (United States)

    Kraft, Vadim; Grützke, Martin; Weber, Waldemar; Winter, Martin; Nowak, Sascha

    2014-08-08

    A method based on the coupling of ion chromatography (IC) and electrospray ionization mass spectrometry (ESI-MS) for the separation and determination of thermal decomposition products of LiPF6-based organic electrolytes is presented. The utilized electrolytes, LP30 and LP50, are commercially available and consist of 1mol/l LiPF6 dissolved in ethylene carbonate/dimethyl carbonate and ethylene carbonate/ethyl methyl carbonate, respectively. For the separation method development three ion chromatographic columns with different capacity and stationary phase were used and compared. Besides the known hydrolysis products of lithium hexafluorophosphate, several new organophosphates were separated and identified with the developed IC-ESI-MS method during aging investigations of the electrolytes. The chemical structures were elucidated with IC-ESI-MS/MS. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Improvement in Thermal-Ionization Mass Spectrometry (TIMS) using Total Flash Evaporation (TFE) method for lanthanides isotope ratio measurements in transmutation targets

    Energy Technology Data Exchange (ETDEWEB)

    Mialle, S.; Gourgiotis, A.; Aubert, M.; Stadelmann, G.; Gautier, C.; Isnard, H. [Commissariat a l' Energie Atomique, CEA Saclay, DEN/DPC/SECR/LANIE, 91191 Gif sur Yvette (France); Chartier, F. [Commissariat a l' Energie Atomique, CEA Saclay, DEN/DPC, 91191 Gif sur Yvette (France)

    2011-07-01

    The experiments involved in the PHENIX french nuclear reactor to obtain precise and accurate data on the total capture cross sections of the heavy isotopes and fission products require isotopic ratios measurements with uncertainty of a few per mil. These accurate isotopic ratio measurements are performed with mass spectrometer equipped with multi-collector system. The major difficulty for the analyses of these actinides and fission products is the low quantity of the initial powder enclosed in steel container (3 to 5 mg) and the very low quantities of products formed (several {mu}g) after irradiation. Specific analytical developments are performed by Thermal Ionization Mass Spectrometry (TIMS) to be able to analyse several nanograms of elements with this technique. A specific method of acquisition named Total Flash Evaporation was adapted in this study in the case of lanthanide measurements for quantity deposited on the filament in the order of 2 ng and applied on irradiated fuel. To validate the analytical approach and discuss about the accuracy of the data, the isotopic ratios obtained by TIMS are compared with other mass spectrometric techniques such as Multiple-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS). (authors)

  18. Improved sample utilization in thermal ionization mass spectrometry isotope ratio measurements: refined development of porous ion emitters for nuclear forensic applications

    Energy Technology Data Exchange (ETDEWEB)

    Baruzzini, Matthew Louis [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-05-08

    The precise and accurate determination of isotopic composition in nuclear forensic samples is vital for assessing origin, intended use and process history. Thermal ionization mass spectrometry (TIMS) is widely accepted as the gold standard for high performance isotopic measurements and has long served as the workhorse in the isotopic ratio determination of nuclear materials. Nuclear forensic and safeguard specialists have relied heavily on such methods for both routine and atypical e orts. Despite widespread use, TIMS methods for the assay of actinide systems continue to be hindered by poor ionization e ciency, often less than tenths of a percent; the majority of a sample is not measured. This represents a growing challenge in addressing nextgeneration nuclear detection needs by limiting the ability to analyze ultratrace quantities of high priority elements that could potentially provide critical nuclear forensic signatures. Porous ion emitter (PIE) thermal ion sources were developed in response to the growing need for new TIMS ion source strategies for improved ionization e ciency, PIEs have proven to be simple to implement, straightforward approach to boosting ion yield. This work serves to expand the use of PIE techniques for the analysis of trace quantities of plutonium and americium. PIEs exhibited superior plutonium and americium ion yields when compared to direct lament loading and the resin bead technique, one of the most e cient methods for actinide analysis, at similar mass loading levels. Initial attempts at altering PIE composition for the analysis of plutonium proved to enhance sample utilization even further. Preliminary investigations of the instrumental fractionation behavior of plutonium and uranium analyzed via PIE methods were conducted. Data collected during these initial trial indicate that PIEs fractionate in a consistent, reproducible manner; a necessity for high precision isotope ratio measurements. Ultimately, PIEs methods were applied for

  19. Standard test method for determination of uranium or plutonium isotopic composition or concentration by the total evaporation method using a thermal ionization mass spectrometer

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2007-01-01

    1.1 This method describes the determination of the isotopic composition and/or the concentration of uranium and plutonium as nitrate solutions by the thermal ionization mass spectrometric (TIMS) total evaporation method. Purified uranium or plutonium nitrate solutions are loaded onto a degassed metal filament and placed in the mass spectrometer. Under computer control, ion currents are generated by heating of the filament(s). The ion beams are continually measured until the sample is exhausted. The measured ion currents are integrated over the course of the run, and normalized to a reference isotope ion current to yield isotopic ratios. 1.2 In principle, the total evaporation method should yield isotopic ratios that do not require mass bias correction. In practice, some samples may require this bias correction. When compared to the conventional TIMS method, the total evaporation method is approximately two times faster, improves precision from two to four fold, and utilizes smaller sample sizes. 1.3 The tot...

  20. Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks

    Science.gov (United States)

    Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C.-Y.; Fujitani, T.; Okano, O.

    2011-01-01

    Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

  1. A comparison using Faraday cups with 10(13) Ω amplifiers and a secondary electron multiplier to measure Os isotopes by negative thermal ionization mass spectrometry.

    Science.gov (United States)

    Wang, Guiqin; Sun, Tiantian; Xu, Jifeng

    2017-10-15

    According to the Johnson-Nyquist noise equation, the value of electron noise is proportional to the square root of the resistor value. This relationship gives a theoretical improvement of 100 in the signal/noise ratio by going from 10(11) Ω to 10(13) Ω amplifiers for Faraday detection in thermal ionization mass spectrometry (TIMS). We measured Os isotopes using static Faraday cups with 10(13) Ω amplifiers in negative thermal ionization mass spectrometry (NTIMS) and compared the results with those obtained with 10(11) Ω amplifiers and by peak-hopping on a single secondary electron multiplier (SEM). We analysed large loads of Os (1 μg) at a range of intensities of (187) OsO3 (0.02-10 mV) in addition to small loads of Os (5-500 pg) to compare the results of the three methods. Using 10(13) Ω amplifiers, the long-term reproducibility determined from Merck Os was (187) Os/(188) Os = 0.1211 ± 0.0086 and 0.120229 ± 0.000034 at 0.02 mV and 10 mV of (187) OsO3 intensities. Meanwhile, the analysed JMC Os loadings of 5 and 500 pg showed (187) Os/(188) Os = 0.10669 ± 0.00036 and 0.106807 ± 0.000023. In comparison, the values measured by the SEM were (187) Os/(188) Os = 0.10704 ± 0.00056 and 0.10690 ± 0.00013. All errors are in 2 standard deviation (SD). Both the accuracy and the precision determined using the 10(13) Ω amplifiers and the SEM are identical when the Os amounts are within 10-50 pg. However, the former analysis time can be shortened by approximately two-thirds. The SEM measurement is still the most precise method for Os amounts 50 pg. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  3. A novel aerosol mass spectrometric approach - Analysis of the organic molecular signature of PM by coupling of thermal EC/OC-carbon analysis to photo-ionization mass spectrometry

    Science.gov (United States)

    Zimmermann, R.; Grabowski, J.; Streibel, T.; Sklorz, M.; Chow, J.

    2012-12-01

    Carbonaceous material in airborne particulate matter (PM) is of increasing interest e.g. due to its adverse health effects and its potential influence on the climate. Its analytical assessment on a molecular level is still very challenging. Hence, analysis of carbonaceous fractions for many studies is often solely carried out by determining sum parameters such as the overall content of organic carbon (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC). The used thermal procedure, however, allows getting additional interesting information: By defining different thermal OC fractions (i.e. temperature steps) also information on the refractory properties of the carbonaceous material is obtained. In this context it is particularly interesting to investigate the release and formation behaviors of the molecular species responsible for the different OC and EC fractions. Thus after initial promising results of pre-studies [1,2] in the current work an EC/OC carbon analyzer (Model DRI 2000) and a homebuilt photo-ionization time-of-flight mass spectrometer (PI-TOFMS) were hyphenated and applied to investigate individual organic compounds especially from the different OC fractions. The carbon analyzer enables the stepwise heating of PM loaded filter samples and provides the sum values of the "carbon" release ("Improve protocol" [2]: OC1 - 120 °C, OC2 - 250°C, OC3 - 450°C OC4 - 550°C). With the on-line coupled PI-TOFMS evolved organic compounds, as released during the thermal program, are detectable in real time. This is possible by MS with soft photo ionization methods (SPI - single photon ionization and REMPI - resonance-enhanced multi photon ionization). Soft ionization suppresses fragmentation upon the ionization step and generates molecular signatures in the MS. The EC/OC-analyzer-PI-TOFMS instrument was applied to several types of PM samples, such as ambient aerosol, emission samples (gasoline/diesel car, wood combustion) or

  4. Ambient aging of rhenium filaments used in thermal ionization mass spectrometry: Growth of oxo-rhenium crystallites and anti-aging strategies

    Directory of Open Access Journals (Sweden)

    Joseph M. Mannion

    2017-01-01

    Full Text Available Degassing is a common preparation technique for rhenium filaments used for thermal ionization mass spectrometric analysis of actinides, including plutonium. Although optimization studies regarding degassing conditions have been reported, little work has been done to characterize filament aging after degassing. In this study, the effects of filament aging after degassing were explored to determine a “shelf-life” for degassed rhenium filaments, and methods to limit filament aging were investigated. Zone-refined rhenium filaments were degassed by resistance heating under high vacuum before exposure to ambient atmosphere for up to 2 months. After degassing the nucleation and preferential growth of oxo-rhenium crystallites on the surface of polycrystalline rhenium filaments was observed by atomic force microscopy and scanning electron microscopy (SEM. Compositional analysis of the crystallites was conducted using SEM-Raman spectroscopy and SEM energy dispersive X-ray spectroscopy, and grain orientation at the metal surface was investigated by electron back-scatter diffraction mapping. Spectra collected by SEM-Raman suggest crystallites are composed primarily of perrhenic acid. The relative extent of growth and crystallite morphology were found to be grain dependent and affected by the dissolution of carbon into filaments during annealing (often referred to as carbonization or carburization. Crystallites were observed to nucleate in region specific modes and grow over time through transfer of material from the surface. Factors most likely to affect the rates of crystallite growth include rhenium substrate properties such as grain size, orientation, levels of dissolved carbon, and relative abundance of defect sites; as well as environmental factors such as length of exposure to oxygen and relative humidity. Thin (∼180 nm hydrophobic films of poly(vinylbenzyl chloride were found to slow the growth of oxo-rhenium crystallites on the filament

  5. Dissociative Ionization and Thermal Decomposition of Cyclopentanone.

    Science.gov (United States)

    Pastoors, Johan I M; Bodi, Andras; Hemberger, Patrick; Bouwman, Jordy

    2017-09-21

    Despite the growing use of renewable and sustainable biofuels in transportation, their combustion chemistry is poorly understood, limiting our efforts to reduce harmful emissions. Here we report on the (dissociative) ionization and the thermal decomposition mechanism of cyclopentanone, studied using imaging photoelectron photoion coincidence spectroscopy. The fragmentation of the ions is dominated by loss of CO, C 2 H 4 , and C 2 H 5 , leading to daughter ions at m/z 56 and 55. Exploring the C 5 H 8 O . + potential energy surface reveals hydrogen tunneling to play an important role in low-energy decarbonylation and probably also in the ethene-loss processes, yielding 1-butene and methylketene cations, respectively. At higher energies, pathways without a reverse barrier open up to oxopropenyl and cyclopropanone cations by ethyl-radical loss and a second ethene-loss channel, respectively. A statistical Rice-Ramsperger-Kassel-Marcus model is employed to test the viability of this mechanism. The pyrolysis of cyclopentanone is studied at temperatures ranging from about 800 to 1100 K. Closed-shell pyrolysis products, namely 1,3-butadiene, ketene, propyne, allene, and ethene, are identified based on their photoion mass-selected threshold photoelectron spectrum. Furthermore, reactive radical species such as allyl, propargyl, and methyl are found. A reaction mechanism is derived incorporating both stable and reactive species, which were not predicted in prior computational studies. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  6. Identification of alkylated phosphates by gas chromatography-mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte.

    Science.gov (United States)

    Weber, Waldemar; Kraft, Vadim; Grützke, Martin; Wagner, Ralf; Winter, Martin; Nowak, Sascha

    2015-05-15

    The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC-MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Electrospray ionization mass spectrometry of metalloporphyrins.

    Science.gov (United States)

    Vandell, V E; Limbach, P A

    1998-03-01

    The magnesium, nickel, copper, zinc and vanadium metalloporphyrins from octaethylporphyrin, etioporphyrin I and tetraphenylporphyrin were characterized using electrospray ionization mass spectrometry (ESI-MS). The ion abundance of each of the porphyrins present in binary mixtures was monitored as a function of the porphyrin concentration and is dependent on the metalloporphyrin oxidation potential. It was found that, for binary mixtures of metalloporphyrins whose oxidation potentials differ by less than 0.1 V, the resulting ion abundance of each species is directly proportional to the concentration of each analyte in the mixture. For binary mixtures whose oxidation potentials differ by more than 0.1 V, relative abundances of the radical cations of each metalloporphyrin are determined by the oxidation potential and concentration of each metalloporphyrin with the analyte of lowest oxidation potential being ionized preferentially. The ability to ionize selectively one porphyrin over another in a binary mixture offers the potential to use ESI-MS for the qualitative analysis of porphyrins present in complex mixtures.

  8. RISK: A Resonance Ionization Mass Spectrometer for Krypton

    Science.gov (United States)

    Strashnov, I.; Blagburn, D. J.; Gilmour, J. D.

    2010-03-01

    A resonance ionization mass spectrometer for krypton (RISK) has been developed. Atoms are released by a step-heating and ionized by pulsed tunable lasers. The sensitivity below 1000 atoms is demonstrated by detecting 81Kr in noncumulate eucrite Stannern.

  9. Substrate-Enhanced Micro Laser Desorption Ionization Mass Spectrometry Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Aerodyne Research, Inc. and the University of Massachusetts at Amherst will collaborate to develop laser desorption ionization (LDI) mass spectrometric analysis of...

  10. Matrix Assisted Ionization Vacuum (MAIV), a New Ionization Method for Biological Materials Analysis Using Mass Spectrometry*

    Science.gov (United States)

    Inutan, Ellen D.; Trimpin, Sarah

    2013-01-01

    The introduction of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) for the mass spectrometric analysis of peptides and proteins had a dramatic impact on biological science. We now report that a wide variety of compounds, including peptides, proteins, and protein complexes, are transported directly from a solid-state small molecule matrix to gas-phase ions when placed into the vacuum of a mass spectrometer without the use of high voltage, a laser, or added heat. This ionization process produces ions having charge states similar to ESI, making the method applicable for high performance mass spectrometers designed for atmospheric pressure ionization. We demonstrate highly sensitive ionization using intermediate pressure MALDI and modified ESI sources. This matrix and vacuum assisted soft ionization method is suitable for the direct surface analysis of biological materials, including tissue, via mass spectrometry. PMID:23242551

  11. Electron Ionization Mass Spectrum of Tellurium Hexafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Richard A.; McNamara, Bruce K.; Barinaga, Charles J.; Peterson, James M.; Govind, Niranjan; Andersen, Amity; Abrecht, David G.; Schwantes, Jon M.; Ballou, Nathan E.

    2015-05-18

    The first electron ionization mass spectrum of tellurium hexafluoride (TeF6) is reported. The starting material was produced by direct fluorination of Te metal or TeO2 with nitrogen trifluoride. Formation of TeF6 was confirmed through cryogenic capture of the tellurium fluorination product and analysis through Raman spectroscopy. The eight natural abundance isotopes were observed for each of the set of fragment ions: TeF5+, TeF4+ TeF3+, TeF2+, TeF1+, and Te+, Te2+. A trend in increasing abundance was observed for the even fluoride bearing ions: TeF1+ < TeF3+ < TeF5+, and a decreasing abundance was observed for the even fragment series: Te(0)+ > TeF2+ > TeF4+ > TeF6+, with the molecular ion TeF6+ not observed at all. Density functional theory based electronic structure calculations were used to calculate optimized ground state geometries of these gas phase species and their relative stabilities explain the trends in the data and the lack of observed signal for TeF6+.

  12. Secondary ionization mass spectrometry analysis in petrochronology: Chapter 7

    Science.gov (United States)

    Schmitt, Axel K.; Vazquez, Jorge A.

    2017-01-01

    The goal of petrochronology is to extract information about the rates and conditions at which rocks and magmas are transported through the Earth’s crust. Garnering this information from the rock record greatly benefits from integrating textural and compositional data with radiometric dating of accessory minerals. Length scales of crystal growth and diffusive transport in accessory minerals under realistic geologic conditions are typically in the range of 1–10’s of μm, and in some cases even substantially smaller, with zircon having among the lowest diffusion coefficients at a given temperature (e.g., Cherniak and Watson 2003). Intrinsic to the compartmentalization of geochemical and geochronologic information from intra-crystal domains is the requirement to determine accessory mineral compositions using techniques that sample at commensurate spatial scales so as to not convolute the geologic signals that are recorded within crystals, as may be the case with single grain or large grain fragment analysis by isotope dilution thermal ionization mass spectrometry (ID-TIMS; e.g., Schaltegger and Davies 2017, this volume; Schoene and Baxter 2017, this volume). Small crystals can also be difficult to extract by mineral separation techniques traditionally used in geochronology, which also lead to a loss of petrographic context. Secondary Ionization Mass Spectrometry, that is SIMS performed with an ion microprobe, is an analytical technique ideally suited to meet the high spatial resolution analysis requirements that are critical for petrochronology (Table 1).

  13. Soft Ionization of Thermally Evaporated Hypergolic Ionic Liquid Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Christine J. [Univ. of California, Berkeley, CA (United States); Liu, Chen-Lin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Harmon, Christopher W. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Strasser, Daniel [Univ. of California, Berkeley, CA (United States); Golan, Amir [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kostko, Oleg [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chambreau, Steven D. [Edwards Air Force Base, ERC Inc., CA (United States); Vaghjiani, Ghanshyam L. [Air Force Research Laboratory, Edwards Air Force Base, CA (United States); Leone, Stephen R. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2011-04-20

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N–]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca–]), are generated by vaporizing ionic liquid submicrometer aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Also, hotoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N] ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~0.3 eV), attributed to reduced internal energy of the isolated ion pairs. Lastly, the method of ionic liquid submicrometer aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally “cooler” source of isolated intact ion pairs in the gas phase compared to effusive sources.

  14. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    Energy Technology Data Exchange (ETDEWEB)

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center (NSRRC); Institute of Chemistry, Hebrew University; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

    2011-07-19

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?]ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  15. Electrospray ionization and matrix assisted laser desorption/ionization mass spectrometry: powerful analytical tools in recombinant protein chemistry

    DEFF Research Database (Denmark)

    Andersen, Jens S.; Svensson, B; Roepstorff, P

    1996-01-01

    Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy is presen......Electrospray ionization and matrix assisted laser desorption/ionization are effective ionization methods for mass spectrometry of biomolecules. Here we describe the capabilities of these methods for peptide and protein characterization in biotechnology. An integrated analytical strategy...

  16. Precise determination of the absolute isotopic abundance ratio and the atomic weight of chlorine in three international reference materials by the positive thermal ionization mass spectrometer-Cs2Cl+-graphite method.

    Science.gov (United States)

    Wei, Hai-Zhen; Jiang, Shao-Yong; Xiao, Ying-Kai; Wang, Jun; Lu, Hai; Wu, Bin; Wu, He-Pin; Li, Qing; Luo, Chong-Guang

    2012-12-04

    Because the variation in chlorine isotopic abundances of naturally occurring chlorine bearing substances is significant, the IUPAC Inorganic Chemistry Division, Commission on Isotopic Abundances and Atomic Weights (CIAAW-IUPAC) decided that the uncertainty of atomic weight of chlorine (A(r)(Cl)) should be increased so that the implied range was related to terrestrial variability in 1999 (Coplen, T. B. Atomic weights of the elements 1999 (IUPAC Technical Report), Pure Appl. Chem.2001, 73(4), 667-683; and then, it emphasized that the standard atomic weights of ten elements including chlorine were not constants of nature but depend upon the physical, chemical, and nuclear history of the materials in 2009 (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396). According to the agreement by CIAAW that an atomic weight could be defined for one specified sample of terrestrial origin (Wieser, M. E.; Coplen, T. B. Pure Appl. Chem.2011, 83(2), 359-396), the absolute isotope ratios and atomic weight of chlorine in standard reference materials (NIST 975, NIST 975a, ISL 354) were accurately determined using the high-precision positive thermal ionization mass spectrometer (PTIMS)-Cs(2)Cl(+)-graphite method. After eliminating the weighing error caused from evaporation by designing a special weighing container and accurately determining the chlorine contents in two highly enriched Na(37)Cl and Na(35)Cl salts by the current constant coulometric titration, one series of gravimetric synthetic mixtures prepared from two highly enriched Na(37)Cl and Na(35)Cl salts was used to calibrate two thermal ionization mass spectrometers in two individual laboratories. The correction factors (i.e., K(37/35) = R(37/35meas)/R(37/35calc)) were obtained from five cycles of iterative calculations on the basis of calculated and determined R((37)Cl/(35)Cl) values in gravimetric synthetic mixtures. The absolute R((37)Cl/(35)Cl) ratios for NIST SRM 975, NIST 975a, and ISL 354 by the precise

  17. Single Photon Thermal Ionization of C60

    Science.gov (United States)

    Hansen, Klavs; Richter, Robert; Alagia, Michele; Stranges, Stefano; Schio, Luca; Salén, Peter; Yatsyna, Vasyl; Feifel, Raimund; Zhaunerchyk, Vitali

    2017-03-01

    We report on experiments which show that C60 can ionize in an indirect, quasithermal boiloff process after absorption of a single photon. The process involves a large number of incoherently excited valence electrons and yields electron spectra with a Boltzmann distribution with temperatures exceeding 104 K . It is expected to be present for other molecules and clusters with a comparatively large number of valence electrons. The astrophysical consequences are briefly discussed.

  18. Method for analyzing the mass of a sample using a cold cathode ionization source mass filter

    Science.gov (United States)

    Felter, Thomas E.

    2003-10-14

    An improved quadrupole mass spectrometer is described. The improvement lies in the substitution of the conventional hot filament electron source with a cold cathode field emitter array which in turn allows operating a small QMS at much high internal pressures then are currently achievable. By eliminating of the hot filament such problems as thermally "cracking" delicate analyte molecules, outgassing a "hot" filament, high power requirements, filament contamination by outgas species, and spurious em fields are avoid all together. In addition, the ability of produce FEAs using well-known and well developed photolithographic techniques, permits building a QMS having multiple redundancies of the ionization source at very low additional cost.

  19. Matrix assisted ionization in vacuum, a sensitive and widely applicable ionization method for mass spectrometry.

    Science.gov (United States)

    Trimpin, Sarah; Inutan, Ellen D

    2013-05-01

    An astonishingly simple new method to produce gas-phase ions of small molecules as well as proteins from the solid state under cold vacuum conditions is described. This matrix assisted ionization vacuum (MAIV) mass spectrometry (MS) method produces multiply charged ions similar to those that typify electrospray ionization (ESI) and uses sample preparation methods that are nearly identical to matrix-assisted laser desorption/ionization (MALDI). Unlike these established methods, MAIV does not require a laser or voltage for ionization, and unlike the recently introduced matrix assisted ionization inlet method, does not require added heat. MAIV-MS requires only introduction of a crystalline mixture of the analyte incorporated with a suitable small molecule matrix compound such as 3-nitrobenzonitrile directly to the vacuum of the mass spectrometer. Vacuum intermediate pressure MALDI sources and modified ESI sources successfully produce ions for analysis by MS with this method. As in ESI-MS, ion formation is continuous and, without a laser, little chemical background is observed. MAIV, operating from a surface offers the possibility of significantly improved sensitivity relative to atmospheric pressure ionization because ions are produced in the vacuum region of the mass spectrometer eliminating losses associated with ion transfer from atmospheric pressure to vacuum. Mechanistic aspects and potential applications for this new ionization method are discussed.

  20. Analytical Properties of Solid-substrate Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Hu, Bin; So, Pui-Kin; Yao, Zhong-Ping

    2013-01-01

    Conventional electrospray ionization mass spectrometry (ESI-MS) uses a capillary for sample loading and ionization. Along with the development of ambient ionization techniques, ESI-MS using noncapillary emitters has attracted more interest in recent years. Following our recent report on ESI-MS using wooden tips ( Anal. Chem. 83, 8201-8207 (2011)), the technique was further investigated and extended in this study. Our results revealed that the wooden tips could serve as a chromatographic column for separation of sample components. Sequential and exhaustive ionization was observed for proteins and salts on wooden tips with salts ionized sooner and proteins later. Nonconductive materials that contain microchannels/pores could be used as tips for ESI-MS analysis with sample solutions loaded to the sharp-ends only, since rapid diffusion of sample solutions by capillary action would enable the tips to become conductive. Tips of inert materials such as bamboo, fabrics, and sponge could be used for sample loading and ionization, while samples such as tissue, mushroom, and bone could form tips to induce ionization for direct analysis with application of a high voltage. [Figure not available: see fulltext.

  1. Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry.

    Science.gov (United States)

    Colizza, Kevin; Mahoney, Keira E; Yevdokimov, Alexander V; Smith, James L; Oxley, Jimmie C

    2016-11-01

    Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression. Graphical Abstract ᅟ.

  2. The average ion charge in the thermal ionization

    Science.gov (United States)

    Kiyokawa, Shuji; Chihara, Junzo

    2017-06-01

    We show verification of our definition previously formulated for the average ion charge ZI of plasmas and liquid metals in the electron-ion model for the case of the thermal ionization. For Rb plasmas of temperatures 5-30 eV and ion density rsI = 5.388 , the form of the electron-ion radial distribution function (RDF) determined by the conventional method shows unphysical behavior just at the moment when the shallow 4d-bound level appears in the plasma state. However, according to our definition of the average ion charge, we show that such unphysical behavior in the RDF of Rb and H plasmas does not exist even at high temperature where the thermal ionization occur.

  3. Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

    Science.gov (United States)

    Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

    2013-11-01

    In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

  4. Subcellular analysis by laser ablation electrospray ionization mass spectrometry

    Science.gov (United States)

    Vertes, Akos; Stolee, Jessica A; Shrestha, Bindesh

    2014-12-02

    In various embodiments, a method of laser ablation electrospray ionization mass spectrometry (LAESI-MS) may generally comprise micro-dissecting a cell comprising at least one of a cell wall and a cell membrane to expose at least one subcellular component therein, ablating the at least one subcellular component by an infrared laser pulse to form an ablation plume, intercepting the ablation plume by an electrospray plume to form ions, and detecting the ions by mass spectrometry.

  5. Development of a Portable Single Photon Ionization-Photoelectron Ionization Time-of-Flight Mass Spectrometer

    Directory of Open Access Journals (Sweden)

    Yunguang Huang

    2015-01-01

    Full Text Available A vacuum ultraviolet lamp based single photon ionization- (SPI- photoelectron ionization (PEI portable reflecting time-of-flight mass spectrometer (TOFMS was designed for online monitoring gas samples. It has a dual mode ionization source: SPI for analyte with ionization energy (IE below 10.6 eV and PEI for IE higher than 10.6 eV. Two kinds of sampling inlets, a capillary inlet and a membrane inlet, are utilized for high concentration and trace volatile organic compounds, respectively. A mass resolution of 1100 at m/z 64 has been obtained with a total size of 40 × 31 × 29 cm, the weight is 27 kg, and the power consumption is only 70 W. A mixture of benzene, toluene, and xylene (BTX, SO2, and discharging products of SF6 were used to test its performance, and the result showed that the limit of quantitation for BTX is as low as 5 ppbv (S/N = 10 : 1 with linear dynamic ranges greater than four orders of magnitude. The portable TOFMS was also evaluated by analyzing volatile organic compounds from wine and decomposition products of SF6 inside of a gas-insulated switchgear.

  6. Electrospray ionizer for mass spectrometry of aerosol particles

    Energy Technology Data Exchange (ETDEWEB)

    He, Siqin; Hogan, Chris; Li, Lin; Liu, Benjamin Y. H.; Naqwi, Amir; Romay, Francisco

    2017-09-19

    A device and method are disclosed to apply ESI-based mass spectroscopy to submicrometer and nanometer scale aerosol particles. Unipolar ionization is utilized to charge the particles in order to collect them electrostatically on the tip of a tungsten rod. Subsequently, the species composing the collected particles are dissolved by making a liquid flow over the tungsten rod. This liquid with dissolved aerosol contents is formed into highly charged droplets, which release unfragmented ions for mass spectroscopy, such as time-of-flight mass spectroscopy. The device is configured to operate in a switching mode, wherein aerosol deposition occurs while solvent delivery is turned off and vice versa.

  7. Experimental factors controlling analyte ion generation in laser desorption/ionization mass spectrometry on porous silicon.

    Science.gov (United States)

    Kruse, R A; Li, X; Bohn, P W; Sweedler, J V

    2001-08-01

    Desorption/ionization on porous silicon (DIOS) is a relatively new laser desorption/ionization technique for the direct mass spectrometric analysis of a wide variety of samples without the requirement of a matrix. Porous silicon substrates were fabricated using the recently developed nonelectrochemical H2O2-metal-HF etching as a versatile platform for investigating the effects of morphology and physical properties of porous silicon on DIOS-MS performance. In addition, laser wavelength, mode of ion detection, pH, and solvent contributions to the desorption/ionization process were studied. Other porous substrates such as GaAs and GaN, with similar surface characteristics but differing in thermal and optical properties from porous silicon, allowed the roles of surface area, optical absorption, and thermal conductivities in the desorption/ionization process to be investigated. Among the porous semiconductors studied, only porous silicon has the combination of large surface area, optical absorption, and thermal conductivity required for efficient analyte ion generation under the conditions studied. In addition to these substrate-related factors, surface wetting, determined by the interaction of deposition solvent with the surface, and charge state of the peptide were found to be important in determining ion generation efficiency.

  8. Proposal on dynamic correction method for resonance ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Noto, Takuma, E-mail: noto.takuma@d.mbox.nagoya-u.ac.jp; Tomita, Hideki [Nagoya University, Department of Quantum Engineering (Japan); Richter, Sven; Schneider, Fabian; Wendt, Klaus [Johannes Gutenberg University Mainz, Institute of Physics (Germany); Iguchi, Tetsuo; Kawarabayashi, Jun [Nagoya University, Department of Quantum Engineering (Japan)

    2013-04-15

    For high precision and accuracy in isotopic ratio measurement of transuranic elements using laser ablation assisted resonance ionization mass spectrometry, a dynamic correction method based on correlation of ion signals with energy and timing of each laser pulse was proposed. The feasibility of this dynamic correction method was investigated through the use of a programmable electronics device for fast acquisition of the energy and timing of each laser pulse.

  9. Rapid fingerprinting of lignin by ambient ionization high resolution mass spectrometry and simplified data mining.

    Science.gov (United States)

    Crawford, Elizabeth A; Gerbig, Stefanie; Spengler, Bernhard; Volmer, Dietrich A

    2017-11-22

    Ambient ionization techniques are typically used to analyze samples in their native states with minimal or no sample pretreatment prior to mass spectrometric (MS) analysis. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) were systematically investigated in this work for direct solid analysis of depolymerized lignin samples, with the goal of rapidly fingerprinting these samples, to efficiently characterize the subunits of this renewable energy source. High resolution MS was required for enhanced selectivity in this study due to the inherent structural complexity of lignin. DESI provided results across a broader mass range (up to m/z 700) than DART and also ionized saturated compounds of low oxygen-to-carbon (O/C) ratios and low double bond equivalents (DBE). While DART detected the same core lignin monomeric and dimeric compounds as seen with DESI and electrospray ionization (ESI), results were restricted to a narrower mass range to m/z 500, due to thermal degradation and losses of methoxy groups. In contrast to DESI and ESI, the DART spectra were nearly void of saturated components. On a structural level, the core lignin compounds were visually fingerprinted and ionization method performances critically assessed by employing simplified Kendrick-based data mining approaches. A novel simplified data visualization approach was developed in this work based on modified Kendrick mass defect (KMD) filtering for lignin subunits and plotting the mass defect values against the degree of unsaturation. Direct visualization of monomeric, dimeric and trimeric lignin species was simplified by the KMD separation plots, easily allowing the core lignin compounds to be visually identified and compared. Modified KMD bases, namely methoxy and phenol bases, which represent monomer-specific lignin constituents, were successfully used to classify and group the complex mixture of lignin species. Further separation of methoxy-related lignin species was

  10. A comparative study of 129I content in environmental standard materials IAEA-375, NIST SRM 4354 and NIST SRM 4357 by Thermal Ionization Mass Spectrometry and Accelerator Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Olson, John; Adamic, Mary; Snyder, Darin; Brookhart, Jacob; Hahn, Paula; Watrous, Matthew

    2016-11-01

    Iodine environmental measurements have consistently been backed up in the literature by standard materials like IAEA-375, Chernobyl Soil. There are not many other sources of a certified reference material for 129I content for mass spectrometry measurements. Some that have been found in the literature include NIST-4354 and NIST-4357. They are still available at the time of this writing. They don’t have certified content or isotopic values. There has been some work in the literature to show that iodine is present, but there hasn’t been enough to establish a consensus value. These materials have been analyzed at INL through two separate mass spectrometry techniques. They involve a combustion method of the starting material in oxygen, followed by TIMS analysis and a leaching preparation analyzed by accelerator mass spectrometry. Combustion/TIMS preparation of NIST SRM-4354 resulted in a 129I/127I ratio of 1.92 x 10-6 which agrees with AMS measurements which measured the 129I/127I ratio to be 1.93 x 10-6.

  11. Characterization of a Continuous Wave Laser for Resonance Ionization Mass Spectroscopy Analysis in Nuclear Forensics

    Science.gov (United States)

    2015-06-01

    OF A CONTINUOUS WAVE LASER FOR RESONANCE IONIZATION MASS SPECTROSCOPY ANALYSIS IN NUCLEAR FORENSICS by Sunny G. Lau June 2015 Thesis...IONIZATION MASS SPECTROSCOPY ANALYSIS IN NUCLEAR FORENSICS 5. FUNDING NUMBERS 6. AUTHOR(S) Sunny G. Lau 7. PERFORMING ORGANIZATION NAME(S) AND...200 words) The application of resonance ionization mass spectroscopy (RIMS) to nuclear forensics involves the use of lasers to selectively ionize

  12. Identification of molecules in graphite furnace by laser ionization time-of-flight mass spectrometry: sulfur and chlorine containing compounds

    CSIR Research Space (South Africa)

    Raseleka, RM

    2004-01-01

    Full Text Available An electro thermal vaporizer (ETV) coupled to a time-of-flight mass spectrometer (TOF-MS) with laser ionization (LI) was applied to the identification of molecules from sulphur and chlorine matrices in the furnace. An interface was developed...

  13. Iron oxide nanomatrix facilitating metal ionization in matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Obena, Rofeamor P; Lin, Po-Chiao; Lu, Ying-Wei; Li, I-Che; del Mundo, Florian; Arco, Susan dR; Nuesca, Guillermo M; Lin, Chung-Chen; Chen, Yu-Ju

    2011-12-15

    The significance and epidemiological effects of metals to life necessitate the development of direct, efficient, and rapid method of analysis. Taking advantage of its simple, fast, and high-throughput features, we present a novel approach to metal ion detection by matrix-functionalized magnetic nanoparticle (matrix@MNP)-assisted MALDI-MS. Utilizing 21 biologically and environmentally relevant metal ion solutions, the performance of core and matrix@MNP against conventional matrixes in MALDI-MS and laser desorption ionization (LDI) MS were systemically tested to evaluate the versatility of matrix@MNP as ionization element. The matrix@MNPs provided 20- to >100-fold enhancement on detection sensitivity of metal ions and unambiguous identification through characteristic isotope patterns and accurate mass (potentials (IP), we formulated a metal ionization mechanism model, alluding to the role of exciton pooling in matrix@MNP-assisted MALDI-MS. Moreover, the detection of Cu in spiked tap water demonstrated the practicability of this new approach as an efficient and direct alternative tool for fast, sensitive, and accurate determination of trace metal ions in real samples.

  14. Cold-spray ionization mass spectrometry: applications in structural coordination chemistry.

    Science.gov (United States)

    Yamaguchi, Kentaro

    2013-01-01

    Electrospray ionization (ESI)-mass spectrometry (MS) is generally used for the characterization of labile supramolecules in which non-covalent bonding interactions are predominant. However, molecular ions are not detected in many cases because of their instability, and even if such ions are detected, thermal decomposition generates fragment ions that also appear in the mass spectrum. Cold-spray ionization (CSI) is designed for the MS detection of labile organic species. It is used to analyze the structures of biomolecular complexes and labile organic species in solution. The method, a variant of ESI-MS, operates at low temperature, allowing simple and precise characterization of labile non-covalent complexes that are difficult or impossible to observe by conventional MS techniques. The CSI method is particularly suitable for elucidating the structures of labile organometallic compounds in solution as it offers a means to investigate the dynamic behavior of unstable molecules and/or labile clusters in solution. Various labile organic compounds are analyzed by using the CSI method in the field of organic chemistry. CSI-MS is also used to investigate the behavior of aggregated steroid compounds, namely, bisguanidinobenzene-benzoic acid complexes, in solution. This method is a powerful tool for analyzing the equilibria of multiply linked self-assembling catenanes in solution. Its application to unstable and complex supramolecules will be shown. We have developed an effective ionization method that uses metal-complex-based ionization probes containing 2,6-bis(oxazolinyl) pyridine (pybox) ligands. Using this method, we were able to detect multiply charged ions of target molecules. This method was proven to effectively ionize large complex molecules, including biomolecules and various supramolecules, as well as carbon clusters, such as fullerenes. Moreover, isotope-labeled pybox-La complexes were used to clearly detect isotopic labeling shifts. Their applications to

  15. Matrix-assisted laser desorption/ionization imaging mass spectrometry.

    Science.gov (United States)

    Zaima, Nobuhiro; Hayasaka, Takahiro; Goto-Inoue, Naoko; Setou, Mitsutoshi

    2010-01-01

    Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a powerful tool that enables the simultaneous detection and identification of biomolecules in analytes. MALDI-imaging mass spectrometry (MALDI-IMS) is a two-dimensional MALDI-mass spectrometric technique used to visualize the spatial distribution of biomolecules without extraction, purification, separation, or labeling of biological samples. MALDI-IMS has revealed the characteristic distribution of several biomolecules, including proteins, peptides, amino acids, lipids, carbohydrates, and nucleotides, in various tissues. The versatility of MALDI-IMS has opened a new frontier in several fields such as medicine, agriculture, biology, pharmacology, and pathology. MALDI-IMS has a great potential for discovery of unknown biomarkers. In this review, we describe the methodology and applications of MALDI-IMS for biological samples.

  16. Monitoring of wine aging process by electrospray ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    Alexandra Christine Helena Frankland Sawaya

    2011-09-01

    Full Text Available The characterization of wine samples by direct insertion electrospray ionization mass spectrometry (ESI-MS, without pre-treatment or chromatographic separation, in a process denominated fingerprinting, has been applied to several samples of wine produced with grapes of the Pinot noir, Merlot and Cabernet Sauvignon varieties from the state o Rio Grande do Sul, in Brazil. The ESI-MS fingerprints of the samples detected changes which occurred during the aging process in the three grape varieties. Principal Component Analysis (PCA of the negative ion mode fingerprints was used to group the samples, pinpoint the main changes in their composition, and indicate marker ions for each group of samples.

  17. Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions

    Science.gov (United States)

    Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

    2017-07-01

    Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)- complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)]- and [MAII-H+(HNO3)]- ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n]3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins.

  18. Geoporphyrin analysis using electrospray ionization-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Van Berkel, G.J.; Quinones, M.A.; Quirke, J.M.E. (Oak Ridge National Laboratory, Oak Ridge, TN (USA). Analytical Chemistry Division)

    The utility of electrospray ionization combined with mass spectrometry (ES-MS) for the analysis of free-base, nickel and vanadyl geoporphyrins is demonstrated. In positive ion mode, free-base alkyl-substituted porphyrins are detected as the protonated molecule, (M + H)[sup +], while the nickel and vanadyl chelates of these same porphyrins are observed as their radical cations, M[sup .+], as is chlorophyll a. Detection of free-base octaethylporphyrin (OEP) using continuous infusion at 1-5 [mu]L/min required sampling as little as 1 fmol of material, while at these same flow rates 18 fmol of OEP could be detected via flow injection. Detection of 500 fmol of mesoporphyrin IX dimethyl ester injected is demonstrated using on-line reverse-phase microbore-HPLC at a solvent flow rate of 40 [mu]L/min. ES-MS is shown to be well-suited for geoporphyrin molecular weight and carbon number determination since no fragment ions are produced by this ionization process. Accuracy in determining the relative abundances of porphyrins within geoporphyrin mixtures is demonstrated using standard solutions containing known molar ratios of OEP and free-base etioporphyrin-III (etio-III) and a total free-base porphyrin mixture isolated from Gilsonite bitumen. On-line separation/mass spectrometric detection of free-base and nickel geoporphyrin mixtures using reverse-phase microbore-HPLC/ES/MS is demonstrated with Gilsonite porphyrins. 51 refs., 11 figs.

  19. Electrostatic thermal noise in a weakly ionized collisional plasma

    Science.gov (United States)

    Martinović, M. M.; Zaslavsky, A.; Maksimović, M.; Å egan, S.

    2017-01-01

    Quasi-thermal noise (QTN) spectroscopy is a plasma diagnostic technique which enables precise measurements of local electron velocity distribution function moments. This technique is based on measurements and analysis of voltage fluctuations at the antenna terminals, induced by thermal motion of charged particles. In this work, we accommodate, for the first time, this technique to weakly ionized collisional plasmas. It turns out that the QTN spectrum is modified both at low frequencies, increasing the level of power spectrum, and around the plasma frequency, where collisions damp the plasma oscillations and therefore broaden and reduce the amplitude of so called "plasma peak," while the spectrum at high frequencies is nearly unmodified compared to the collisionless case. Based on these results, we show that QTN spectroscopy enables independent measurements of the collision frequency, electron density, and temperature, provided the ratio of collision frequency to plasma frequency is ν/ωp˜0.1. The method presented here can be used for precise estimation of plasma parameters in laboratory devices and unmagnetized ionospheres, while application in the ionosphere of Earth is possible but limited to small, low-frequency range due to magnetic field influence.

  20. Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

    Directory of Open Access Journals (Sweden)

    Shibdas Banerjee

    2012-01-01

    Full Text Available The Electrospray Ionization (ESI is a soft ionization technique extensively used for production of gas phase ions (without fragmentation of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

  1. All-solid-state deep ultraviolet laser for single-photon ionization mass spectrometry.

    Science.gov (United States)

    Yuan, Chengqian; Liu, Xianhu; Zeng, Chenghui; Zhang, Hanyu; Jia, Meiye; Wu, Yishi; Luo, Zhixun; Fu, Hongbing; Yao, Jiannian

    2016-02-01

    We report here the development of a reflectron time-of-flight mass spectrometer utilizing single-photon ionization based on an all-solid-state deep ultraviolet (DUV) laser system. The DUV laser was achieved from the second harmonic generation using a novel nonlinear optical crystal KBe2BO3F2 under the condition of high-purity N2 purging. The unique property of this laser system (177.3-nm wavelength, 15.5-ps pulse duration, and small pulse energy at ∼15 μJ) bears a transient low power density but a high single-photon energy up to 7 eV, allowing for ionization of chemicals, especially organic compounds free of fragmentation. Taking this advantage, we have designed both pulsed nanospray and thermal evaporation sources to form supersonic expansion molecular beams for DUV single-photon ionization mass spectrometry (DUV-SPI-MS). Several aromatic amine compounds have been tested revealing the fragmentation-free performance of the DUV-SPI-MS instrument, enabling applications to identify chemicals from an unknown mixture.

  2. New Types of Ionization Sources for Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    None

    2008-12-01

    The purpose of this Cooperative Research and Development Agreement (CRADA) between UT-Battelle (Contractor) and MDS Sciex (Participant) and ESA, Inc. (Participant) is to research, develop and apply new types of ionization sources and sampling/inlet systems for analytical mass spectrometry making use of the Participants state-of-the-art atmospheric sampling mass spectrometry electrochemical cell technology instrumentation and ancillary equipment. The two overriding goals of this research project are: to understand the relationship among the various instrumental components and operational parameters of the various ion sources and inlet systems under study, the chemical nature of the gases, solvents, and analytes in use, and the nature and abundances of the ions ultimately observed in the mass spectrometer; and to develop new and better analytical and fundamental applications of these ion sources and inlet systems or alternative sources and inlets coupled with mass spectrometry on the basis of the fundamental understanding obtained in Goal 1. The end results of this work are expected to be: (1) an expanded utility for the ion sources and inlet systems under study (such as the analysis of new types of analytes) and the control or alteration of the ionic species observed in the gas-phase; (2) enhanced instrument performance as judged by operational figures-of-merit such as dynamic range, detection limits, susceptibility to matrix signal suppression and sensitivity; and (3) novel applications (such as surface sampling with electrospray) in both applied and fundamental studies. The research projects outlined herein build upon work initiated under the previous CRADA between the Contractor and MDS Sciex on ion sources and inlet systems for mass spectrometry. Specific ion source and inlet systems for exploration of the fundamental properties and practical implementation of these principles are given.

  3. Electrostatic-spray ionization mass spectrometry sniffing for perfume fingerprinting.

    Science.gov (United States)

    Tobolkina, Elena; Qiao, Liang; Xu, Guobin; Girault, Hubert H

    2013-11-15

    The perfume market is growing significantly, and it is easy to find imitative fragrances of probably all types of perfume. Such imitative fragrances are usually of lower quality than the authentic ones, creating a possible threat for perfume companies. Therefore, it is important to develop efficient chemical analysis techniques to screen rapidly perfume samples. Electrostatic-spray ionization (ESTASI) was used to analyze directly samples sprayed or deposited on different types of paper. A linear ion trap mass spectrometer was used to detect the ions produced by ESTASI with a modified extended transfer capillary for 'sniffing' ions from the paper. Several commercial perfumes and a model perfume were analyzed by ESTASI-sniffing. The results obtained by paper ESTASI-MS of commercial fragrances were compared with those obtained from ESI-MS. In addition, a commercial fragrance was first nebulized on the hand and then soaked up by blotting paper, which was afterwards placed on an insulating plate for ESTASI-MS analysis. Analysis of peptides and proteins was also performed to show that the paper ESTASI-MS could be used for samples with very different molecular masses. Paper ESTASI-MS yields a rapid fingerprinting characterization of perfume fragrances, avoiding time-consuming sample-preparation steps, and thereby performing a rapid screening in a few seconds. Copyright © 2013 John Wiley & Sons, Ltd.

  4. Dehydrodimerization of pterostilbene during electrospray ionization mass spectrometry

    KAUST Repository

    Raji, Misjudeen

    2013-04-30

    RATIONALE Pterostilbene is a member of the hydroxystilbene family of compounds commonly found in plants such as blueberry and grapes. During the analysis of this compound by electrospray ionization mass spectrometry (ESI-MS), an ion was observed that corresponds to the dehydrodimer of pterostilbene in mass-to-charge ratio. Since such unexpected dimerization may lead to decreased monomer signal during quantitative analysis, it was of interest to identify the origin and structure of the observed pterostilbene dimer and examine the experimental conditions that influence its formation. METHODS Liquid Chromatography/Mass Spectrometry (LC/MS), Nuclear Magnetic Resonance (NMR), and High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) were used to examine the origin of the dimerization products. The structure of the formed pterostilbene dimer was examined by performing MSn analysis on the dimer ion. Effects of solvent composition, analyte concentration, radical scavenger, and other experimental conditions on the dimerization were also studied. RESULTS LC/MS and NMR analyses clearly showed that the starting solution did not contain the pterostilbene dimer. Solvent type and radical scavenger concentration were found to have pronounced effects on the dimer formation. Particularly, presence of acetonitrile or ammonium acetate had favorable effects on the extent of dimerization during ESI-MS analysis whereas hydroquinone and butylated hydroquinone had negative effects. Dimer formation decreased at high flow rates and when fused-silica capillary was used as the spray needle. CONCLUSIONS The data indicate that this dimerization occurs as a result of solution-phase electrochemical reactions taking place during the electrospray process. A possible structure for this dimer was proposed based on the MSn analysis and was similar to that of the enzymatically derived pterostilbene dehydrodimer already reported in the literature. Copyright © 2013 John Wiley & Sons, Ltd

  5. Role of opposite charges in protein electrospray ionization mass spectrometry.

    Science.gov (United States)

    Samalikova, Maria; Grandori, Rita

    2003-09-01

    The conformation dependence of protein spectra recorded by electrospray ionization mass spectrometry (ESI-MS) is an interesting and useful phenomenon, whose origin is still the object of debate. Different mechanisms have been invoked in the attempt to explain the lower charge state of folded versus unfolded protein ions in ESI-MS, such as electrostatic repulsions, solvent accessibility, charge availability, and native-like interactions. In this work we try to subject to direct experimental test the hypothesis that conformation-dependent neutralization of charges with polarity opposite to the net charge of the protein ion could play a critical role in such an effect. We present results of time-of-flight nano-ESI-MS on the peptide angiotensin II, indicating that negative charges of carboxylate groups can contribute to spectra recorded in positive-ion mode when stabilized by favorable electrostatic interactions, which is the central assumption of our hypothesis. Comparison of horse and spermwhale myoglobin (Mb) shows that changing the total number of basic residues within a given three-dimensional structure shifts the charge-state distribution (CSD) of the folded protein in positive-ion mode. This result appears to be in contrast to models in which electrostatic repulsions or availability of charges in the ESI droplets represent the limiting factor for the ionization of folded protein ions in ESI-MS. At the same time, it suggests a role of acidic residues in conformational effects in positive-ion mode. Furthermore, an attempt is made to rationalize those cases in which, in contrast, the main charge state observed in ESI-MS under non-denaturing conditions deviates considerably from the net charge expected on the basis of the amino-acid composition. These cases usually correspond to proteins with quite balanced content in basic and acidic residues, suggesting that this might be a factor influencing their charging behavior in ESI-MS. Experiments on mutants of

  6. Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

    Science.gov (United States)

    Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

    2017-06-01

    Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. [Figure not available: see fulltext.

  7. Modeling of Plutonium Ionization Probabilities for Use in Nuclear Forensic Analysis by Resonance Ionization Mass Spectrometry

    Science.gov (United States)

    2016-12-01

    DISTRIBUTION CODE A 13. ABSTRACT (maximum 200 words) Recent advancements in nuclear forensics have enabled the use of lasers via resonance ...release. Distribution is unlimited. MODELING OF PLUTONIUM IONIZATION PROBABILITIES FOR USE IN NUCLEAR FORENSIC ANALYSIS BY RESONANCE IONIZATION...bandwidth, irradiance, relative timing and spatial distribution all of which allow for optimization of the RIMS performance [6]. The LION system uses

  8. Cold-spray ionization mass spectrometry: principle and applications.

    Science.gov (United States)

    Yamaguchi, Kentaro

    2003-05-01

    A direct solution analysis method, cold-spray ionization (CSI) mass spectrometry (MS), a variant of electrospray (ESI) MS operating at low temperature (ca -80 to 10 degrees C), allows the facile and precise characterization of labile organic species, especially those in which non-covalent bonding interactions are prominent. We applied this method to investigations of the solution structures of many labile organic species, including unstable reagents and reaction intermediates, asymmetric catalysts, supramolecules and even primary biomolecules. Remarkable analytical results were obtained for highly ordered supramolecules using the CSI method. Whereas conventional ESI is not applicable to these compounds because of their instability to heat and/or air, CSI affords multiply charged molecular ions with many solvent molecules attached. Investigation of the constitution of Grignard reagents in solution is extremely challenging, but CSI-MS allowed us to identify one of the key structures in THF solution. Recently, this method was adopted for investigations of the solution structures of primary biomolecules such as nucleosides, amino acids, sugars and lipids, revealing singly charged Na(+) adducts of large clusters (chain structures), presumably linked by non-covalent interactions, including hydrogen bonding and/or hydrophobic interactions. The principle of the CSI method and applications of the method to a wide variety of labile organic species and primary biomolecules in solution are described. Copyright 2003 John Wiley & Sons, Ltd.

  9. Characterization of nonpolar lipids and steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Z; Daiya, S; Kenttämaa, Hilkka I

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H{sub 2}O){sup +} chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H{sub 2}O) upon reaction with the ClMn(H{sub 2}O){sup +} ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H{sub 2}O ions, but less abundant adduct-2H{sub 2}O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusively the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H{sub 2}O){sup +} chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.

  10. Chemistry of Aliphatic Unconjugated Nitramines. Part 7. Interrelations between the Thermal, Photochemical and Mass Spectral Fragmentation of RDX,

    Science.gov (United States)

    The mass spectral fragmentation of RDX and HMX has been described in terms of their metastable transitions, mass measurements and ionization...efficiency curves. The ring migration of an NO2 group is noted. The known interrelation between the thermal, photochemical and mass spectral fragmentation of

  11. Gas chromatography/chemical ionization triple quadrupole mass spectrometry analysis of anabolic steroids: ionization and collision-induced dissociation behavior.

    Science.gov (United States)

    Polet, Michael; Van Gansbeke, Wim; Van Eenoo, Peter; Deventer, Koen

    2016-02-28

    The detection of new anabolic steroid metabolites and new designer steroids is a challenging task in doping analysis. Switching from electron ionization gas chromatography triple quadrupole mass spectrometry (GC/EI-MS/MS) to chemical ionization (CI) has proven to be an efficient way to increase the sensitivity of GC/MS/MS analyses and facilitate the detection of anabolic steroids. CI also extends the possibilities of GC/MS/MS analyses as the molecular ion is retained in its protonated form due to the softer ionization. In EI it can be difficult to find previously unknown but expected metabolites due to the low abundance or absence of the molecular ion and the extensive (and to a large extent unpredictable) fragmentation. The main aim of this work was to study the CI and collision-induced dissociation (CID) behavior of a large number of anabolic androgenic steroids (AAS) as their trimethylsilyl derivatives in order to determine correlations between structures and CID fragmentation. Clarification of these correlations is needed for the elucidation of structures of unknown steroids and new metabolites. The ionization and CID behavior of 65 AAS have been studied using GC/CI-MS/MS with ammonia as the reagent gas. Glucuronidated AAS reference standards were first hydrolyzed to obtain their free forms. Afterwards, all the standards were derivatized to their trimethylsilyl forms. Full scan and product ion scan analyses were used to examine the ionization and CID behavior. Full scan and product ion scan analyses revealed clear correlations between AAS structure and the obtained mass spectra. These correlations were confirmed by analysis of multiple hydroxylated, methylated, chlorinated and deuterated analogs. AAS have been divided into three groups according to their ionization behavior and into seven groups according to their CID behavior. Correlations between fragmentation and structure were revealed and fragmentation pathways were postulated. Copyright © 2016 John Wiley

  12. Laser vaporization/ionization interface for coupling microscale separation techniques with mass spectrometry

    Science.gov (United States)

    Yeung, E.S.; Chang, Y.C.

    1999-06-29

    The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent. 8 figs.

  13. Laser vaporization/ionization interface for coupling microscale separation techniques with mass spectrometry

    Science.gov (United States)

    Yeung, Edward S.; Chang, Yu-chen

    1999-06-29

    The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent.

  14. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    Energy Technology Data Exchange (ETDEWEB)

    Isselhardt, Brett H. [Univ. of California, Berkeley, CA (United States)

    2011-09-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

  15. Determination of equilibrium composition of thermally ionized monoatomic gas under different physical conditions

    Science.gov (United States)

    Romanova, M. S.; Rydalevskaya, M. A.

    2017-05-01

    Perfect gas mixtures that result from thermal ionization of spatially and chemically homogeneous monoatomic gases are considered. Equilibrium concentrations of the components of such mixtures are determined using integration over the momentum space and summation with respect to energy levels of the distribution functions that maximize the entropy of system under condition for constancy of the total number of nuclei and electrons. It is demonstrated that such a method allows significant simplification of the calculation of the equilibrium composition for ionized mixtures at different temperatures and makes it possible to study the degree of ionization of gas versus gas density and number in the periodic table of elements.

  16. Reproducing impact ionization mass spectra of E and F ring ice grains at different impact speeds

    Science.gov (United States)

    Klenner, F.; Reviol, R.; Postberg, F.

    2017-09-01

    As impact speeds of E and F ring ice grains impinging onto the target of impact ionization mass spectrometers in space can vary greatly, the resulting cationic or anionic mass spectra can have very different appearances. The mass spectra can be accurately reproduced with an analog experimental setup IR-FL-MALDI-ToF-MS (Infrared Free Liquid Matrix Assisted Laser Desorption and Ionization Time of Flight Mass Spectrometry). We compare mass spectra of E and F ring ice grains taken by the Cosmic Dust Analyzer (CDA) onboard Cassini recorded at different impact speeds with our analog spectra and prove the capability of the analog experiment.

  17. Characterization of Microdialysis Acidification for Capillary Isoelectric Focusing Microelectrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Liyu (ASSOC WESTERN UNIVERSITY); Lee, Cheng S.(UNIVERSITY OF MARYLAND); Hofstadler, Steven A.(BATTELLE (PACIFIC NW LAB)); Smith, Richard D.(BATTELLE (PACIFIC NW LAB))

    1998-01-01

    A microdialysis junction, based on a microdialysis membrane connecting a separate capillary and a short, sharply tapered microelectrospray emitter capillary, is demonstrated for on-line combination of capillary isoelectric focusing (CIEF) with electrospray ionization mass spectrometry (ESI-MS).

  18. Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

    Directory of Open Access Journals (Sweden)

    Shu Taira, Kenji Kitajima, Hikaru Katayanagi, Eiichiro Ichiishi and Yuko Ichiyanagi

    2009-01-01

    Full Text Available We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm and developed nanoparticle-assited laser desorption/ionization (nano-PALDI mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB, 4-hydroxy-α-cinnamic acid (CHCA and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

  19. High-Speed Tandem Mass Spectrometric in Situ Imaging by Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Short, Joshua TL; Carson, James P.; Cha, Jeeyeon; Dey, Sudhansu K.; Yang, Pengxiang; Prieto Conaway, Maria C.; Laskin, Julia

    2013-10-15

    Nanospray desorption electrospray ionization (nano-DESI) combined with tandem mass spectrometry (MS/MS), high-resolution mass analysis (m/m=17,500 at m/z 200), and rapid spectral acquisition enabled simultaneous imaging and identification of more than 300 molecules from 92 selected m/z windows (± 1 Da) with a spatial resolution of better than 150 um. Uterine sections of implantation sites on day 6 of pregnancy were analyzed in the ambient environment without any sample pre-treatment. MS/MS imaging was performed by scanning the sample under the nano-DESI probe at 10 um/s while acquiring higher-energy collision-induced dissociation (HCD) spectra for a targeted inclusion list of 92 m/z values at a rate of ~6.3 spectra/s. Molecular ions and their corresponding fragments, separated using high-resolution mass analysis, were assigned based on accurate mass measurement. Using this approach, we were able to identify and image both abundant and low-abundance isobaric species within each m/z window. MS/MS analysis enabled efficient separation and identification of isobaric sodium and potassium adducts of phospholipids. Furthermore, we identified several metabolites associated with early pregnancy and obtained the first 2D images of these molecules.

  20. Thermal Mass & Dynamic Effects Danish Building Regulation

    DEFF Research Database (Denmark)

    Le Dreau, Jerome; Selman, Ayser Dawod; Heiselberg, Per

    will focus on three main aspects: ♦ Assess the robustness of the monthly calculation method by varying the input parameters (Part 3) ♦ Better take into consideration the thermal mass in the actual tool by updating the utilisation factors used for the calculation of cooling and heating (Part 3) ♦ Find...... a method to evaluate night-time ventilation in the monthly calculation (Part 4)...

  1. Reduced Sampling Size with Nanopipette for Tapping-Mode Scanning Probe Electrospray Ionization Mass Spectrometry Imaging.

    Science.gov (United States)

    Kohigashi, Tsuyoshi; Otsuka, Yoichi; Shimazu, Ryo; Matsumoto, Takuya; Iwata, Futoshi; Kawasaki, Hideya; Arakawa, Ryuichi

    2016-01-01

    Mass spectrometry imaging (MSI) with ambient sampling and ionization can rapidly and easily capture the distribution of chemical components in a solid sample. Because the spatial resolution of MSI is limited by the size of the sampling area, reducing sampling size is an important goal for high resolution MSI. Here, we report the first use of a nanopipette for sampling and ionization by tapping-mode scanning probe electrospray ionization (t-SPESI). The spot size of the sampling area of a dye molecular film on a glass substrate was decreased to 6 μm on average by using a nanopipette. On the other hand, ionization efficiency increased with decreasing solvent flow rate. Our results indicate the compatibility between a reduced sampling area and the ionization efficiency using a nanopipette. MSI of micropatterns of ink on a glass and a polymer substrate were also demonstrated.

  2. Analysis of solvent dyes in refined petroleum products by electrospray ionization mass spectrometry

    Science.gov (United States)

    Rostad, C.E.

    2010-01-01

    Solvent dyes are used to color refined petroleum products to enable differentiation between gasoline, diesel, and jet fuels. Analysis for these dyes in the hydrocarbon product is difficult due to their very low concentrations in such a complex matrix. Flow injection analysis/electrospray ionization/mass spectrometry in both negative and positive mode was used to optimize ionization of ten typical solvent dyes. Samples of hydrocarbon product were analyzed under similar conditions. Positive electrospray ionization produced very complex spectra, which were not suitably specific for targeting only the dyes. Negative electrospray ionization produced simple spectra because aliphatic and aromatic moieties were not ionized. This enabled screening for a target dye in samples of hydrocarbon product from a spill.

  3. Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

    Science.gov (United States)

    Harris, Glenn A.

    Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in Chapter 1. Chapter 2 presents the first investigations into the atmospheric pressure ion transport

  4. Thermal conductivity of mass-graded graphene flakes

    OpenAIRE

    Cheh, Jigger; Zhao, Hong

    2011-01-01

    In this letter we study thermal conduction in mass-graded graphene flakes by nonequilibrium molecular dynamics simulations. It is found that mass-graded graphene flakes reveal no thermal rectification effect in thermal conduction process. The dependence of thermal conductivity upon the heat flux and the mass gradient are studied to confirm the generality of the result.The mechanism leading to the absence of thermal rectification effect is also discussed.

  5. Aerosol matrix-assisted laser desorption ionization for liquid chromatography/time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Murray, K.K.; Lewis, T.M.; Beeson, M.D.; Russell, D.H. (Texas A M Univ., College Station, TX (United States))

    1994-05-15

    We report the application of aerosol matrix-assisted laser desorption ionization (MALDI) to liquid chromatography/mass spectrometry (LC/MS). The aerosol MALDI experiment uses aerosol liquid introduction in conjunction with pulsed UV laser ionization to form ions from large biomolecules in solution. Mass analysis is achieved in a time-of-flight mass spectrometer. In the LC/MALDI-MS experiment, the matrix solution is combined with the column effluent in a mixing tee, LC/MALDI-MS is demonstrated for the separation of bradykinin, gramicidin S, and myoglobin. 32 refs., 8 figs., 1 tab.

  6. Liquid chromatography/mass spectrometry in anabolic steroid analysis--optimization and comparison of three ionization techniques: electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization.

    Science.gov (United States)

    Leinonen, Antti; Kuuranne, Tiia; Kostiainen, Risto

    2002-07-01

    The applicability of liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the detection of the free anabolic steroid fraction in human urine was examined. Electrospray ionization (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization methods were optimized regarding eluent composition, ion source parameters and fragmentation. The methods were compared with respect to specificity and detection limit. Although all methods proved suitable, LC/ESI-MS/MS with a methanol-water gradient including 5 mM ammonium acetate and 0.01% acetic acid was found best for the purpose. Multiple reaction monitoring allowed the determination of steroids in urine at low nanogram per milliliter levels. LC/MS/MS exhibited high sensitivity and specificity for the detection of free steroids and may be a suitable technique for screening for the abuse of anabolic steroids in sports. Copyright 2002 John Wiley & Sons, Ltd.

  7. Confirmatory assay for ivermectin in cattle tissue using chemical ionization mass spectrometry/mass spectrometry (MS/MS).

    Science.gov (United States)

    Tway, P C; Downing, G V; Slayback, J R; Rahn, G S; Isensee, R K

    1984-04-01

    A method based on direct exposure, positive ion, chemical ionization mass spectrometry/mass spectrometry (ms/ms) was developed for the confirmatory assay of the antiparasitic drug, ivermectin, in animal tissue. Following extraction, column and preparative liquid chromatography, mass spectrometric/mass spectrometric analysis of the drug in liver samples provided reliable detection limits to 8-10 parts-per-billion at a signal: noise of greater than 10:1. Blank tissue consistently displayed no chemical/matrix interference. Besides the development of a confirmatory assay, the study also demonstrates the analytical capability and the role of MS/MS vis-a-vis other applied mass spectrometric techniques.

  8. Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemica lionization

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikova, Olga S [ORNL; Van Berkel, Gary J [ORNL

    2010-01-01

    An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

  9. Recent progress in application of carbon nanomaterials in laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Wang, Jing; Liu, Qian; Liang, Yong; Jiang, Guibin

    2016-04-01

    Carbon nanomaterials have attracted great interest over past decades owing to their unique physical properties, versatile functionalization chemistry, and biological compatibility. In this article, we review recent progress in application of carbon nanomaterials in laser desorption/ionization mass spectrometry (LDI MS). Various types of carbon nanomaterials, including fullerenes, carbon nanotubes, graphene, carbon nanodots, nanodiamond, nanofibers, nanohorns, and their derivative forms, are involved. The applications of these materials as new matrices or probes in matrix-assisted or surface-enhanced laser desorption/ionization mass spectrometry (MALDI or SELDI MS) are discussed. Finally, we summarize current challenges and give our perspectives on the future of applications of carbon nanomaterials in LDI MS.

  10. The Application of Resonance-Enhanced Multiphoton Ionization Technique in Gas Chromatography Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Adan Li

    2014-01-01

    Full Text Available Gas chromatography resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (GC/REMPI-TOFMS using a nanosecond laser has been applied to analyze the 16 polycyclic aromatic hydrocarbons (PAHs. The excited-state lifetime, absorption characters, and energy of electronic states of the 16 PAHs were investigated to optimize the ionization yield. A river water sample pretreated by means of solid phase extraction was analyzed to evaluate the performance of the analytical instrument. The results suggested that REMPI is superior to electron impact ionization method for soft ionization and suppresses the background signal due to aliphatic hydrocarbons. Thus, GC/REMPI-TOFMS is a more reliable method for the determination of PAHs present in the environment.

  11. Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

    Science.gov (United States)

    Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

    2002-01-01

    The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

  12. An open port sampling interface for liquid introduction atmospheric pressure ionization mass spectrometry.

    Science.gov (United States)

    Van Berkel, Gary J; Kertesz, Vilmos

    2015-10-15

    A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the ionization source of the mass spectrometer via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate, creating a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time-of-flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling-ready mass spectrometer system. The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with the liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination. Copyright © 2015 John Wiley & Sons, Ltd.

  13. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim

    2013-10-01

    Rationale Polycyclic aromatic sulfur heterocycles (PASHs) are detrimental species for refining processes in petroleum industry. Current mass spectrometric Methods that determine their composition are often preceded by derivatization and dopant addition approaches. Different ionization Methods have different impact on the molecular assignment of complex PASHs. The analysis of such species under atmospheric pressure chemical ionization (APCI) is still considered limited due to uncontrolled ion generation with low- and high-mass PASHs. Methods The ionization behavior of a model mixture of five selected PASH standards was investigated using an APCI source with nitrogen as the reagent gas. A complex thiophenic fraction was separated from a vacuum gas oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same ionization pattern was observed for the real thiophenic sample. It was found that S1 class species were the major sulfur-containing species found in the VGO sample. These species indicated the presence of alkylated benzothiophenic (BT), dibenzothiophenic (DBT) and benzonaphthothiophenic (BNT) series that were detected by APCI-FTICR MS. CONCLUSIONS This study provides an established APCI-FTICR MS method for the analysis of complex PASHs. PASHs were detected without using any derivatization and without fragmentation. The method can be used for the analysis of S-containing crude oil samples. © 2013 John Wiley & Sons, Ltd.

  14. Flow injection of liquid samples to a mass spectrometer with ionization under vacuum conditions: a combined ion source for single-photon and electron impact ionization.

    Science.gov (United States)

    Schepler, Claudia; Sklorz, Martin; Passig, Johannes; Famiglini, Giorgio; Cappiello, Achille; Zimmermann, Ralf

    2013-09-01

    Electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photo-ionization (APPI) are the most important techniques for the ionization of liquid samples. However, working under atmospheric pressure conditions, all these techniques involve some chemical rather than purely physical processes, and therefore, side reactions often yield to matrix-dependent ionization efficiencies. Here, a system is presented that combines both soft single-photon ionization (SPI) and hard 70 eV electron impact ionization (EI) of dissolved compounds under vacuum conditions. A quadrupole mass spectrometer was modified to enable direct EI, a technique developed by Cappiello et al. to obtain library-searchable EI mass spectra as well as soft SPI mass spectra of sample solutions. An electron beam-pumped rare gas excimer lamp working at 126 nm was used as well as a focusable vacuum UV light source for single-photon ionization. Both techniques, EI and SPI, were applied successfully for flow injection experiments providing library-matchable EI fragment mass spectra and soft SPI mass spectra, showing dominant signals for the molecular ion. Four model compounds were analyzed: hexadecane, propofol, chlorpropham, and eugenol, with detection limits in the picomolar range. This novel combination of EI and SPI promises great analytical benefits, thanks to the possibility of combining database alignment for EI data and molecular mass information provided by SPI. Possible applications for the presented ionization technology system are a matrix-effect-free detection and a rapid screening of different complex mixtures without time-consuming sample preparation or separation techniques (e.g., for analysis of reaction solutions in combinatorial chemistry) or a switchable hard (EI) and soft (SPI) MS method as detection step for liquid chromatography.

  15. Ambient femtosecond laser vaporization and nanosecond laser desorption electrospray ionization mass spectrometry.

    Science.gov (United States)

    Flanigan, Paul; Levis, Robert

    2014-01-01

    Recent investigations of ambient laser-based transfer of molecules into the gas phase for subsequent mass spectral analysis have undergone a renaissance resulting from the separation of vaporization and ionization events. Here, we seek to provide a snapshot of recent femtosecond (fs) duration laser vaporization and nanosecond (ns) duration laser desorption electrospray ionization mass spectrometry experiments. The former employs pulse durations of vaporization with little or no fragmentation. When coupled to electrospray ionization, femtosecond laser vaporization provides a universal, rapid mass spectral analysis method requiring no sample workup. Remarkably, laser pulses with intensities exceeding 10(13) W cm(-2) desorb intact macromolecules, such as proteins, and even preserve the condensed phase of folded or unfolded protein structures according to the mass spectral charge state distribution, as demonstrated for cytochrome c and lysozyme. Because of the ability to vaporize and ionize multiple components from complex mixtures for subsequent analysis, near perfect classification of explosive formulations, plant tissue phenotypes, and even the identity of the manufacturer of smokeless powders can be determined by multivariate statistics. We also review the more mature field of nanosecond laser desorption for ambient mass spectrometry, covering the wide range of systems analyzed, the need for resonant absorption, and the spatial imaging of complex systems like tissue samples.

  16. First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

    Science.gov (United States)

    Hu, S. X.; Collins, L. A.; Goncharov, V. N.; Kress, J. D.; McCrory, R. L.; Skupsky, S.

    2016-04-01

    Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations of the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm3 and T = 15 625 to 500 000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a "Saha-type" model as a function of the CH plasma density and temperature, which gives an increasing ionization as the CH density increases even at low temperatures (T hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic deuterium-tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted ˜20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.

  17. Laser-induced surface ionization in a time-of-flight mass spectrometer

    Science.gov (United States)

    Schriemer, David C.; Li, Liang

    1995-01-01

    A laser-induced ionization scheme based on laser-metal interaction is described. It is found that when a low power, pulsed UV laser beam is directed to the repeller plate of a Wiley-McLaren time-of-flight mass spectrometer (TOFMS), which is held at much higher positive potential than the extraction grid, extensive ionization of gas phase species can take place. For monatomic species such as Ar and Xe, multiply charged ions up to Ar6+ and Xe9+ are obtained. For both aromatic and aliphatic organic molecules, classical electron-impact-type mass spectra are observed. Mass resolution is in the range of 300-400, comparable to that obtained using laser-induced resonant two-photon ionization (R2PI) in the same linear TOFMS. It is shown that this technique can be quite efficient in ionizing organic species. A detection limit of 5 ng and a linear dynamic range of four orders of magnitude for benzene are demonstrated. While not as sensitive as R2PI, it has a much wider applicability and more uniform ionization efficiency than R2PI. It also appears about 1000 times more sensitive than the incorporation of an electron gun in TOFMS. The technique can be interchanged with R2PI very readily by simply adjusting the position and focus of the laser beam. While the ionization mechanism involved in the technique is currently unknown, some preliminary investigation of the ionization process is reported. It is suspected that photoelectron generation from the plate surface may play some important role in producing the ions detected.

  18. Pharmaceutical Analysis by Solid-Substrate Electrospray Ionization Mass Spectrometry with Wooden Tips

    Science.gov (United States)

    Yang, Yunyun; Deng, Jiewei; Yao, Zhong-Ping

    2014-01-01

    Electrospray ionization (ESI) using wooden tips as solid substrates allows direct ionization of various samples and their simple and efficient analyses by mass spectrometry (MS). In this study, wooden-tip ESI-MS was used for pharmaceutical analysis. A wide variety of active components present in pharmaceuticals with forms of tablets, capsules, granules, dry suspensions, suspensions, drops, and oral liquids, etc., were all successfully ionized directly for mass spectrometric analysis. Trace degradation products were also sensitively detected using wooden-tip ESI-MS. This strategy was extended to construct chemical fingerprints of herbal products containing complex and unknown components, and the fingerprints provided valuable information for their quality assessment and origin tracing. Our experimental data demonstrated that wooden-tip ESI-MS is a useful tool for rapid pharmaceutical analysis, with high sensitivity and wide applicability, showing promising perspectives for quality assessment and control, authentication, and origin tracing of pharmaceuticals.

  19. ARE MOLECULAR OUTFLOWS AROUND HIGH-MASS STARS DRIVEN BY IONIZATION FEEDBACK?

    Energy Technology Data Exchange (ETDEWEB)

    Peters, Thomas; Klessen, Ralf S. [Institut fuer Theoretische Astrophysik, Universitaet Heidelberg, Zentrum fuer Astronomie, Albert-Ueberle-Str. 2, D-69120 Heidelberg (Germany); Klaassen, Pamela D. [European Southern Observatory, Karl-Schwarzschild-Strasse 2, D-85748 Garching (Germany); Mac Low, Mordecai-Mark [Department of Astrophysics, American Museum of Natural History, 79th Street at Central Park West, New York, NY 10024-5192 (United States); Banerjee, Robi, E-mail: tpeters@physik.uzh.ch [Hamburger Sternwarte, Gojenbergsweg 112, D-21029 Hamburg (Germany)

    2012-11-20

    The formation of massive stars exceeding 10 M {sub Sun} usually results in large-scale molecular outflows. Numerical simulations, including ionization, of the formation of such stars show evidence for ionization-driven molecular outflows. Here we examine whether the outflows seen in these models reproduce the observations. We compute synthetic ALMA and CARMA maps of CO emission lines of the outflows, and compare their signatures to existing single-dish and interferometric data. We find that the ionization-driven models can only reproduce weak outflows around high-mass star-forming regions. We argue that expanding H II regions probably do not represent the dominant mechanism for driving observed outflows. We suggest instead that observed outflows are driven by the collective action of the outflows from the many lower-mass stars that inevitably form around young massive stars in a cluster.

  20. Laser desorption ionization and MALDI time-of-flight mass spectrometry for low molecular mass polyethylene analysis.

    Science.gov (United States)

    Chen, R; Yalcin, T; Wallace, W E; Guttman, C M; Li, L

    2001-11-01

    Polyethylene's inert nature and difficulty to dissolve in conventional solvents at room temperature present special problems for sample preparation and ionization in mass spectrometric analysis. We present a study of ionization behavior of several polyethylene samples with molecular masses up to 4000 Da in laser desorption ionization (LDI) time-of-flight mass spectrometers equipped with a 337 nm laser beam. We demonstrate unequivocally that silver or copper ion attachment to saturated polyethylene can occur in the gas phase during the UV LDI process. In LDI spectra of polyethylene with molecular masses above approximately 1000 Da, low mass ions corresponding to metal-alkene structures are observed in addition to the principal distribution. By interrogating a well-characterized polyethylene sample and a long chain alkane, C94H190, these low mass ions are determined to be the fragmentation products of the intact metal-polyethylene adduct ions. It is further illustrated that fragmentation can be reduced by adding matrix molecules to the sample preparation.

  1. Matrix-Assisted Laser Desorption/Ionization Mass Spectrometric Analysis of Uncomplexed Highly Sulfated Oligosaccharides Using Ionic Liquid Matrices

    Science.gov (United States)

    Laremore, Tatiana N.; Murugesan, Saravanababu; Park, Tae-Joon; Avci, Fikri Y.; Zagorevski, Dmitri V.; Linhardt, Robert J.

    2014-01-01

    Direct UV matrix-assisted laser desorption/ionization (MALDI) mass spectrometric analysis of uncomplexed, underivatized, highly sulfated oligosaccharides has been carried out using ionic liquids as matrices. Under conventionally used MALDI time-of-flight experimental conditions, uncomplexed polysulfated oligosaccharides do not produce any signal. We report that 1-methylimidazolium α-cyano-4-hydroxycinnamate and butylammonium 2,5-dihydroxybenzoate ionic liquid matrices allow the detection of picomole amounts of the sodium salts of a disaccharide, sucrose octasulfate, and an octasulfated pentasaccharide, Arixtra. The experimental results indicate that both analytes undergo some degree of thermal fragmentation with a mass loss corresponding to cleavage of O–SO3Na bonds in the matrix upon laser irradiation, reflecting lability of sulfo groups. PMID:16536411

  2. Determination of the ionization potentials of security-relevant substances with single photon ionization mass spectrometry using synchrotron radiation.

    Science.gov (United States)

    Schramm, E; Mühlberger, F; Mitschke, S; Reichardt, G; Schulte-Ladbeck, R; Pütz, M; Zimmermann, R

    2008-02-01

    Several ionization potentials (IPs) of security relevant substances were determined with single photon ionization time of flight mass spectrometry (SPI-TOFMS) using monochromatized synchrotron radiation from the "Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung" (BESSY). In detail, the IPs of nine explosives and related compounds, seven narcotics and narcotics precursors, and one chemical warfare agent (CWA) precursor were determined, whereas six IPs already known from the literature were verified correctly. From seven other substances, including one CWA precursor, the IP could not be determined as the molecule ion peak could not be detected. For these substances the appearance energy (AE) of a main fragment was determined. The analyzed security-relevant substances showed IPs significantly below the IPs of common matrix compounds such as nitrogen and oxygen. Therefore, it is possible to find photon energies in between, whereby the molecules of interest can be detected with SPI in very low concentrations due to the shielding of the matrix. All determined IPs except the one of the explosive EGDN were below 10.5 eV. Hence, laser-generated 118 nm photons can be applied for detecting almost all security-relevant substances by, e.g., SPI-TOFMS.

  3. Feasibility of nonvolatile buffers in capillary electrophoresis-electrospray ionization-mass spectrometry of proteins

    NARCIS (Netherlands)

    Eriksson, Jonas H.C.; Mol, Roelof; Somsen, Govert W.; Hinrichs, Wouter L.J.; Frijlink, Henderik W.; de Jong, Gerhardus J.

    2004-01-01

    The combination of capillary electrophoresis (CE) and electrospray ionization-mass spectrometry (ESI-MS) via a triaxial interface was studied as a potential means for the characterization of intact proteins. To evaluate the possibility to use a nonvolatile electrolyte for CE, the effect of sodium

  4. Real-Time Flavor Release from French Fries Using Atmospheric Pressure Chemical Ionization-Mass Spectrometry

    NARCIS (Netherlands)

    Loon, W.A.M.; Linssen, J.P.H.; Boelrijk, A.E.M.; Burgering, M.J.M.; Voragen, A.G.J.

    2005-01-01

    Flavor release from French fries was measured with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) using both assessors (in vivo) and a mouth model system (in vitro). Several volatiles measured with APCI were identified with MS-MS. The effect of frying time, salt addition, and

  5. Characterization of typical chemical background interferences in atmospheric pressure ionization liquid chromatography-mass spectrometry

    NARCIS (Netherlands)

    Guo, Xinghua; Bruins, Andries P.; Covey, Thomas R.

    2006-01-01

    The structures and origins of typical chemical background noise ions in positive atmospheric pressure ionization liquid chromatography/mass spectrometry (API LC/MS) are investigated and summarized in this study. This was done by classifying chemical background ions using precursor and product ion

  6. Desorption electrospray ionization mass spectrometry in the analysis of chemical food contaminants in food

    NARCIS (Netherlands)

    Nielen, M.W.F.; Hooijerink, H.; Zomer, P.; Mol, J.G.J.

    2011-01-01

    Since its introduction, desorption electrospray ionization (DESI) mass spectrometry (MS) has been mainly applied in pharmaceutical and forensic analysis. We expect that DESI will find its way in many different fields, including food analysis. In this review, we summarize DESI developments aimed at

  7. Effect of Ionizing Beta Radiation on the Mechanical Properties of Poly(ethylene under Thermal Stress

    Directory of Open Access Journals (Sweden)

    Bednarik Martin

    2016-01-01

    Full Text Available It was found in this study, that ionizing beta radiation has a positive effect on the mechanical properties of poly(ethylene. In recent years, there have been increasing requirements for quality and cost effectiveness of manufactured products in all areas of industrial production. These requirements are best met with the polymeric materials, which have many advantages in comparison to traditional materials. The main advantages of polymer materials are especially in their ease of processability, availability, and price of the raw materials. Radiation crosslinking is one of the ways to give the conventional plastics mechanical, thermal, and chemical properties of expensive and highly resistant construction polymers. Several types of ionizing radiation are used for crosslinking of polymers. Each of them has special characteristics. Electron beta and photon gamma radiation are used the most frequently. The great advantage is that the crosslinking occurs after the manufacturing process at normal temperature and pressure. The main purpose of this paper has been to determine the effect of ionizing beta radiation on the tensile modulus, strength and elongation of low and high density polyethylene (LDPE and HDPE. These properties were examined in dependence on the dosage of the ionizing beta radiation (non-irradiated samples and those irradiated by dosage 99 kGy were compared and on the test temperature. Radiation cross-linking of LDPE and HDPE results in increased tensile strength and modulus, and decreased of elongation. The measured results indicate that ionizing beta radiation treatment is effective tool for improvement of mechanical properties of LDPE and HDPE under thermal stress.

  8. Mass spectrometric characterization of a pyrolytic radical source using femtosecond ionization

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H.M.; Beaud, P.; Mischler, B.; Radi, P.P.; Tzannis, A.P.; Gerber, T. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Radicals play, as reactive species, an important role in the chemistry of combustion. In contrast to atmospheric flames where spectra are congested due to high vibrational and rotational excitation, experiments in the cold environment of a molecular beam (MB) yield clean spectra that can be easily attributed to one species by Resonantly Enhanced Multi Photon Ionization (REMP). A pyrolytic radical source has been set up. To characterize the efficiency of the source `soft` ionization with femto second pulses is applied which results in less fragmentation, simplifying the interpretation of the mass spectrum. (author) figs., tabs., refs.

  9. Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry.

    Science.gov (United States)

    Setner, Bartosz; Rudowska, Magdalena; Klem, Ewelina; Cebrat, Marek; Szewczuk, Zbigniew

    2014-10-01

    Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1-azabicyclo[2.2.2]octane (ABCO) or 1,4-diazabicyclo[2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI-MS) and longer retention times on the reverse-phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision-induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a- and b-type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision-induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI-MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.

  10. U-series dating using thermal ionisation mass spectrometry (TIMS)

    Energy Technology Data Exchange (ETDEWEB)

    McCulloch, M.T. [Australian National University, Canberra, ACT (Australia). Research School of Earth Science

    1999-11-01

    U-series dating is based on the decay of the two long-lived isotopes{sup 238}U({tau}{sub 1/2}=4.47 x 10{sup 9} years) and {sup 235}U ({tau}{sub 1/2} 0.7 x 10{sup 9} years). {sup 238}U and its intermediate daughter isotopes {sup 234}U ({tau}{sub 1/2} = 245.4 ka) and {sup 230}Th ({tau}{sub 1/2} = 75.4 ka) have been the main focus of recently developed mass spectrometric techniques (Edwards et al., 1987) while the other less frequently used decay chain is based on the decay {sup 235}U to {sup 231}Pa ({tau}{sub 1/2} = 32.8 ka). Both the {sup 238}U and {sup 235}U decay chains terminate at the stable isotopes {sup 206}Pb and {sup 207}Pb respectively. Thermal ionization mass spectrometry (TIMS) has a number of inherent advantages, mainly the ability to measure isotopic ratios at high precision on relatively small samples. In spite of these now obvious advantages, it is only since the mid-1980`s when Chen et al., (1986) made the first precise measurements of {sup 234}U and {sup 232}Th in seawater followed by Edwards et al., (1987) who made combined {sup 234}U-{sup 230}Th measurements, was the full potential of mass spectrometric methods first realised. Several examples are given to illustrate various aspects of TIMS U-series 9 refs., 3 figs.

  11. Development of Soft Ionization for Particulate Organic Detection with the Aerodyne Aerosol Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Trimborn, A; Williams, L R; Jayne, J T; Worsnop, D R

    2008-06-19

    During this DOE SBIR Phase II project, we have successfully developed several soft ionization techniques, i.e., ionization schemes which involve less fragmentation of the ions, for use with the Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS). Vacuum ultraviolet single photon ionization was demonstrated in the laboratory and deployed in field campaigns. Vacuum ultraviolet single photon ionization allows better identification of organic species in aerosol particles as shown in laboratory experiments on single component particles, and in field measurements on complex multi-component particles. Dissociative electron attachment with lower energy electrons (less than 30 eV) was demonstrated in the measurement of particulate organics in chamber experiments in Switzerland, and is now a routine approach with AMS systems configured for bipolar, negative ion detection. This technique is particularly powerful for detection of acidic and other highly oxygenated secondary organic aerosol (SOA) chemical functionality. Low energy electron ionization (10 to 12 eV) is also a softer ionization approach routinely available to AMS users. Finally, Lithium ion attachment has been shown to be sensitive to more alkyl-like chemical functionality in SOA. Results from Mexico City are particularly exciting in observing changes in SOA molecular composition under different photochemical/meteorological conditions. More recent results detecting biomass burns at the Montana fire lab have demonstrated quantitative and selective detection of levoglucosan. These soft ionization techniques provide the ToF-AMS with better capability for identifying organic species in ambient atmospheric aerosol particles. This, in turn, will allow more detailed study of the sources, transformations and fate of organic-containing aerosol.

  12. [Development of a membrane inlet-single photon ionization/chemical ionization-mass spectrometer for online analysis of VOCs in water].

    Science.gov (United States)

    Hua, Lei; Wu, Qing-Hao; Hou, Ke-Yong; Cui, Hua-Peng; Chen, Ping; Zhao, Wu-Duo; Xie, Yuan-Yuan; Li, Hai-Yang

    2011-12-01

    A home-made membrane inlet- single photon ionization/chemical ionization- time-of-flight mass spectrometer has been described. A vacuum ultraviolet (VUV) lamp with photon energy of 10.6 eV was used as the light source for single photon ionization (SPI). Chemical ionization (CI) was achieved through ion-molecule reactions with O2- reactant ions generated by photoelectron ionization. The two ionization modes could be rapidly switched by adjusting electric field in the ionization region within 2 s. Membrane inlet system used for rapid enrichment of volatile organic compounds (VOCs) in water was constructed by using a polydimethylsiloxane (PDMS) membrane with a thickness of 50 microm. A purge gas was added to accelerate desorption of analytes from the membrane surface. The purge gas could also help to prevent the pump oil back-streaming into the ionization region from the analyzer chamber and improve the signal to noise ratio (S/N). Achieved detection limits were 2 microg x L(-1) for methyl tert-butyl ether (MTBE) in SPI mode and 1 microg x L(-1) for chloroform in SPI-CI mode within 10 s analysis time, respectively. The instrument has been successfully applied to the rapid analysis of MTBE in simulated underground water nearby petrol station and VOCs in disinfected drinking water. The results indicate that the instrument has a great application prospect for online analysis of VOCs in water.

  13. Near-infrared laser desorption/ionization aerosol mass spectrometry for measuring organic aerosol at atmospherically relevant aerosol mass loadings

    Directory of Open Access Journals (Sweden)

    S. Geddes

    2010-08-01

    Full Text Available A new method, near-infrared laser desorption/ionization aerosol mass spectrometry (NIR-LDI-AMS, is described for the real time analysis of organic aerosols at atmospherically relevant total mass loadings. Particles are sampled with an aerodynamic lens onto an aluminum probe. A moderate energy NIR laser pulse at 1064 nm is directed onto the probe to vaporize and ionize particle components. Delayed pulse extraction is then used to sample the ions into a reflectron time of flight mass spectrometer for chemical analysis. The soft ionization afforded by the NIR photons results in minimal fragmentation (loss of a hydrogen atom producing intact pseudo-molecular anions at [M-H]. The limit of detection measured for pure oleic acid particles (geometric mean diameter and standard deviation of 180 nm and 1.3, respectively was 140 fg (or 1.7 ng m−3 per minute sampling time. As an example of the utility of NIR-LDI-AMS to measurements of atmospheric importance, the method was applied to laboratory chamber measurements of the secondary organic aerosol formation from ozonolysis of α-pinene. High quality mass spectra were recorded with a 2-min time resolution for total aerosol mass loadings ranging from 1.5 to 8.7 μg m−3. These results demonstrate the potential of NIR-LDI-AMS to allow for more accurate measurements of the organic fraction of atmospheric particulate at realistic mass loadings. Measurements at ambient-levels of SOA mass loading are important to improve parameterizations of chamber-based SOA formation for modeling regional and global SOA fluxes and to aid in remediating the discrepancy between modeled and observed atmospheric total SOA production rates and concentrations.

  14. Characterization of phosphoantigens by high-performance anion-exchange chromatography-electrospray ionization ion trap mass spectrometry and nanoelectrospray ionization ion trap mass spectrometry.

    Science.gov (United States)

    Pont, F; Luciani, B; Belmant, C; Fournié, J J

    2001-08-01

    New phosphorylated microbial metabolites referred to as phosphoantigens activate immune responses in humans. Although these molecules have leading applications in medical research, no direct method allows their rapid and unambiguous structural identification. Here, we interfaced online HPAEC (high performance anion-exchange chromatography) with ESI-ITMS (electrospray ionization ion trap mass spectrometry) to identify such pyrophosphorylated molecules. A self-regenerating anion suppressor located upstream of electrospray ionization enabled the simultaneous detection of pyrophosphoester by conductimetry, UV and MS. By HPAEC-ITMS and HPAEC-ITMS2, a single run permitted characterization of reference phosphoantigens and of related structures. Although all compounds were resolved by HPAEC, MS enabled their detection and identification by [M-H]- and fragment ions. Isobaric phosphoantigen analogues were also separated by HPAEC and distinguished by MS2. The relevance of this device was demonstrated for phosphoantigens analysis in human urine and plasma. Furthermore, identification of natural phosphoantigens by automatically generated 2D mass spectra from nano-ESI-ITMS is presented. This last technique permits the simultaneous performance of molecular screening of natural phosphoantigen extracts and their identification.

  15. Fragmentation pathways and structural characterization of organophosphorus compounds related to the Chemical Weapons Convention by electron ionization and electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Hosseini, Seyed Esmaeil; Saeidian, Hamid; Amozadeh, Ali; Naseri, Mohammad Taghi; Babri, Mehran

    2016-12-30

    For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Detection of methyl-, dimethyl- and diethylamine using a nitrate-based chemical ionization mass spectrometer

    Science.gov (United States)

    Jokinen, T.; Smith, J. N.

    2016-12-01

    New particle formation is one of the main sources of cloud condensation nuclei (CCN) contributing approximately half of the global CCN budget. The initial steps of nucleation have been studied for decades and it is widely accepted that in most places nucleation requires presence of sulphuric acid (SA) and cluster-stabilizing vapours. Recent results from the CLOUD chamber show that only a few pptv levels of dimethylamine (DMA) with SA forms stable clusters at boundary layer conditions. Ambient sulphuric acid is typically measured using nitrate-based chemical ionization mass spectrometers. Unfortunately, because of higher volatilities and stickiness of amines to surfaces, amine measurement techniques suffer from memory effects and high detection limits. Recently it was discovered that DMA can be detected by utilizing nitrate ionization, simultaneously with sulphuric acid measurements. Here we present results of detecting methylamine, dimethylamine and diethylamine using nitrate-based chemical ionization. We conducted a series of measurements with a home-built transverse chemical ionization inlet and a high resolution time-of-flight mass spectrometer (CI-HToF). Amine vapour was produced using permeation tubes. Three stages of dilution were applied at roughly one order-of-magnitude dilution per stage. The diluted flow of selected amine was then introduced to a sample flow rate of 7 slpm, thus achieving a final amine concentration of 10 pptv. All selected amines were detected as clusters with HNO3NO3- and showed linear response with increasing concentrations (0.5-minute integration time). Zero measurements were performed using clean nitrogen gas right after injection of a selected amine. Memory effects were only observed when using high amine concentrations (ppbv levels). Our results indicate that a variety of amines can be detected using nitrate-based chemical ionization mass spectrometers. However, more experiments are required to see if this presented method will be

  17. Laser Desorption Ionization Mass Spectrometry Imaging of Drosophila Brain Using Matrix Sublimation versus Modification with Nanoparticles.

    Science.gov (United States)

    Phan, Nhu T N; Mohammadi, Amir Saeid; Dowlatshahi Pour, Masoumeh; Ewing, Andrew G

    2016-02-02

    Laser desorption ionization mass spectrometry (LDI-MS) is used to image brain lipids in the fruit fly, Drosophila, a common invertebrate model organism in biological and neurological studies. Three different sample preparation methods, including sublimation with two common organic matrixes for matrix-assisted laser desorption ionization (MALDI) and surface-assisted laser desorption ionization (SALDI) using gold nanoparticles, are examined for sample profiling and imaging the fly brain. Recrystallization with trifluoroacetic acid following matrix deposition in MALDI is shown to increase the incorporation of biomolecules with one matrix, resulting in more efficient ionization, but not for the other matrix. The key finding here is that the mass fragments observed for the fly brain slices with different surface modifications are significantly different. Thus, these approaches can be combined to provide complementary analysis of chemical composition, particularly for the small metabolites, diacylglycerides, phosphatidylcholines, and triacylglycerides, in the fly brain. Furthermore, imaging appears to be beneficial using modification with gold nanoparticles in place of matrix in this application showing its potential for cellular and subcellular imaging. The imaging protocol developed here with both MALDI and SALDI provides the best and most diverse lipid chemical images of the fly brain to date with LDI.

  18. Quasar Black Hole Mass Estimates from High-Ionization Lines: Breaking a Taboo?

    Directory of Open Access Journals (Sweden)

    Paola Marziani

    2017-09-01

    Full Text Available Can high ionization lines such as CIV λ 1549 provide useful virial broadening estimators for computing the mass of the supermassive black holes that power the quasar phenomenon? The question has been dismissed by several workers as a rhetorical one because blue-shifted, non-virial emission associated with gas outflows is often prominent in CIV λ 1549 line profiles. In this contribution, we first summarize the evidence suggesting that the FWHM of low-ionization lines like H β and MgII λ 2800 provide reliable virial broadening estimators over a broad range of luminosity. We confirm that the line widths of CIV λ 1549 is not immediately offering a virial broadening estimator equivalent to the width of low-ionization lines. However, capitalizing on the results of Coatman et al. (2016 and Sulentic et al. (2017, we suggest a correction to FWHM CIV λ 1549 for Eddington ratio and luminosity effects that, however, remains cumbersome to apply in practice. Intermediate ionization lines (IP ∼ 20–30 eV; AlIII λ 1860 and SiIII] λ 1892 may provide a better virial broadening estimator for high redshift quasars, but larger samples are needed to assess their reliability. Ultimately, they may be associated with the broad-line region radius estimated from the photoionization method introduced by Negrete et al. (2013 to obtain black hole mass estimates independent from scaling laws.

  19. Ambient Femtosecond Laser Vaporization and Nanosecond Laser Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Flanigan, Paul; Levis, Robert

    2014-06-01

    Recent investigations of ambient laser-based transfer of molecules into the gas phase for subsequent mass spectral analysis have undergone a renaissance resulting from the separation of vaporization and ionization events. Here, we seek to provide a snapshot of recent femtosecond (fs) duration laser vaporization and nanosecond (ns) duration laser desorption electrospray ionization mass spectrometry experiments. The former employs pulse durations of proteins, and even preserve the condensed phase of folded or unfolded protein structures according to the mass spectral charge state distribution, as demonstrated for cytochrome c and lysozyme. Because of the ability to vaporize and ionize multiple components from complex mixtures for subsequent analysis, near perfect classification of explosive formulations, plant tissue phenotypes, and even the identity of the manufacturer of smokeless powders can be determined by multivariate statistics. We also review the more mature field of nanosecond laser desorption for ambient mass spectrometry, covering the wide range of systems analyzed, the need for resonant absorption, and the spatial imaging of complex systems like tissue samples.

  20. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry of large biomolecules in complex buffer systems

    Energy Technology Data Exchange (ETDEWEB)

    Hofstadler, S.A.; Bruce, J.E.; Cheng, X.; Anderson, G.A.; Smith, R.D. [Pacific Northwest Lab., Richland, WA (United States); Wang, K. [Univ.of Texas, Austin, TX (United States); Swanek, F.; Ewing, A.G. [Penn State Univ., University Park, PA (United States)

    1994-12-31

    Recent advances in electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry allow ultra-high resolution, precision mass measurements of a wide range of biochemically relevant species including proteins, glycoproteins, DNA, and non-covalent complexes. One of the most common difficulties encountered when analyzing biological samples derived from multi-step extraction procedures is obtaining an {open_quotes}electrosprayable{close_quotes} analyte solution which keeps the protein(s) of interest in solution and which does not create numerous background ions which overwhelm the analyte signal or adversely affect the electrospray ionization process. In addition to loss of sensitivity, ionized buffer ions introduce undesirable space charge to the trapped ion cell which limits dynamic range and adversely affects mass measurement precision. Thus, it is highly desirable to minimize the number of background ions in the trapped ion cell. In this poster the authors will present two distinct, and potentially complimentary, techniques which allow high performance mass analysis of biomolecules from complex buffer systems. The first technique, which is particularly well suited for larger analytes, discriminates against low mass matrix ions by the combination of kinetic energy dependent ion accumulation and mass dependent ion loss due to collisionally enhanced magnetron radii. An alternative technique, which is particularly applicable to smaller analytes, is based on electrophoretic separations using on-line capillary zone electrophoresis prior to mass analysis. Preliminary results are presented in which two classes of biomolecules were analyzed from complex buffer systems. These examples include large muscle proteins electrosprayed directly from a 5 M urea buffer and mass analysis from whole human erthrocytes extracted from a buffer which mimics physiological conditions.

  1. Electrospray ionization mass spectrometry of terrestrial humic substances and their size fractions

    Energy Technology Data Exchange (ETDEWEB)

    Piccolo, A. [Dipartimento di Scienze del Suolo, della Pianta e dell' Ambiente, Universita di Napoli Federico II, Via Universita 100, 80055, Portici (Italy); Spiteller, M. [Institute of Environmental Research (INFU), University of Dortmund, Otto-Hahn-Strasse 6, 44227, Dortmund (Germany)

    2003-11-01

    Electrospray ionization mass spectrometry (ESI-MS) was used to evaluate the average molecular mass of terrestrial humic substances, such as humic (HA) and fulvic (FA) acids from a soil, and humic acid from a lignite (NDL). Their ESI mass spectra, by direct infusion, gave average molecular masses comparable to those previously obtained for aquatic humic materials. The soil HA and FA were further separated in size-fractions by preparative high performance size exclusion chromatography (HPSEC) and analyzed with ESI-MS by both direct infusion and a further on-line analytical HPSEC. Unexpectedly, their average molecular mass was only slightly less than for the bulk sample and, despite different nominal molecular size, did not substantially vary among size-fractions. The values increased significantly (up to around 1200 Da) after on-line analytical HPSEC for the HA bulk sample, at both pH 8 and 4, and for the HA size-fractions when pH was reduced from 8 to 4. It was noticed that HA size-fractions at pH 8 were separated by on-line HPSEC in further peaks showing average masses which progressively increased with elution volume. Furthermore, when the HA and NDL bulk samples were sequentially ultracentrifuged at increasing rotational speed, their supernatants showed mass values which were larger than bulk samples and increased with rotational speed. These variations in mass values indicate that the electrospray ionization is dependent on the composition of the humic molecular mixtures and increases when their heterogeneity is progressively reduced. It is suggested that the dominance of hydrophobic compounds in humic supramolecular associations may inhibit the electrospray ionization of hydrophilic components. Our results show that ESI-MS is reasonably applicable to humic substances only after an extensive reduction of their chemical complexity. (orig.)

  2. Observation of water molecules bound to a protein using cold-spray ionization mass spectrometry.

    Science.gov (United States)

    Sei, Yoshihisa; Shimotakahara, Sakurako; Ishii, Juri; Shindo, Heisaburo; Seki, Hiroko; Yamaguchi, Kentaro; Tashiro, Mitsuru

    2005-04-01

    The characterization of water molecules bound to ribonuclease T1 (RNase T1) was carried out using cold-spray ionization mass spectrometry (CSI-MS). CSI-MS is a variant of electrospray ionization mass spectrometry (ESI-MS) operating at low temperature, and is particularly suitable for investigating the weaker molecular associations, since the temperature at the spray interface is much lower than that in the conventional ESI-MS. In this approach, ion peaks due to the addition of nine water molecules were identified at a spray temperature of 48 degrees C. This result showed good agreement with that inferred by the combinational analysis of NMR and X-ray crystallography, indicating that CSI-MS is capable of rapidly providing reliable information to characterize the number of water molecules bound to a macromolecule.

  3. High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Hourani, Nadim; Kuhnert, Nikolai

    2012-10-15

    High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

  4. On plate graphite supported sample processing for simultaneous lipid and protein identification by matrix assisted laser desorption ionization mass spectrometry.

    Science.gov (United States)

    Calvano, Cosima Damiana; van der Werf, Inez Dorothé; Sabbatini, Luigia; Palmisano, Francesco

    2015-05-01

    The simultaneous identification of lipids and proteins by matrix assisted laser desorption ionization-mass spectrometry (MALDI-MS) after direct on-plate processing of micro-samples supported on colloidal graphite is demonstrated. Taking advantages of large surface area and thermal conductivity, graphite provided an ideal substrate for on-plate proteolysis and lipid extraction. Indeed proteins could be efficiently digested on-plate within 15 min, providing sequence coverages comparable to those obtained by conventional in-solution overnight digestion. Interestingly, detection of hydrophilic phosphorylated peptides could be easily achieved without any further enrichment step. Furthermore, lipids could be simultaneously extracted/identified without any additional treatment/processing step as demonstrated for model complex samples such as milk and egg. The present approach is simple, efficient, of large applicability and offers great promise for protein and lipid identification in very small samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Chemometric optimization of a low-temperature plasma source design for ambient desorption/ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Albert, Anastasia [University of Muenster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 30, 48149 Muenster (Germany); Engelhard, Carsten, E-mail: engelhard@chemie.uni-siegen.de [University of Siegen, Department of Chemistry and Biology, Adolf-Reichwein-Straße 2, 57076 Siegen (Germany)

    2015-03-01

    Low-temperature plasmas (LTPs) are attractive sources for atomic and molecular mass spectrometry (MS). In the past, the LTP probe, which was first described by Harper et al., was used successfully for direct molecular mass spectrometric analysis with minimal sample pretreatment in a variety of applications. Unfortunately, the desorption/ionization source itself is commercially not available and custom-built LTP set-ups with varying geometry and operational configurations were utilized in the past. In the present study, a rapid chemometrics approach based on systematic experiments and multivariate data analysis was used to optimize the LTP probe geometry and positioning relative to the atmospheric-pressure inlet of a mass spectrometer. Several parameters were studied including the probe geometry, electrode configuration, quartz tube dimensions, probe positioning and operating conditions. It was found that the plasma-to-MS-inlet distance, the plasma-to-sample-plate distance, and the angle between the latter are very important. Additional effects on the analytical performance were found for the outer electrode width, the positioning of the electrodes, the inner diameter of the quartz tube, the quartz wall thickness, and the gas flow. All experiments were performed using additional heating of the sample to enhance thermal desorption and maximize the signal (T = 150 °C). After software-assisted optimization, attractive detection limits were achieved (e.g., 1.8 × 10{sup −7} mol/L for 4-acetamidothiophenol). Moreover, relative standard deviation (RSD) improved from values of up to 30% before optimization to < 15% RSD after the procedure was completed. This chemometrics approach for method optimization is not limited to LTP-MS and considered to be attractive for other plasma-based instrumentation as well. - Highlights: • Plasmas are useful in ambient desorption/ionization mass spectrometry. • Rapid and direct analysis is performed without sample preparation.

  6. Interferometric characterization of ultrashort deep ultraviolet pulses using a multiphoton ionization mass spectrometer.

    Science.gov (United States)

    Zaitsu, Shin-ichi; Miyoshi, Yuki; Kira, Fumiaki; Yamaguchi, Satoshi; Uchimura, Tomohiro; Imasaka, Tatoro

    2007-06-15

    The temporal characterization of a femtosecond laser pulse in the deep ultraviolet region using an interferometric autocorrelation scheme is demonstrated. Two-photon ionization of a molecule in a time-of-flight mass spectrometer was used as a nonlinear detector to obtain an autocorrelation trace. This setup proved useful in not only providing a temporal characterization of a pulse but also investigating the ultrafast dynamics of photochemical processes.

  7. Cold-spray ionization mass spectrometric detection of a coordination oligomer.

    Science.gov (United States)

    Ohara, Kazuaki; Yamaguchi, Kentaro

    2012-01-01

    Coordination polymer (CP) formation is an unexplored area in weak-interaction chemistry due to the difficulty of monitoring the coordination process. By using cold-spray ionization mass spectrometry (CSI-MS), several kinds of coordination compounds were detected when CuI metal and the 4,7-phenanthroline organic bridged ligand were mixed in solution. The observed ion peaks could be reasonably and simply assigned to various combinations of the metal and the ligand without any fragmentation.

  8. Determination of triacetone triperoxide using ultraviolet femtosecond multiphoton ionization time-of-flight mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ezoe, Ryota [Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Imasaka, Tomoko [Laboratory of Chemistry, Graduate School of Design, Kyushu University, 4-9-1, Shiobaru, Minami-ku, Fukuoka 815-8540 (Japan); Imasaka, Totaro, E-mail: imasaka@cstf.kyushu-u.ac.jp [Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan); Division of Optoelectronics and Photonics, Center for Future Chemistry, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 (Japan)

    2015-01-01

    Highlights: • A UV ultrashort laser pulse was useful for ionization of triacetone triperoxide. • A molecular ion was strongly enhanced in multiphoton ionization mass spectrometry. • Triacetone triperoxide in the human blood was measured without any interferences. • An organic compound of phorone was formed in the human blood from acetone. - Abstract: Triacetone triperoxide (TATP), an explosive compound, was measured using gas chromatography combined with multiphoton ionization time-of-flight mass spectrometry (GC/MPI-TOFMS). By decreasing the pulse width of a femtosecond laser from 80 to 35 fs, a molecular ion was drastically enhanced and was measured as one of the major ions in the mass spectrum. The detection limits obtained using the molecular (M·{sup +}) and fragment (C{sub 2}H{sub 3}O{sup +}) ions were similar or slightly superior to those obtained using conventional mass spectrometry based on electron and chemical ionization. In order to improve the reliability, an isotope of TATP, i.e., TATP-d18, was synthesized and used as an internal standard in the trace analysis of TATP in a sample of human blood. TATP could be identified in a two-dimensional display, even though numerous interfering compounds were present in the sample. Acetone, which is frequently used as a solvent in sampling TATP, produced a chemical species with a retention time nearly identical to that of TATP and provided a C{sub 2}H{sub 3}O{sup +} fragment ion that was employed for measuring a chromatogram of TATP in conventional MS. This compound, the structure of which was assigned as phorone, was clearly differentiated from TATP based on a molecular ion observable in MPI-TOFMS.

  9. High explosives vapor detection by atmospheric sampling glow discharge ionization/tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    McLuckey, S.A.; Goeringer, D.E.; Asano, K.G. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1996-02-01

    The combination of atmospheric sampling glow discharge ionization with tandem mass spectrometry for the detection of traces of high explosives is described. Particular emphasis is placed on use of the quadrupole ion trap as the type of tandem mass spectrometer. Atmospheric sampling glow discharge provides a simple, rugged, and efficient means for anion formation while the quadrupole ion trap provides for efficient tandem mass spectrometry. Mass selective ion accumulation and non-specific ion activation methods can be used to overcome deleterious effects arising from ion/ion interactions. Such interactions constitute the major potential technical barrier to the use of the ion trap for real-time monitoring of targeted compounds in uncontrolled and highly variable matrices. Tailored waveforms can be used to effect both mass selective ion accumulation and ion activation. Concatenated tailored waveforms allow for both functions in a single experiment thereby providing the capability for monitoring several targeted species simultaneously. The combination of atmospheric sampling glow discharge ionization with a state-of-the-art analytical quadrupole ion trap is a highly sensitive and specific detector for traces of high explosives. The combination is also small and inexpensive relative to virtually any other form of tandem mass spectrometry. The science and technology underlying the glow discharge/ion trap combination is sufficiently mature to form the basis for an engineering effort to make the detector portable. 85 refs.

  10. Coffee-ring effects in laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Hu, Jie-Bi; Chen, Yu-Chie; Urban, Pawel L

    2013-03-05

    This report focuses on the heterogeneous distribution of small molecules (e.g. metabolites) within dry deposits of suspensions and solutions of inorganic and organic compounds with implications for chemical analysis of small molecules by laser desorption/ionization (LDI) mass spectrometry (MS). Taking advantage of the imaging capabilities of a modern mass spectrometer, we have investigated the occurrence of "coffee rings" in matrix-assisted laser desorption/ionization (MALDI) and surface-assisted laser desorption/ionization (SALDI) sample spots. It is seen that the "coffee-ring effect" in MALDI/SALDI samples can be both beneficial and disadvantageous. For example, formation of the coffee rings gives rise to heterogeneous distribution of analytes and matrices, thus compromising analytical performance and reproducibility of the mass spectrometric analysis. On the other hand, the coffee-ring effect can also be advantageous because it enables partial separation of analytes from some of the interfering molecules present in the sample. We report a "hidden coffee-ring effect" where under certain conditions the sample/matrix deposit appears relatively homogeneous when inspected by optical microscopy. Even in such cases, hidden coffee rings can still be found by implementing the MALDI-MS imaging technique. We have also found that to some extent, the coffee-ring effect can be suppressed during SALDI sample preparation. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Identification of Microalgae by Laser Desorption/Ionization Mass Spectrometry Coupled with Multiple Nanomatrices.

    Science.gov (United States)

    Peng, Lung-Hsiang; Unnikrishnan, Binesh; Shih, Chi-Yu; Hsiung, Tung-Ming; Chang, Jeng; Hsu, Pang-Hung; Chiu, Tai-Chia; Huang, Chih-Ching

    2016-04-01

    In this study, we demonstrate a simple method to identify microalgae by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using three different substrates: HgSe, HgTe, and HgTeSe nanostructures. The fragmentation/ionization processes of complex molecules in algae varied according to the heat absorption and transfer efficiency of the nanostructured matrices (NMs). Therefore, the mass spectra obtained for microalgae showed different patterns of m/z values for different NMs. The spectra contained both significant and nonsignificant peaks. Constructing a Venn diagram with the significant peaks obtained for algae when using HgSe, HgTe, and HgTeSe NMs in m/z ratio range 100-1000, a unique relationship among the three sets of values was obtained. This unique relationship of sets is different for each species of microalgae. Therefore, by observing the particular relationship of sets, we successfully identified different algae such as Isochrysis galbana, Emiliania huxleyi, Thalassiosira weissflogii, Nannochloris sp., Skeletonema cf. costatum, and Tetraselmis chui. This simple and cost-effective SALDI-MS analysis method coupled with multi-nanomaterials as substrates may be extended to identify other microalgae and microorganisms in real samples. Graphical Abstract Identification of microalgae by surface-assisted laser desorption/ionization mass spectrometry coupled with three different mercury-based nanosubstrates.

  12. Fast detection of narcotics by single photon ionization mass spectrometry and laser ion mobility spectrometry

    Science.gov (United States)

    Laudien, Robert; Schultze, Rainer; Wieser, Jochen

    2010-10-01

    In this contribution two analytical devices for the fast detection of security-relevant substances like narcotics and explosives are presented. One system is based on an ion trap mass spectrometer (ITMS) with single photon ionization (SPI). This soft ionization technique, unlike electron impact ionization (EI), reduces unwanted fragment ions in the mass spectra allowing the clear determination of characteristic (usually molecular) ions. Their enrichment in the ion trap and identification by tandem MS investigations (MS/MS) enables the detection of the target substances in complex matrices at low concentrations without time-consuming sample preparation. For SPI an electron beam pumped excimer light source of own fabrication (E-Lux) is used. The SPI-ITMS system was characterized by the analytical study of different drugs like cannabis, heroin, cocaine, amphetamines, and some precursors. Additionally, it was successfully tested on-site in a closed illegal drug laboratory, where low quantities of MDMA could be directly detected in samples from floors, walls and lab equipments. The second analytical system is based on an ion mobility (IM) spectrometer with resonant multiphoton ionization (REMPI). With the frequency quadrupled Nd:YAG laser (266 nm), used for ionization, a selective and sensitive detection of aromatic compounds is possible. By application of suited aromatic dopants, in addition, also non-aromatic polar compounds are accessible by ion molecule reactions like proton transfer or complex formation. Selected drug precursors could be successfully detected with this device as well, qualifying it to a lower-priced alternative or useful supplement of the SPI-ITMS system for security analysis.

  13. Matrix-assisted ultraviolet laser desorption/ionization mass spectrometry applied to multiple forms of lipases.

    Science.gov (United States)

    Hedrich, H C; Isobe, K; Stahl, B; Nokihara, K; Kordel, M; Schmid, R D; Karas, M; Hillenkamp, F; Spener, F

    1993-06-01

    Matrix-assisted ultraviolet laser desorption/ionization mass spectrometry was used to investigate heterogeneous patterns and molecular masses of microbial lipases from Penicillium camembertii, Geotrichum candidum, and Pseudomonas sp. Mass spectral peaks of the native, glycosylated lipases from P. camembertii and G. candidum were broader than those of the corresponding deglycosylated enzymes, indicative of heterogeneous glycosylations. The broader peaks in the mass spectra were caused by an overlapping of unresolved peaks, derived from single glycoprotein species. Molecular masses determined for the deglycosylated proteins were in excellent agreement with those deduced from amino acid composition and sequence data, whereas with conventional biochemical methods (gelfiltration, sodium dodecyl sulfate-polyacrylamide gel electrophoresis) only very rough estimations of molecular masses were possible. By mass spectrometric analysis of the four fractions of chromatographically separated P. camembertii lipase molecular masses of 29,990, 34,030, 31,990, and 32,140 Da were found before and 29,960, 29,980, 29,990 and 30,010 Da, respectively, after deglycosylation. Thus from the four native fractions of P. camembertii lipase three were glycoproteins. G. candidum lipase showed an average molecular mass of 63,500 Da for the heterogeneously deglycosylated native form and a molecular mass of 59,650 Da for the deglycosylated enzyme. For the Pseudomonas lipase, which could only be isolated with lipids firmly attached, a molecular mass of 32,890 Da was determined, in close agreement with that derived from the cDNA sequence.

  14. Thermal ionization and thermally activated crossover quenching processes for 5d-4f luminescence in Y3 A l5-x G ax O12 : P r3+

    NARCIS (Netherlands)

    Ueda, J.; Meijerink, Andries; Dorenbos, P.; Bos, A.J.J.; Tanabe, Setsuhisa

    2017-01-01

    We investigated thermally activated ionization and thermally activated crossover as the two possibilities of quenching of 5d luminescence in Pr3+-doped Y3Al5-xGaxO12. Varying the Ga content x gives the control over the relative energy level location of the 5d and 4f2:PJ3 states of Pr3+ and the

  15. Standard addition strip for quantitative electrostatic spray ionization mass spectrometry analysis: determination of caffeine in drinks.

    Science.gov (United States)

    Tobolkina, Elena; Qiao, Liang; Roussel, Christophe; Girault, Hubert H

    2014-12-01

    Standard addition strips were prepared for the quantitative determination of caffeine in different beverages by electrostatic spray ionization mass spectrometry (ESTASI-MS). The gist of this approach is to dry spots of caffeine solutions with different concentrations on a polymer strip, then to deposit a drop of sample mixed with an internal standard, here theobromine on each spot and to measure the mass spectrometry signals of caffeine and theobromine by ESTASI-MS. This strip approach is very convenient and provides quantitative analyses as accurate as the classical standard addition method by MS or liquid chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Ionization Suppression and Recovery in Direct Biofluid Analysis Using Paper Spray Mass Spectrometry

    Science.gov (United States)

    Vega, Carolina; Spence, Corina; Zhang, Chengsen; Bills, Brandon J.; Manicke, Nicholas E.

    2016-04-01

    Paper spray mass spectrometry is a method for the direct analysis of biofluid samples in which extraction of analytes from dried biofluid spots and electrospray ionization occur from the paper on which the dried sample is stored. We examined matrix effects in the analysis of small molecule drugs from urine, plasma, and whole blood. The general method was to spike stable isotope labeled analogs of each analyte into the spray solvent, while the analyte itself was in the dried biofluid. Intensity of the labeled analog is proportional to ionization efficiency, whereas the ratio of the analyte intensity to the labeled analog in the spray solvent is proportional to recovery. Ion suppression and recovery were found to be compound- and matrix-dependent. Highest levels of ion suppression were obtained for poor ionizers (e.g., analytes lacking basic aliphatic amine groups) in urine and approached -90%. Ion suppression was much lower or even absent for good ionizers (analytes with aliphatic amines) in dried blood spots. Recovery was generally highest in urine and lowest in blood. We also examined the effect of two experimental parameters on ion suppression and recovery: the spray solvent and the sample position (how far away from the paper tip the dried sample was spotted). Finally, the change in ion suppression and analyte elution as a function of time was examined by carrying out a paper spray analysis of dried plasma spots for 5 min by continually replenishing the spray solvent.

  17. Anisole, a new dopant for atmospheric pressure photoionization mass spectrometry of low proton affinity, low ionization energy compounds

    NARCIS (Netherlands)

    Kauppila, TJ; Kostiainen, R; Bruins, AP

    2004-01-01

    Atmospheric pressure photoionization (APPI) is a novel method of ionization in liquid chromatography/mass spectrometry (LC/MS). It was originally developed in order to broaden the range of LC/MS ionizable compounds towards less polar compounds that cannot be analyzed by electrospray (ESI) and

  18. Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

    OpenAIRE

    Renata Raina; Patricia Hall

    2008-01-01

    A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) with gas chromatography-tandem mass spectrometry (GC-MS/MS) in selected reaction monitoring (SRM) mode with both electron ionization (EI) and negative-ion chemical ionization (NCI) are presented for over 50 pesticides ranging from organochlorines (OCs), organophosphorus pesticides (OPs) and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalflurali...

  19. The Effect of Thermal Mass on Annual Heat Load and Thermal Comfort in Cold Climate Construction

    DEFF Research Database (Denmark)

    Stevens, Vanessa; Kotol, Martin; Grunau, Bruno

    2016-01-01

    Thermal mass in building construction refers to a building material's ability to absorb and release heat based on changing environmental conditions. In building design, materials with high thermal mass used in climates with a diurnal temperature swing around the interior set-point temperature have...... been shown to reduce the annual heating demand. However, few studies exist regarding the effects of thermal mass in cold climates. The purpose of this research is to determine the effect of high thermal mass on the annual heat demand and thermal comfort in a typical Alaskan residence using energy...... that while increased thermal mass does have advantages in all climates, such as a decrease in summer overheating, it is not an effective strategy for decreasing annual heat demand in typical residential buildings in Alaska. (C) 2015 American Society of Civil Engineers....

  20. Microscopy ambient ionization top-down mass spectrometry reveals developmental patterning.

    Science.gov (United States)

    Hsu, Cheng-Chih; White, Nicholas M; Hayashi, Marito; Lin, Eugene C; Poon, Tiffany; Banerjee, Indroneal; Chen, Ju; Pfaff, Samuel L; Macagno, Eduardo R; Dorrestein, Pieter C

    2013-09-10

    There is immense cellular and molecular heterogeneity in biological systems. Here, we demonstrate the utility of integrating an inverted light microscope with an ambient ionization source, nanospray electrospray desorption ionization, attached to a high-resolution mass spectrometer to characterize the molecular composition of mouse spinal cords. We detected a broad range of molecules, including peptides and proteins, as well as metabolites such as lipids, sugars, and other small molecules, including S-adenosyl methionine and glutathione, through top-down MS. Top-down analysis revealed variation in the expression of Hb, including the transition from fetal to adult Hb and heterogeneity in Hb subunits consistent with the genetic diversity of the mouse models. Similarly, temporal changes to actin-sequestering proteins β-thymosins during development were observed. These results demonstrate that interfacing microscopy with ambient ionization provides the means to perform targeted in situ ambient top-down mass spectral analysis to study the pattern of proteins, lipids, and sugars in biologically heterogeneous samples.

  1. Study of Electrochemical Reactions Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Pengyuan; Lanekoff, Ingela T.; Laskin, Julia; Dewald, Howard D.; Chen, Hao

    2012-07-03

    The combination of electrochemistry (EC) and mass spectrometry (MS) is a powerful analytical tool for studying mechanisms of redox reactions, identification of products and intermediates, and online derivatization/recognition of analytes. This work reports a new coupling interface for EC/MS by employing nanospray desorption electrospray ionization (nano-DESI), a recently developed ambient ionization method. We demonstrate online coupling of nano-DESI-MS with a traditional electrochemical flow cell, in which the electrolyzed solution emanating from the cell is ionized by nano-DESI for MS analysis. Furthermore, we show first coupling of nano-DESI-MS with an interdigitated array (IDA) electrode enabling chemical analysis of electrolyzed samples directly from electrode surfaces. Because of its inherent sensitivity, nano-DESI enables chemical analysis of small volumes and concentrations of sample solution. Specifically, good-quality signal of dopamine and its oxidized form, dopamine ortho-quinone, was obtained using 10 μL of 1 μM solution of dopamine on the IDA. Oxidation of dopamine, reduction of benzodiazepines, and electrochemical derivatization of thiol groups were used to demonstrate the performance of the technique. Our results show the potential of nano-DESI as a novel interface for electrochemical mass spectrometry research.

  2. Derivatization of Dextran for Multiply Charged Ion Formation and Electrospray Ionization Time-of-Flight Mass Spectrometric Analysis

    Science.gov (United States)

    Tapia, Jesus B.; Hibbard, Hailey A. J.; Reynolds, Melissa M.

    2017-10-01

    We present the use of a simple, one-pot derivatization to allow the polysaccharide dextran to carry multiple positive charges, shifting its molecular weight distribution to a lower m/ z range. We performed this derivatization because molecular weight measurements of polysaccharides by mass spectrometry are challenging because of their lack of readily ionizable groups. The absence of ionizable groups limits proton abstraction and suppresses proton adduction during the ionization process, producing mass spectra with predominantly singly charged metal adduct ions, thereby limiting the detection of large polysaccharides. To address this challenge, we derivatized dextran T1 (approximately 1 kDa) by attaching ethylenediamine, giving dextran readily ionizable, terminal amine functional groups. The attached ethylenediamine groups facilitated proton adduction during the ionization process in positive ion mode. Using the low molecular weight dextran T1, we tracked the number of ethylenediamine attachments by measuring the mass shift from underivatized to derivatized dextran T1. Using electrospray ionization time-of-flight mass spectrometry, we observed derivatized dextran chains ranging from two to nine glucose residues with between one and four attachments/charges. Our success in shifting derivatized dextran T1 toward the low m/ z range suggests potential for this derivatization as a viable route for analysis of high molecular weight polysaccharides using electrospray ionization time-of-flight mass spectrometry. [Figure not available: see fulltext.

  3. Ambient ionization and direct identification of volatile organic compounds with microwave-induced plasma mass spectrometry.

    Science.gov (United States)

    Li, Dandan; Tian, Yong-Hui; Zhao, Zhongjun; Li, Wenwen; Duan, Yixiang

    2015-02-01

    An innovative method of volatile organic compounds analysis by using microwave-induced plasma ionization (MIPI) source in combination with an ambient ion trap mass spectrometer is presented here. Using MIPI for direct sample vapor, analysis was achieved without any sample preparation or subsequent heating. The relative abundance of the target compounds can be obtained almost instantly within a few seconds. The ionization processes of different volatile compounds was optimized, and the limits of detection were identified in the range of 0.15-4.5 pptv or 0.73-8.80 pg ml(-1). The relative standard deviation (RSD) is in the range of 4-14%, while correlation coefficients of the working curves (R(2)) are better than 0.98. The new method possesses advantages of ease operation, time-saving, high sensitivity and inexpensive setup. In addition, the ionization processes of short n-alkane chains were investigated with the MIPI technique, and a unique [M + 13](+) was detected, which has not been reported in detail by any other related ionization techniques. An ionization mechanism was proposed on the basis of the experimental results obtained in this work and available information in literatures, in which the n-alkanes in the plasma environment possibly generate protonated cyclopentadiene [M - 5](+) or alkyl-substituted analogues as well as hydrous ions [M + 13](+) and [M + 13 + 18](+), as shown in Scheme 1 in the main text. Copyright © 2015 John Wiley & Sons, Ltd.

  4. Shotgun Approach for Quantitative Imaging of Phospholipids Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Thomas, Mathew; Laskin, Julia

    2014-02-04

    Mass spectrometry imaging (MSI) has been extensively used for determining spatial distributions of molecules in biological samples, and there is increasing interest in using MSI for quantification. Nanospray desorption electrospray ionization, or nano-DESI, is an ambient MSI technique where a solvent is used for localized extraction of molecules followed by nanoelectrospray ionization. Doping the nano-DESI solvent with carefully selected standards enables online quantification during MSI experiments. In this proof-of-principle study, we demonstrate this quantification approach can be extended to provide shotgun-like quantification of phospholipids in thin brain tissue sections. Specifically, two phosphatidylcholine (PC) standards were added to the nano-DESI solvent for simultaneous imaging and quantification of 22 PC species observed in nano-DESI MSI. Furthermore, by combining the quantitative data obtained in the individual pixels, we demonstrate quantification of these PC species in seven different regions of a rat brain tissue section.

  5. Complexation between the fungicide tebuconazole and copper(II) probed by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Dytrtová, Jana Jaklová; Jakl, Michal; Schröder, Detlef; Čadková, Eva; Komárek, Michael

    2011-04-30

    Electrospray ionization mass spectrometry (ESI-MS) is used to probe the complex formation between tebuconazole (1) and copper(II) salts, which both are commonly used fungicides in agriculture. Experiments with model solutions containing 1 and CuCl(2) reveal the initial formation of the copper(II) species [(1)CuCl](+) and [(1)(2)CuCl](+) which undergo reduction to the corresponding copper(I) ions [(1)Cu](+) and [(1)(2)Cu](+) under more drastic ionization conditions in the ESI source. In additional experiments, copper/tebuconazole complexes were also detected in samples made from soil solutions of various origin and different amount of mineralization. The direct sampling of such solutions via ESI-MS is thus potentially useful for understanding of the interactions between copper(II) salts and tebuconazole in environmental samples. Copyright © 2011 John Wiley & Sons, Ltd.

  6. Laser Microdissection and Atmospheric Pressure Chemical Ionization Mass Spectrometry Coupled for Multimodal Imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, Matthias [ORNL; Ovchinnikova, Olga S [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL

    2013-01-01

    This paper describes the coupling of ambient laser ablation surface sampling, accomplished using a laser capture microdissection system, with atmospheric pressure chemical ionization mass spectrometry for high spatial resolution multimodal imaging. A commercial laser capture microdissection system was placed in close proximity to a modified ion source of a mass spectrometer designed to allow for sampling of laser ablated material via a transfer tube directly into the ionization region. Rhodamine 6G dye of red sharpie ink in a laser etched pattern as well as cholesterol and phosphatidylcholine in a cerebellum mouse brain thin tissue section were identified and imaged from full scan mass spectra. A minimal spot diameter of 8 m was achieved using the 10X microscope cutting objective with a lateral oversampling pixel resolution of about 3.7 m. Distinguishing between features approximately 13 m apart in a cerebellum mouse brain thin tissue section was demonstrated in a multimodal fashion including co-registered optical and mass spectral chemical images.

  7. Characterization of post translational modifications of histones by electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lipton, M.S.W.; Hofstadler, S.A.; Springer, D.L.; Edmonds, C.G. [Pacific Northwest Lab., Richland, WA (United States)

    1994-12-31

    Histones, which together with other specialized protein and DNA, form the complex structure of chromatin in the nucleus, are post-translationally modified. In the case of histone proteins, such post-translational modifications include acetylation, methylation, and phosphorylation. These modifications are known to be associated with the alteration in chromatin structure which occurs through the cell cycle or in response to chemical or radiation induced damage and repair to the cell nucleus. Such modifications effect of the protein-protein and protein-DNA associations of chromatin through ionic, H-bonds and hydrophobic interactions. The authors hypothesize that the distinct temporal and spatial patterns of these modifications, although complex, are non-random and predictably related to cellular responses to physical or chemical insult. Electrospray ionization mass spectrometry permits the direct analysis of the intact modified protein with precise mass measurement unambiguous evaluation of the nature and extent of posttranslational modification. Preliminary experiments of HPLC-purified histones from chick erythrocyte cells revealed protein species, which have mass values which closely correlate to the mass values predicted from the gene sequence. The mass spectra of all the proteins were found to contain additional species which appear to correspond to sequence varients and/or post translational modifications to the proteins. Histones H2B and H3 were examined more closely by mass spectrometry on a linear triple quadrupole mass spectrometer as well as a Fourier transform ion cyclotron resonance mass spectrometer.

  8. Affinity surface-assisted laser desorption/ionization mass spectrometry for peptide enrichment.

    Science.gov (United States)

    Coffinier, Yannick; Nguyen, Nhung; Drobecq, Hervé; Melnyk, Oleg; Thomy, Vincent; Boukherroub, Rabah

    2012-12-07

    In this paper, we report on the functionalization of silicon nanostructured (NanoSi) surface with an organic layer of nitrilotriacetic acid (NTA) and its subsequent use as an affinity surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) interface for histidine-tagged peptide enrichment and mass spectrometry analysis. The NTA terminal groups are immobilized onto the NanoSi surface via very stable Si-C covalent bonds. The NTA-modified NanoSi (NTA-NanoSi) interface was characterized by contact angle measurements, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The NTA-NanoSi interface has shown a good selectivity toward His-tagged peptide and permits its enrichment from an artificial mixture of both tagged and untagged peptides and its subsequent mass spectrometry detection with good signal/noise ratio.

  9. Imaging of Lipids and Metabolites Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela; Laskin, Julia

    2015-01-17

    In recent years, mass spectroscopy imaging (MSI) has emerged as a foundational technique in metabolomics and drug screening providing deeper understanding of complex mechanistic pathways within biochemical systems and biological organisms. We have been invited to contribute a chapter to a new Springer series volume, entitled “Mass Spectrometry Imaging of Small Molecules”. The volume is planned for the highly successful lab protocol series Methods in Molecular Biology, published by Humana Press, USA. The volume is aimed to equip readers with step-by-step mass spectrometric imaging protocols and bring rapidly maturing methods of MS imaging to life science researchers. The chapter will provide a detailed protocol of ambient MSI by use of nanospray desorption electrospray ionization.

  10. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Perdian, David C. [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  11. Graphene coated silica applied for high ionization matrix assisted laser desorption/ionization mass spectrometry: A novel approach for environmental and biomolecule analysis.

    Science.gov (United States)

    Nasser Abdelhamid, Hani; Wu, Bo-Sgum; Wu, Hui-Fen

    2014-08-01

    The integration of nanotechnology with mass spectrometry for sensitive and selective detection of molecules is a hot/important field of research. Synthesis of graphene (G) coated with mesoporous silica (SiO2, G@SiO2) for mass spectrometric application has been demonstrated. For the first time, we proposed the significant role of surfactant that used during the synthesis of mesorporous silicate (SiO2) in mass spectrometry. It was noticed that G could initiate SiO2 via surfactants which work as initiators for further ionization. The porosity of SiO2 trapped the analytes that was released and ionized with the surfactant fragments. Undoubtedly, strong background interferences were present in the case of organic matrix, which greatly obscured the detection of low molecular weight compounds. G@SiO2 nanocomposite affords several advantages, such as the ability to detect small molecules (silica mesoporosity, and high ionization efficiency over than G or conventional matrices. The high performance of G@SiO2 is not only due to the large surface area but also due to high desorption/ionization efficiency of inevitably surfactant (cetyltrimethylammonium chloride, CATB). Unlike the conventional MALDI-MS, the G@SiO2-MS is capable of generating multiply charged polysaccharides. The present method was validated to detect surfactants with low limits of detection. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Analysis of xyloglucans by ambient chloride attachment ionization tandem mass spectrometry.

    Science.gov (United States)

    Vinueza, Nelson R; Gallardo, Vanessa A; Klimek, John F; Carpita, Nicholas C; Kenttämaa, Hilkka I

    2013-10-15

    Xyloglucan oligomers obtained upon enzyme digestion from Hymenaea courbaril, Arabidopsis Columbia-0 and mur3 were ionized and analyzed by using chloride anion attachment electrospray ionization (ESI) and tandem mass spectrometry. MW determination and structural elucidation of several xyloglucan oligomers was performed directly from the mixture solutions without sample pretreatment or derivatization. Sodium cation attachment was used to determine the number of xyloglucans present in the mixtures and their MWs. However, tandem mass spectrometry results showed that structure elucidation based on the sodium adducts is ambiguous. Chloride anion also forms stable adducts with these xyloglucans upon ESI. These adducts can be readily identified due to the chlorine isotope pattern. The mass spectral profile of xyloglucans obtained for the mixtures matches the HPAEC results, thus validating this methodology for the determination of the xyloglucan composition and the MW of each xyloglucan. Upon collisional activation in MS(2) experiments, the chloride anion adducts readily lose HCl, which helps verify the molecular weight of each xyloglucan. Isolating the resulting anion (deprotonated oligomer) and subjecting it to further collision-activated dissociation experiments (MS(n); n=3-4) yields useful structural information that allows the differentiation between isomeric anions and hence determination of the sequence of the xyloglucan oligomers. The deprotonated oligomers fragment by a stepwise loss of sugar units from the reducing end. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

  13. Determination of triacetone triperoxide using ultraviolet femtosecond multiphoton ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Ezoe, Ryota; Imasaka, Tomoko; Imasaka, Totaro

    2015-01-01

    Triacetone triperoxide (TATP), an explosive compound, was measured using gas chromatography combined with multiphoton ionization time-of-flight mass spectrometry (GC/MPI-TOFMS). By decreasing the pulse width of a femtosecond laser from 80 to 35 fs, a molecular ion was drastically enhanced and was measured as one of the major ions in the mass spectrum. The detection limits obtained using the molecular (M(+)) and fragment (C2H3O(+)) ions were similar or slightly superior to those obtained using conventional mass spectrometry based on electron and chemical ionization. In order to improve the reliability, an isotope of TATP, i.e., TATP-d18, was synthesized and used as an internal standard in the trace analysis of TATP in a sample of human blood. TATP could be identified in a two-dimensional display, even though numerous interfering compounds were present in the sample. Acetone, which is frequently used as a solvent in sampling TATP, produced a chemical species with a retention time nearly identical to that of TATP and provided a C2H3O(+) fragment ion that was employed for measuring a chromatogram of TATP in conventional MS. This compound, the structure of which was assigned as phorone, was clearly differentiated from TATP based on a molecular ion observable in MPI-TOFMS. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Thermal /Soret/ diffusion effects on interfacial mass transport rates

    Science.gov (United States)

    Rosner, D. E.

    1980-01-01

    It is shown that thermal (Soret) diffusion significantly alters convective mass transport rates and important transition temperatures in highly nonisothermal flow systems involving the transport of 'heavy' species (vapors or particles). Introduction of the Soret transport term is shown to result in mass transfer effects similar to those of 'suction' and a homogeneous chemical 'sink'. It is pointed out that this analogy provides a simple method of correlating and predicting thermal diffusion effects in the abovementioned systems.

  15. Convective Concrete : Additive Manufacturing to facilitate activation of thermal mass

    NARCIS (Netherlands)

    de Witte, D.; de Klijn-Chevalerias, M.L.; Loonen, R.C.G.M.; Hensen, JLM; Knaack, U.; Zimmermann, G

    2017-01-01

    This paper reports on the research-driven design process of an innovative thermal mass concept: Convective Concrete. The goal is to improve building energy efficiency and comfort levels by addressing some of the shortcomings of conventional building slabs with high thermal storage capacity. Such

  16. A Comparison of Alternating Current and Direct Current Electrospray Ionization for Mass Spectrometry

    Science.gov (United States)

    Sarver, Scott A.; Chetwani, Nishant; Dovichi, Norman J.; Go, David B.; Gartner, Carlos A.

    2014-04-01

    A series of studies comparing the performance of alternating current electrospray ionization (AC ESI) mass spectrometry (MS) and direct current electrospray ionization (DC ESI) MS have been conducted, exploring the absolute signal intensity and signal-to-background ratios produced by both methods using caffeine and a model peptide as targets. Because the high-voltage AC signal was more susceptible to generating gas discharges, the operating voltage range of AC ESI was significantly smaller than that for DC ESI, such that the absolute signal intensities produced by DC ESI at peak voltages were one to two orders of magnitude greater than those for AC ESI. Using an electronegative nebulizing gas, sulfur hexafluoride (SF6), instead of nitrogen (N2) increased the operating range of AC ESI by ~50 %, but did not appreciably improve signal intensities. While DC ESI generated far greater signal intensities, both ionization methods produced comparable signal-to-background noise, with AC ESI spectra appearing qualitatively cleaner. A quantitative calibration analysis was performed for two analytes, caffeine and the peptide MRFA. AC ESI utilizing SF6 outperforms all other techniques for the detection of MRFA, producing chromatographic limits of detection nearly one order of magnitude lower than that of DC ESI utilizing N2, and one-half that of DC ESI utilizing SF6. However, DC ESI outperforms AC ESI for the analysis of caffeine, indicating that improvements in spectral quality may benefit certain compounds or classes of compounds, on an individual basis.

  17. Electrospray-ionization mass spectrometry of mixtures of triterpene glycosides with paracetamol

    Science.gov (United States)

    Lekar, A. V.; Vetrova, E. V.; Borisenko, N. I.; Yakovishin, L. A.; Grishkovets, V. I.

    2010-11-01

    Molecular complexation of paracetamol with hederagenin 3-O-α-L-rhamnopyranosyl-(1 → 2)-O-α-L-arabinopyranoside (α-hederin) and its 28-O-α-L-rhamnopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 6)-O-β-Dglucopyranosyl ether (hederasaponin C) was investigated for the first time using electrospray-ionization mass spectrometry (ESI-MS). The glycosides form complexes with paracetamol in a 1:1 molar ratio. The hederasaponin C complex is more stable. The structures of the glycosides and paracetamol are concluded to have an impact on the complexation process.

  18. Cosmetic Analysis Using Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging (MALDI-MSI

    Directory of Open Access Journals (Sweden)

    Rodrigo Ramos Catharino

    2013-03-01

    Full Text Available A new “omic” platform—Cosmetomics—that proves to be extremely simple and effective in terms of sample preparation and readiness for data acquisition/interpretation is presented. This novel approach employing Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Imaging (MALDI-MSI for cosmetic analysis has proven to readily identify and quantify compounds of interest. It also allows full control of all the production phases, as well as of the final product, by integration of both analytical and statistical data. This work has focused on products of daily use, namely nail polish, lipsticks and eyeliners of multiple brands sold in the worldwide market.

  19. Chlorine and Bromine Isotope Fractionation of Halogenated Organic Compounds in Electron Ionization Mass Spectrometry

    OpenAIRE

    Tang, Caiming; Tan, Jianhua; Shi, Zhiqiang; Tang, Caixing; Xiong, Songsong; Liu, Jun; Fan, Yujuan; Peng, Xianzhi

    2017-01-01

    Revelation of chlorine and bromine isotope fractionation of halogenated organic compounds (HOCs) in electron ionization mass spectrometry (EI-MS) is crucial for compound-specific chlorine/bromine isotope analysis (CSIA-Cl/Br) using gas chromatography EI-MS (GC-EI-MS). This study systematically investigated chlorine/bromine isotope fractionation in EI-MS of HOCs including 12 organochlorines and 5 organobromines using GC-double focus magnetic-sector high resolution MS (GC-DFS-HRMS). Chlorine/br...

  20. Generation of CsI cluster ions for mass calibration in matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Lou, Xianwen; van Dongen, Joost L J; Meijer, E W

    2010-07-01

    A simple method was developed for the generation of cesium iodide (CsI) cluster ions up to m/z over 20,000 in matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Calibration ions in both positive and negative ion modes can readily be generated from a single MALDI spot of CsI(3) with 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) matrix. The major cluster ion series observed in the positive ion mode is [(CsI)(n)Cs](+), and in the negative ion mode is [(CsI)(n)I](-). In both cluster series, ions spread evenly every 259.81 units. The easy method described here for the production of CsI cluster ions should be useful for MALDI MS calibrations. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  1. Comparing and combining capillary electrophoresis electrospray ionization mass spectrometry and nano-liquid chromatography electrospray ionization mass spectrometry for the characterization of post-translationally modified histones.

    Science.gov (United States)

    Sarg, Bettina; Faserl, Klaus; Kremser, Leopold; Halfinger, Bernhard; Sebastiano, Roberto; Lindner, Herbert H

    2013-09-01

    We present the first comprehensive capillary electrophoresis electrospray ionization mass spectrometry (CESI-MS) analysis of post-translational modifications derived from H1 and core histones. Using a capillary electrophoresis system equipped with a sheathless high-sensitivity porous sprayer and nano-liquid chromatography electrospray ionization mass spectrometry (nano-LC-ESI-MS) as two complementary techniques, we characterized H1 histones isolated from rat testis. Without any pre-separation of the perchloric acid extraction, a total of 70 different modified peptides, including 50 phosphopeptides, were identified in the rat linker histones H1.0, H1a-H1e, and H1t. Out of the 70 modified H1 histone peptides, 27 peptides could be identified with CESI-MS only, and 11 solely with LC-ESI-MS. Immobilized metal-affinity chromatography enrichment prior to MS analysis yielded a total of 55 phosphopeptides; 22 of these peptides could be identified only by CESI-MS, and 19 only by LC-ESI-MS, showing the complementarity of the two techniques. We mapped 42 H1 modification sites, including 31 phosphorylation sites, of which 8 were novel sites. For the analysis of core histones, we chose a different strategy. In a first step, the sulfuric-acid-extracted core histones were pre-separated using reverse-phase high-performance liquid chromatography. Individual rat testis core histone fractions obtained in this way were digested and analyzed via bottom-up CESI-MS. This approach yielded the identification of 42 different modification sites including acetylation (lysine and N(α)-terminal); mono-, di-, and trimethylation; and phosphorylation. When we applied CESI-MS for the analysis of intact core histone subtypes from butyrate-treated mouse tumor cells, we were able to rapidly detect their degree of modification, and we found this method very useful for the separation of isobaric trimethyl and acetyl modifications. Taken together, our results highlight the need for additional techniques

  2. Detection and imaging of thermochromic ink compounds in erasable pens using desorption electrospray ionization mass spectrometry.

    Science.gov (United States)

    Khatami, Amin; Prova, Shamina S; Bagga, Aafreen K; Yan Chi Ting, Michelle; Brar, Gurnoor; Ifa, Demian R

    2017-06-30

    Thermochromic ink pens are widely accessible worldwide and have gained popularity among the general public. These pens are very useful to undo mistakes while writing important documents or exams. They are also, however, misused in committing crimes such as counterfeiting checks or wills. Thus, the forensics community is in need of techniques that will allow these forgeries to be detected rapidly, reliably and conveniently. Thermochromic ink compounds were investigated using Desorption Electrospray Ionization (DESI) coupled with an LTQ mass spectrometer and Thin-Layer Chromatography (TLC). Tandem mass spectrometric analysis was conducted using Electrospray Ionization (ESI) coupled with an Orbitrap LTQ mass spectrometer performing Collision-Induced Dissociation (CID) for identification of ink traces. Chemical marker ions characteristic of the state of ink (visible or invisible) were identified and mapped in ink traces by the use of DESI-MS imaging. These ions can be employed by forensic experts as fingerprint markers in forged documents. The marker ions were also characterised by conducting tandem mass spectrometry using paper spray in an Orbitrap LTQ mass spectrometer. Specific chemical components yielding ions of m/z 400, 405, 615 and 786 were distinguished as only being apparent in the invisible and reappeared state of the ink. The absence of these compounds in the original state of the ink enabled their recognition as useful chemical determinants in detecting forgery. DESI-MSI was thus shown to be a very useful, convenient and reliable technique for detecting forgery in paper documents due to its fast and reproducible mode of analysis, with no sample preparation and minimal damage to the document under investigation. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  3. Rapid analysis of drug dissolution by paper spray ionization mass spectrometry.

    Science.gov (United States)

    Liu, Yang; Liu, Ning; Zhou, Ya-Nan; Lin, Lan; He, Lan

    2017-03-20

    With a great quantity of solid dosage tested by dissolution technology, developing a rapid and sensitive method to access the content of drug within dissolution media is highly desired by analysts and scientists. Traditionally, dissolution media is not compatible with mass spectrometry since the inorganic salts in the media might damage the mass spectrometer. Here, paper spray ionization mass spectrometry (PSI-MS), one of the ambient mass spectrometry technologies, is developed to characterize the content of drugs in dissolution media. The porous structure of paper can effectively retain salts from entering mass spectrometer. This makes the measurement of drug content within dissolution media by mass spectrometer possible. After the experimental parameters were optimized, calibration curves of model drugs - enalapril, quinapril and benazepril were established by using corresponding deuterated internal standards. PSI-MS was then deployed to characterize the content of enalapril from the dissolution testing of enalapril tablets. The results from PSI-MS are comparable to those from HPLC characterization. More importantly, the analysis time of 6 samples is shortened from 90min to 6min. Detection limit of enalapril maleate tablets by PSI-MS is 1/300 of LC. PSI-MS is rapid, sensitive and accurate in analyzing drug content from dissolution tests. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Metal powder substrate-assisted laser desorption/ionization mass spectrometry for polyethylene analysis.

    Science.gov (United States)

    Yalcin, Talat; Wallace, William E; Guttman, Charles M; Li, Liang

    2002-09-15

    Polyethylene is one of the most important industrial polymers and is also one of the most challenging polymers to be characterized by mass spectrometry. We have developed a substrate-assisted laser desorption/ionization (LDI) mass spectrometric method for polyethylene analysis. In this method, cobalt, copper, nickel, or iron metal powders are used as a sample substrate and silver nitrate is used as the cationization reagent. Using a conventional UV LDI time-of-flight mass spectrometer, intact oligomer ions having masses up to 5000 u can be detected. Cobalt is found to produce spectra with the highest signal-to-noise ratio and the lowest level of fragmentation. Cobalt powder size is shown to have some effect on the spectra produced. The best results are obtained with the use of cobalt powders with diameters ranging from 30 to 100 microm. Fragmentation cannot be totally eliminated, but the fragment ion peaks can be readily discerned from the intact polyethylene ions in the substrate-assisted LDI spectrum. Thus, the average molecular masses of low-mass polyethylene samples can be determined by using this method. A rapid heating model is used to account for the effectiveness of using the coarse metal powders to assist the analysis of intact polyethylene molecules by LDI.

  5. Single photon ionization and chemical ionization combined ion source based on a vacuum ultraviolet lamp for orthogonal acceleration time-of-flight mass spectrometry.

    Science.gov (United States)

    Hua, Lei; Wu, Qinghao; Hou, Keyong; Cui, Huapeng; Chen, Ping; Wang, Weiguo; Li, Jinghua; Li, Haiyang

    2011-07-01

    A novel combined ion source based on a vacuum ultraviolet (VUV) lamp with both single photon ionization (SPI) and chemical ionization (CI) capabilities has been developed for an orthogonal acceleration time-of-flight mass spectrometer (oaTOFMS). The SPI was accomplished using a commercial 10.6 eV krypton discharge lamp with a photon flux of about 10(11) photons s(-1), while the CI was achieved through ion-molecule reactions with O(2)(+) reactant ions generated by photoelectron ionization at medium vacuum pressure (MVP). To achieve high ionization efficiency, the ion source pressure was elevated to 0.3 mbar and the photoionization length was extended to 36 mm. As a result, limits of detection (LODs) down to 3, 4, and 6 ppbv were obtained for benzene, toluene, and p-xylene in MVP-SPI mode, and values of 8 and 10 ppbv were obtained for toluene and chloroform, respectively, in SPI-CI mode. As it is feasible to switch between MVP-SPI mode and SPI-CI mode rapidly, this system is capable of monitoring complex organic mixtures with a wide range of ionization energies (IEs). The analytical capacity of this system was demonstrated by measuring dehydrogenation products of long-chain paraffins to olefins through direct capillary sampling and drinking water disinfection byproducts from chlorine through a membrane interface.

  6. Laser desorption ionization mass spectrometry of protein tryptic digests on nanostructured silicon plates.

    Science.gov (United States)

    Dupré, Mathieu; Coffinier, Yannick; Boukherroub, Rabah; Cantel, Sonia; Martinez, Jean; Enjalbal, Christine

    2012-04-03

    We report on the simple application of a new nanostructured silicon (NanoSi) substrate as laser desorption/ionization (LDI)-promoting surface for high-throughput identification of protein tryptic digests by a rapid MS profiling and subsequent MS/MS analysis. The NanoSi substrate is easily prepared by chemical etching of crystalline silicon in NH(4)F/HNO(3)/AgNO(3) aqueous solution. To assess the LDI performances in terms of sensitivity, repeatability and robustness, the detection of small synthetic peptides (380-1700Da) was investigated. Moreover, peptide sequencing was tackled. Various tryptic synthetic peptide mixtures were first characterized in MS and MS/MS experiments carried out on a single deposit. Having illustrated the capability to achieve peptide detection and sequencing on these ionizing surfaces in the same run, protein tryptic digests from Cytochrome C, β-Casein, BSA and Fibrinogen were then analyzed in the femtomolar range (from 50 fmol for Cytochrome C down to 2 fmol for Fibrinogen). Comparison of the NanoSi MS and MS/MS data with those obtained with sample conditioned in organic matrix demonstrated a great behavior for low mass responses. We demonstrated the capability of LDI on NanoSi to be a complementary method to MALDI peptide mass fingerprinting ensuring determination of peptide molecular weights and sequences for more efficient protein database searches. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Chemical derivatization for electrospray ionization mass spectrometry. 1. Alkyl halides, alcohols, phenols, thiols, and amines

    Energy Technology Data Exchange (ETDEWEB)

    Quirke, J.M.E.; Adams, C.L.; Van Berkel, G.J. (Oak Ridge National Lab., TN (United States))

    1994-04-15

    Derivatization strategies and specific derivatization reactions for conversion of simple alkyl halides, alcohols, phenols, thiols, and amines to ionic or solution-ionizable derivatives, that is [open quotes]electrospray active[close quotes] (ES-active) forms of the analyte, are presented. Use of these reactions allows detection of analytes among those listed that are not normally amenable to analysis by electrospray ionization mass spectrometry (ES-MS). In addition, these reactions provide for analysis specificity and flexibility through functional group specific derivatization and through the formation of derivatives that can be detected in positive ion or in negative ion mode. For a few of the functional groups, amphoteric derivatives are formed that can be analyzed in either positive or negative ion modes. General synthetic strategies for transformation of members of these five compound classes to ES-active species are presented along with illustrative examples of suitable derivatives. Selected derivatives were prepared using model compounds and the ES mass spectra obtained for these derivatives are discussed. The analytical utility of derivatization for ES-MS analysis is illustrated in three experiments: (1) specific detection of the major secondary alcohol in oil of peppermint, (2) selective detection of phenols within a synthetic mixture of phenols, and (3) identification of the medicinal amines within a commercially available cold medication as primary, secondary or tertiary. 65 refs., 3 figs., 3 tabs.

  8. In situ analysis of soybeans and nuts by probe electrospray ionization mass spectrometry.

    Science.gov (United States)

    Petroselli, Gabriela; Mandal, Mridul K; Chen, Lee C; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

    2015-04-01

    The probe electrospray ionization (PESI) is an ESI-based ionization technique that generates electrospray from the tip of a solid metal needle. In the present work, we describe the PESI mass spectra obtained by in situ measurement of soybeans and several nuts (peanuts, walnuts, cashew nuts, macadamia nuts and almonds) using different solid needles as sampling probes. It was found that PESI-MS is a valuable approach for in situ lipid analysis of these seeds. The phospholipid and triacylglycerol PESI spectra of different nuts and soybean were compared by principal component analysis (PCA). PCA shows significant differences among the data of each family of seeds. Methanolic extracts of nuts and soybean were exposed to air and sunlight for several days. PESI mass spectra were recorded before and after the treatment. Along the aging of the oil (rancidification), the formation of oxidated species with variable number of hydroperoxide groups could be observed in the PESI spectra. The relative intensity of oxidated triacylglycerols signals increased with days of exposition. Monitoring sensitivity of PESI-MS was high. This method provides a fast, simple and sensitive technique for the analysis (detection and characterization) of lipids in seed tissue and degree of oxidation of the oil samples. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    CERN Document Server

    Rondo, L.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosolnucleation. Based on quantum chemical calculations it has been suggested that the quantitative detectionof gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased inthe presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was setup at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection ofH2SO4in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time inthe CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF(Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutralsulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presenceof dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS...

  10. Thin-layer chromatography/laser-induced acoustic desorption/electrospray ionization mass spectrometry.

    Science.gov (United States)

    Cheng, Sy-Chyi; Huang, Min-Zong; Shiea, Jentaie

    2009-11-15

    The combination of laser-induced acoustic desorption and electrospray ionization mass spectrometry (LIAD/ESI/MS) can be used to rapidly characterize chemical compounds separated on a thin layer chromatography (TLC) plate. We performed LIAD analysis by irradiating the rear side of an aluminum-based TLC plate with a pulsed infrared (IR) laser. To efficiently generate and transfer acoustic and shock waves to ablate the analyte-containing TLC gels, a glass slide was attached to the rear of the TLC plate and the gap between the glass slide and the TLC plate was filled with a viscous solution (glycerol). Although the diameter of the laser spot created on the rear of the TLC plate was approximately 0.35 mm, the ablated areas on the front sides of the silica gel bed and the C(18) reverse-phase gel bed had diameters of approximately 1.3 and 3 mm, respectively. The ablated analyte molecules were ionized in an ESI plume and then detected by an ion trap mass analyzer. This TLC/LIAD/ESI/MS approach allowed the components in mixtures of dye standards, drug standards, and rosemary essential oil to be separated and rapidly characterized.

  11. Identification of the Species of Origin for Meat Products by Rapid Evaporative Ionization Mass Spectrometry.

    Science.gov (United States)

    Balog, Julia; Perenyi, Dora; Guallar-Hoyas, Cristina; Egri, Attila; Pringle, Steven D; Stead, Sara; Chevallier, Olivier P; Elliott, Chris T; Takats, Zoltan

    2016-06-15

    Increasingly abundant food fraud cases have brought food authenticity and safety into major focus. This study presents a fast and effective way to identify meat products using rapid evaporative ionization mass spectrometry (REIMS). The experimental setup was demonstrated to be able to record a mass spectrometric profile of meat specimens in a time frame of <5 s. A multivariate statistical algorithm was developed and successfully tested for the identification of animal tissue with different anatomical origin, breed, and species with 100% accuracy at species and 97% accuracy at breed level. Detection of the presence of meat originating from a different species (horse, cattle, and venison) has also been demonstrated with high accuracy using mixed patties with a 5% detection limit. REIMS technology was found to be a promising tool in food safety applications providing a reliable and simple method for the rapid characterization of food products.

  12. Lipidomics: analysis of the lipid composition of cells and subcellular organelles by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Brügger, Britta

    2014-01-01

    Lipidomics aims to quantitatively define lipid classes, including their molecular species, in biological systems. Lipidomics has experienced rapid progress, mainly because of continuous technical advances in instrumentation that are now enabling quantitative lipid analyses with an unprecedented level of sensitivity and precision. The still-growing category of lipids includes a broad diversity of chemical structures with a wide range of physicochemical properties. Reflecting this diversity, different methods and strategies are being applied to the quantification of lipids. Here, I review state-of-the-art electrospray ionization tandem mass spectrometric approaches and direct infusion to quantitatively assess lipid compositions of cells and subcellular fractions. Finally, I discuss a few examples of the power of mass spectrometry-based lipidomics in addressing cell biological questions.

  13. Development of a Compact Resonance Ionization Mass Spectrometer for Trace Element Analysis of Potassium

    CERN Document Server

    Iwata, Yoshihiro; Minowa, Makoto

    2010-01-01

    A compact resonance ionization mass spectrometer is developed using two laser diodes and a quadrupole mass spectrometer to perform trace element analysis of potassium. With the help of a narrow linewidth of the laser diode, the isotope shifts of $^{40}{\\rm K}$ and $^{41}{\\rm K}$ of the 405~nm line with respect to $^{39}{\\rm K}$, corresponding to the transition of $4\\,^2$S$_{1/2}\\rightarrow$ $5\\,^2$P$^\\circ_{1/2}$, are measured to be $207\\pm13$~MHz and $451\\pm10$~MHz, respectively, by comparing them to the known hyperfine splitting widths of the $4\\,^2{\\rm S}_{1/2}$ ground state of each potassium isotope. The overall detection efficiency of an order of $\\sim10^{-6}$ in our setup indicates the availability of RIMS to the analysis of the trace metal impurities on or in a certain material such as the contamination assessment of semiconductor wafers.

  14. Communication: Transfer Ionization in a Thermal Reaction of a Cation and Anion: Ar+ with Br and I (Postprint)

    Science.gov (United States)

    2016-01-29

    The Journal of Chemical Physics : 17 October 2013. Government Purpose...Rainer Johnsen, and Albert A. Viggiano Citation: The Journal of Chemical Physics 139, 171102 (2013); doi: 10.1063/1.4828455 View online: http...release; distribution is unlimited. 1 THE JOURNAL OF CHEMICAL PHYSICS 139, 171102 (2013) Communication: Transfer ionization in a thermal reaction of

  15. Laser desorption/ionization mass spectrometric analysis of small molecules using fullerene-derivatized silica as energy-absorbing material.

    Science.gov (United States)

    Szabo, Zoltan; Vallant, Rainer M; Takátsy, Anikó; Bakry, Rania; Najam-ul-Haq, Muhammad; Rainer, Matthias; Huck, Christian W; Bonn, Günther K

    2010-05-01

    In spite of the growing acceptance of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the analysis of a wide variety of compounds, including polymers and proteins, its use in analyzing low-molecular-weight molecules (silica particles with different pore sizes are applied as thin layer for laser desorption/ionization (LDI) mass spectrometric analysis. Thus, an interference of intrinsic matrix ions can be eliminated or minimized in comparison with the state-of-the-art weak organic acid matrices. The desorption/ionization ability of the developed fullerene-silica materials depends on the applied laser power, sample preparation and pore size of the silica particles. Thus, fullerene-silica serves as an LDI support for mass spectrometric analysis of molecules (silica is demonstrated by the mass analysis of variety of small molecules such as carbohydrates, amino acids, peptides, phospholipids and drugs. 2010 John Wiley & Sons, Ltd.

  16. Evaluation of gas chromatography – electron ionization – full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis

    NARCIS (Netherlands)

    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

  17. Gas chromatography interfaced with atmospheric pressure ionization-quadrupole time-of-flight-mass spectrometry by low-temperature plasma ionization

    DEFF Research Database (Denmark)

    Norgaard, Asger W.; Kofoed-Sorensen, Vivi; Svensmark, Bo

    2013-01-01

    of mixtures of common volatile organic compounds. Amounts down to ca. 0.5 ng (on column) could be detected for most compounds and with a chromatographic performance comparable to that of GC/EIMS. In the positive mode, LTP ionization resulted in a compound specific formation of molecular ions M+center dot......A low temperature plasma (LTP) ionization interface between a gas chromatograph (GC) and an atmospheric pressure inlet mass spectrometer, was constructed. This enabled time-of-flight mass spectrometric detection of GC-eluting compounds. The performance of the setup was evaluated by injection......, protonated molecules [M + H](+), and adduct ions such as [(M + O) + H](+) and [M + NO](+). The ion patterns seemed unique for each of the analyzed compound classes and can therefore be useful for identification of functional groups. A total of 20 different compounds within 8 functional groups were analyzed....

  18. Development of high resolution resonance ionization mass spectrometry for trace analysis of {sup 93m}Nb

    Energy Technology Data Exchange (ETDEWEB)

    Takatsuka, Takaaki; Tomita, Hideki, E-mail: tomita@nagoya-u.jp [Nagoya University (Japan); Sonoda, Tetsu [RIKEN Nishina Center (Japan); Sonnenschein, Volker [Johannes Gutenberg University (Germany); Sakamoto, Chika [Nagoya University (Japan); Mita, Hiroki [University of Tsukuba, Institute of Physics (Japan); Noto, Takuma [Nagoya University (Japan); Ito, Chikara; Maeda, Shigetaka [Japan Atomic Energy Agency, Oarai Research and Development Center (Japan); Iguchi, Tetsuo [Nagoya University (Japan); Wada, Michiharu [RIKEN Nishina Center (Japan); Wendt, Klaus [Johannes Gutenberg University (Germany); Moore, Iain [University of Jyvaeskylae, Department of Physics (Finland)

    2013-04-15

    {sup 93}Nb(n, n Prime ){sup 93m}Nb reaction allows retrospective estimation of integrated fast neutron dose in nuclear reactor. We proposed isomer-selective trace analysis of {sup 93m}Nb by Resonance Ionization Mass Spectrometry (RIMS) combined with a gas-jet atomic source and an injection locked Ti:Sapphire laser system operated at several kHz. Resonant ionization spectroscopy of Nb in gas-jet using Ti:Sapphire laser was demonstrated.

  19. Investigation of diazepam drug using thermal analyses, mass spectrometry and semi-empirical MO calculation

    Science.gov (United States)

    Zayed, M. A.; Fahmey, M. A.; Hawash, M. F.

    2005-03-01

    In the present work diazepam (Dz) drug was investigated using thermal analyses (TA) measurements (TG/DTG) in comparison with EI mass spectral (MS) fragmentation at 70 and 20 eV. Semi-empirical MO calculations, MNDO procedure, have been carried out on diazepam both as neutral molecule and the corresponding positively charged molecular ion. These include molecular geometry, bond order, charge distribution, heats of formation and ionization energy. Thermogravimetric and kinetic analysis, reveal a high response of the drug to the temperature variation with very fast rate. It is completely decomposed in the temperature range between 204 and 340 °C with average kinetic energy (KE) at 164.69 kJ mol -1. On the other hand, diazepam can easily fragmented at low energy after ionization by electron energy at 9.56 eV. The losses of CO gas molecules followed by chlorine gas from the entity of diazepam (both neutral and charged molecular ion) as the best selected pathway were observed in both mass spectra (MS) and thermal analyses (TA). MNDO calculation was applied to declare both TA and MS observations.

  20. Enhanced capabilities for imaging gangliosides in murine brain with matrix-assisted laser desorption/ionization and desorption electrospray ionization mass spectrometry coupled to ion mobility separation.

    Science.gov (United States)

    Škrášková, Karolina; Claude, Emmanuelle; Jones, Emrys A; Towers, Mark; Ellis, Shane R; Heeren, Ron M A

    2016-07-15

    The increased interest in lipidomics calls for improved yet simplified methods of lipid analysis. Over the past two decades, mass spectrometry imaging (MSI) has been established as a powerful technique for the analysis of molecular distribution of a variety of compounds across tissue surfaces. Matrix-assisted laser desorption/ionization (MALDI) MSI is widely used to study the spatial distribution of common lipids. However, a thorough sample preparation and necessity of vacuum for efficient ionization might hamper its use for high-throughput lipid analysis. Desorption electrospray ionization (DESI) is a relatively young MS technique. In DESI, ionization of molecules occurs under ambient conditions, which alleviates sample preparation. Moreover, DESI does not require the application of an external matrix, making the detection of low mass species more feasible due to the lack of chemical matrix background. However, irrespective of the ionization method, the final information obtained during an MSI experiment is very complex and its analysis becomes challenging. It was shown that coupling MSI to ion mobility separation (IMS) simplifies imaging data interpretation. Here we employed DESI and MALDI MSI for a lipidomic analysis of the murine brain using the same IMS-enabled instrument. We report for the first time on the DESI IMS-MSI of multiply sialylated ganglioside species, as well as their acetylated versions, which we detected directly from the murine brain tissue. We show that poly-sialylated gangliosides can be imaged as multiply charged ions using DESI, while they are clearly separated from the rest of the lipid classes based on their charge state using ion mobility. This represents a major improvement in MSI of intact fragile lipid species. We additionally show that complementary lipid information is reached under particular conditions when DESI is compared to MALDI MSI. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. GUMBOS matrices of variable hydrophobicity for matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Al Ghafly, Hashim; Siraj, Noureen; Das, Susmita; Regmi, Bishnu P; Magut, Paul K S; Galpothdeniya, Waduge Indika S; Murray, Kermit K; Warner, Isiah M

    2014-11-15

    Detection of hydrophobic peptides remains a major obstacle for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). This stems from the fact that most matrices for MALDI are hydrophilic and therefore have low affinities for hydrophobic peptides. Herein, 1-aminopyrene (AP) and AP-derived group of uniform materials based on organic salts (GUMBOS) as novel matrices for MALDI-MS analyses of peptides were investigated for hydrophobic and hydrophilic peptides. A number of solid-phase AP-based GUMBOS are synthesized with variable hydrophobicity simply by changing the counterions. Structures were confirmed by use of (1)H NMR and electrospray ionization mass spectrometry (ESI-MS). 1-Octanol/water partition coefficients (Ko/w) were used to measure the hydrophobicity of the matrices. A dried-droplet method was used for sample preparation. All spectra were obtained using a MALDI-TOF mass spectrometer in positive ion reflectron mode. A series of AP-based GUMBOS was synthesized including [AP][chloride] ([AP][Cl]), [AP][ascorbate] ([AP][Asc]) and [AP][bis(trifluoromethane)sulfonimide] ([AP][NTf2]). The relative hydrophobicities of these compounds and α-cyano-4-hydroxycinnamic acid (CHCA, a common MALDI matrix) indicated that AP-based GUMBOS can be tuned to be much more hydrophobic than CHCA. A clear trend is observed between the signal intensities of hydrophobic peptides and hydrophobicity of the matrix. MALDI matrices of GUMBOS with tunable hydrophobicities are easily obtained simply by varying the counterion. We have found that hydrophobic matrix materials are very effective for MALDI determination of hydrophobic peptides and, similarly, the more hydrophilic peptides displayed greater intensity in the more hydrophilic matrix. Copyright © 2014 John Wiley & Sons, Ltd.

  2. Comprehensive biothreat cluster identification by PCR/electrospray-ionization mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Rangarajan Sampath

    Full Text Available Technology for comprehensive identification of biothreats in environmental and clinical specimens is needed to protect citizens in the case of a biological attack. This is a challenge because there are dozens of bacterial and viral species that might be used in a biological attack and many have closely related near-neighbor organisms that are harmless. The biothreat agent, along with its near neighbors, can be thought of as a biothreat cluster or a biocluster for short. The ability to comprehensively detect the important biothreat clusters with resolution sufficient to distinguish the near neighbors with an extremely low false positive rate is required. A technological solution to this problem can be achieved by coupling biothreat group-specific PCR with electrospray ionization mass spectrometry (PCR/ESI-MS. The biothreat assay described here detects ten bacterial and four viral biothreat clusters on the NIAID priority pathogen and HHS/USDA select agent lists. Detection of each of the biothreat clusters was validated by analysis of a broad collection of biothreat organisms and near neighbors prepared by spiking biothreat nucleic acids into nucleic acids extracted from filtered environmental air. Analytical experiments were carried out to determine breadth of coverage, limits of detection, linearity, sensitivity, and specificity. Further, the assay breadth was demonstrated by testing a diverse collection of organisms from each biothreat cluster. The biothreat assay as configured was able to detect all the target organism clusters and did not misidentify any of the near-neighbor organisms as threats. Coupling biothreat cluster-specific PCR to electrospray ionization mass spectrometry simultaneously provides the breadth of coverage, discrimination of near neighbors, and an extremely low false positive rate due to the requirement that an amplicon with a precise base composition of a biothreat agent be detected by mass spectrometry.

  3. Gene analysis using mass spectrometric cleaved amplified polymorphic sequence (MS-CAPS) with matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF).

    Science.gov (United States)

    Kajiwara, Hideyuki

    2015-01-01

    Mass spectrometric cleaved amplified polymorphic sequence (MS-CAPS) is a method for detecting genes using a combination of short PCR and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). MS-CAPS can identify a single nucleotide polymorphism (SNP) in less than one hour and is suitable for plants, animals, bacteria, and food.

  4. Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins

    NARCIS (Netherlands)

    Bavel, Van Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-01-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of

  5. Structure determination of two conotoxins from Conus textile by a combination of matrix-assisted laser desorption/ionization time-of-flight and electrospray ionization mass spectrometry and biochemical methods

    DEFF Research Database (Denmark)

    Kalume, D E; Stenflo, J; Czerwiec, E

    2000-01-01

    Two highly modified conotoxins from the mollusc Conus textile, epsilon-TxIX and Gla(1)-TxVI, were characterized by matrix-assisted laser desorption/ionization and electrospray mass spectrometry and also by electrospray ionization tandem and triple mass spectrometry in combination with enzymatic c...

  6. Sampling analytes from cheese products for fast detection using neutral desorption extractive electrospray ionization mass spectrometry.

    Science.gov (United States)

    Wu, Zhongchen; Chingin, Konstantin; Chen, Huanwen; Zhu, Liang; Jia, Bin; Zenobi, Renato

    2010-06-01

    The development of analytical techniques suitable for sensitive, high-throughput, and nondestructive food analysis has been of increasing interest in recent years. In this study, mass-spectral fingerprints of various cheese products were rapidly recorded in the mass range of m/z 50-300 Da without any sample pretreatment, using neutral desorption extractive electrospray ionization mass spectrometry (ND-EESI-MS) in negative ion mode. The results demonstrate that both volatile and nonvolatile analytes on greasy cheese surfaces can be directly sampled by a neutral desorption gas beam. The influence of the neutral desorption gas flow on the analyte signal was systematically investigated. Under optimized experimental conditions, reproducible results were obtained using ND-EESI-MS. Principal component analysis was applied to differentiate a total of 49 individual cheese samples (four different types), which were purchased from three different supermarkets. All samples were successfully classified according to their types; but distributors and sensory properties were not distinguishable from the spectra data. The principal components 2, 3, and 4 scores showed an excellent capacity of distinguishing types of cheese. Molecular markers of interest can be identified using tandem mass spectrometry and matching the data with those from reference compounds. The experimental data show that ND-EESI-MS is able to sensitively and directly detect analytes on greasy surfaces without chemical contamination, providing a convenient method for high-throughput food analysis with a high degree of safety.

  7. Low Mass Ions in Laser Desorption/Ionization Mass Spectrometry of 1-Methoxy-5-aminotetrazole

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Soo Gyeong; Bae, Kwang Tae; Goh, Eun Mee; Bae, Se Won [Agency for Defense Development, Daejeon (Korea, Republic of); Shin, Ik-Soo [Soongsil University, Seoul (Korea, Republic of)

    2016-01-15

    The development of novel energetic molecules (EMs) with high power, good safety features, great chemical stability, and environmentally less harmful nature is of great interest in the satellite launcher, missile warhead, ammunition, and pyrotechnic researches. Recently, many researchers have focused on aromatic nitrogen heterocycles such as pyrazole, imidazole, triazole, tetrazole, and pentazole as promising candidates to replace the current EMs used in civilian and military applications. We performed MALDI and LDI experiments with energetic tetrazole derivatives which were of great interest for the application of high performance explosives and fast burning propellants. Particularly, LDI experiments provided low mass ion peaks from decomposition of MAT, which were useful to analyze decomposition mechanism of tetrazoles at TOF MS in high vacuum. The LDI experiments showed various decomposed ion products, which implied several decomposition mechanisms including the detachment of side function groups and the fragmentation of tetrazole ring. The high-level DFT calculations also supported the peaks obtained from LDI experiments.

  8. Analysis of noncovalent chitinase-chito-oligosaccharide complexes by infrared-matrix assisted laser desorption ionization and nanoelectrospray ionization mass spectrometry.

    Science.gov (United States)

    Dybvik, Anette I; Norberg, Anne Line; Schute, Veronika; Soltwisch, Jens; Peter-Katalinić, Jasna; Vårum, Kjell M; Eijsink, Vincent G H; Dreisewerd, Klaus; Mormann, Michael; Sørlie, Morten

    2011-06-01

    Transferring noncovalently bound complexes from the condensed phase into the gas phase represents a challenging task due to weak intermolecular bonds that have to be maintained during the phase transition. Currently, electrospray ionization (ESI) is the standard mass spectrometric (MS) technique to analyze noncovalent complexes. Although infrared matrix-assisted laser desorption ionization (IR-MALDI)-MS also provides particular soft desorption/ionization conditions, this method has so far hardly been applied for the analysis of noncovalent complexes. In this study, we employed IR-MALDI orthogonal time-of-flight (o-TOF)-MS in combination with the liquid matrix glycerol to characterize the specific complex formation of chito-oligosaccharide (CHOS) ligands with two variants of Chitinase A (ChiA) from Serratia marcescens, the inactive E315Q mutant and the active W167A mutant, respectively. The IR-MALDI-o-TOF-MS results were compared to those obtained using nano-ESI-quadrupole (q)-TOF-MS and ultraviolet (UV)-MALDI-o-TOF-MS. Using IR-MALDI-o-TOF-MS, specific noncovalent complexes between ChiA and CHOS were detected with distributions between enzymes with bound oligosaccharides vs free enzymes that were essentially identical to those obtained by nano-ESI-q-TOF-MS. Chitinase-CHOS complexes were not detected when UV-MALDI was employed for desorption/ionization. The results show that IR-MALDI-MS can be a valuable tool for fast and simple screening of noncovalent enzyme-ligand interactions.

  9. Application of desorption electrospray ionization mass spectrometry imaging in breast cancer margin analysis.

    Science.gov (United States)

    Calligaris, David; Caragacianu, Diana; Liu, Xiaohui; Norton, Isaiah; Thompson, Christopher J; Richardson, Andrea L; Golshan, Mehra; Easterling, Michael L; Santagata, Sandro; Dillon, Deborah A; Jolesz, Ferenc A; Agar, Nathalie Y R

    2014-10-21

    Distinguishing tumor from normal glandular breast tissue is an important step in breast-conserving surgery. Because this distinction can be challenging in the operative setting, up to 40% of patients require an additional operation when traditional approaches are used. Here, we present a proof-of-concept study to determine the feasibility of using desorption electrospray ionization mass spectrometry imaging (DESI-MSI) for identifying and differentiating tumor from normal breast tissue. We show that tumor margins can be identified using the spatial distributions and varying intensities of different lipids. Several fatty acids, including oleic acid, were more abundant in the cancerous tissue than in normal tissues. The cancer margins delineated by the molecular images from DESI-MSI were consistent with those margins obtained from histological staining. Our findings prove the feasibility of classifying cancerous and normal breast tissues using ambient ionization MSI. The results suggest that an MS-based method could be developed for the rapid intraoperative detection of residual cancer tissue during breast-conserving surgery.

  10. Identification of Molds by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry.

    Science.gov (United States)

    Sanguinetti, Maurizio; Posteraro, Brunella

    2017-02-01

    Although to a lesser extent than diagnostic bacteriology, matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) has recently revolutionized the diagnostic mycology workflow. With regard to filamentous fungi (or molds), the precise recognition of pathogenic species is important for rapid diagnosis and appropriate treatment, especially for invasive diseases. This review summarizes the current experience with MALDI-TOF MS-based identification of common and uncommon mold species of Aspergillus, Fusarium, Mucorales, dimorphic fungi, and dermatophytes. This experience clearly shows that MALDI-TOF MS holds promise as a fast and accurate identification tool, particularly with common species or typical strains of filamentous fungi. Copyright © 2017 American Society for Microbiology.

  11. Shotgun sequencing small oligonucleotides by nozzle-skimmer dissociation and electrospray ionization mass spectrometry.

    Science.gov (United States)

    Meng, Zhaojing; Limbach, Patrick A

    2005-01-01

    Nozzle-skimmer dissociation in combination with de novo sequencing was investigated as an approach for increasing the throughput of oligonucleotide analysis attainable by electrospray ionization mass spectrometry. An experimental method allowing for the sequential generation of precursor and fragment ion data during direct infusion of sample was developed. These data can then be used with readily available de novo sequencing software to characterize small oligonucleotides. When this approach was applied to mixtures of oligonucleotides, it was found that de novo sequencing becomes limited due to spectral congestion and overlapping oligonucleotide m/z dissociation product values. Self-packed C(18) microspray emitters were investigated as a means of reducing spectral complexity. It was found that such emitters allow for the analysis of oligonucleotide mixtures with minimal component overlap, and these emitters provide additional benefits of pre- concentrating and desalting the sample. These developments can provide a route for the more rapid characterization of ribonucleic acid endonuclease digestion mixtures.

  12. Product analysis of caffeic acid oxidation by on-line electrochemistry/electrospray ionization mass spectrometry.

    Science.gov (United States)

    Arakawa, Ryuichi; Yamaguchi, Masashi; Hotta, Hiroki; Osakai, Toshiyuki; Kimoto, Takashi

    2004-08-01

    On-line electrochemistry/electrospray ionization mass spectrometry (EC/ESI-MS) was developed using a microflow electrolytic cell. This technique was applied to electrochemical oxidation of caffeic acid (CAF) which is known to be a highly antioxidative agent. Effects of electrolytic potentials on ion intensities of product ions and on electrolytic currents were examined at different pHs. Dimer products were detected at electrolytic potentials of E = 0.7 V (vs. Ag/AgCl) and trimer products at 1.0 V at pH 9. Dimer products were distinguished from hydrogen-bonded complexes by MS/MS experiments. Hydrogen/deuterium exchange experiments determined the number of hydroxyl and carboxyl groups in the Dimers formed by electrolysis. The mechanism of oxidative polymerization of CAF is discussed with speculation as to the structure of the dimer product.

  13. New methods and instrumentation for the characterization of biopolymers using electrospray ionization-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R.D.; Udseth, H.R.; Rockwood, A.L.; Winger, B.E.; Hofstadler, S.A.; Goodlett, D.R.; Light-Wahl, K.J.

    1992-09-01

    The technique of electrospray ionization (ESI) has significantly extended the ability to characterize large molecules by mass spectrometry. Proteins to at least 200,000 D can be transferred intact to the gas phase and molecular weights determined with precisions as high as 0.001% if individual charge states can be resolved. The ESI-MS can also serve as a near ideal interface and detector for capillary column separations providing a basis for highly efficient sample utilization. Using capillary electrophoresis (CE)-MS, injection quantities in the 10[sup [minus]18] mole range can be detected for smaller polypeptides using selected ion monitoring, and separation efficiencies as high as 5[center dot]10[sup 5] theoretical plates have been realized. We have recently shown that the use of small 5 [mu]m i.d. capillaries allows CE-MS with scanning detection for proteins for injection of 600 attomoles.

  14. New methods and instrumentation for the characterization of biopolymers using electrospray ionization-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R.D.; Udseth, H.R.; Rockwood, A.L.; Winger, B.E.; Hofstadler, S.A.; Goodlett, D.R.; Light-Wahl, K.J.

    1992-09-01

    The technique of electrospray ionization (ESI) has significantly extended the ability to characterize large molecules by mass spectrometry. Proteins to at least 200,000 D can be transferred intact to the gas phase and molecular weights determined with precisions as high as 0.001% if individual charge states can be resolved. The ESI-MS can also serve as a near ideal interface and detector for capillary column separations providing a basis for highly efficient sample utilization. Using capillary electrophoresis (CE)-MS, injection quantities in the 10{sup {minus}18} mole range can be detected for smaller polypeptides using selected ion monitoring, and separation efficiencies as high as 5{center_dot}10{sup 5} theoretical plates have been realized. We have recently shown that the use of small 5 {mu}m i.d. capillaries allows CE-MS with scanning detection for proteins for injection of 600 attomoles.

  15. Electrospray ionization mass spectrometry fingerprinting of perfumes: Rapid classification and counterfeit detection.

    Science.gov (United States)

    Marques, Lygia de Azevedo; Catharino, Rodrigo Ramos; Bruns, Roy E; Eberlin, Marcos N

    2006-01-01

    A fast procedure to classify perfumes and identify counterfeit samples is described. Dilution of a few microL of the sample in a 1:1 methanol/water solution is followed by detection of its major polar components via direct infusion electrospray ionization mass spectrometry (ESI-MS) in the positive ion mode. As proof-of-principle cases, three famous brands of perfumes were used. The ESI+-MS fingerprints of authentic samples were very characteristic, showing distinctive sets of polar markers for each sample. Principal component analysis (PCA) placed samples of the three perfume brands in well-defined groups. Counterfeit samples were also clearly detected owing to contrasting ESI-MS fingerprints, with PCA placing these samples far away from the authentic samples. Copyright 2006 John Wiley & Sons, Ltd.

  16. Direct Surface Analysis of Fungal Species by Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Valentine, Nancy B.(BATTELLE (PACIFIC NW LAB)); Wahl, Jon H.(BATTELLE (PACIFIC NW LAB)); Kingsley, Mark T.(BATTELLE (PACIFIC NW LAB)); Wahl, Karen L.(BATTELLE (PACIFIC NW LAB))

    2001-12-01

    Intact spores and/or hyphae of Aspergillus niger, Rhizopus oryzae, Trichoderma reesei and Phanerochaete chrysosporium are analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). This study investigates various methods of sample preparation and matrices to determine optimum collection and analysis criteria for fungal analysis by MALDI-MS. Fungi are applied to the MALDI sample target as untreated, sonicated, acid/heat treated, or blotted directly from the fungal culture with double-stick tape. Ferulic acid or sinapinic acid matrix solution is layered over the dried samples and analyzed by MALDI-MS. Statistical analysis of the data show that simply using double stick tape to collect and transfer to a MALDI sample plate typically worked as well as the other preparation methods, but requires the least sample handling.

  17. Membrane-Based Emitter for Coupling Microfluidics with Ultrasensitive Nanoelectrospray Ionization-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xuefei; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.

    2011-06-09

    An integrated poly(dimethylsiloxane) (PDMS) membrane-based microfluidic emitter for high performance nanoelectrospray ionization-mass spectrometry (nanoESI-MS) has been fabricated and evaluated. The ~100-μm-thick emitter was created by cutting a PDMS membrane that protrudes beyond the bulk substrate. The reduced surface area at the emitter enhances the electric field and reduces wetting of the surface by the electrospray solvent. As such, the emitter provides highly stable electrospray at flow rates as low as 10 nL/min, and is compatible with electrospray solvents containing a large organic component (e.g., 90% methanol). This approach enables facile emitter construction, and provides excellent stability, reproducibility and sensitivity, as well as compatibility with multilayer soft lithography.

  18. Facilitated diffusion of acetonitrile revealed by quantitative breath analysis using extractive electrospray ionization mass spectrometry.

    Science.gov (United States)

    Li, Ming; Ding, Jianhua; Gu, Haiwei; Zhang, Yan; Pan, Susu; Xu, Ning; Chen, Huanwen; Li, Hongmei

    2013-01-01

    By using silver cations (Ag⁺) as the ionic reagent in reactive extractive electrospray ionization mass spectrometry (EESI-MS), the concentrations of acetonitrile in exhaled breath samples from the volunteers including active smokers, passive smokers, and non-smokers were quantitatively measured in vivo, without any sample pretreatment. A limit of detection (LOD) and relative standard deviation (RSD) were 0.16 ng/L and 3.5% (n = 8), respectively, for the acetonitrile signals in MS/MS experiments. Interestingly, the concentrations of acetonitrile in human breath continuously increased for 1-4 hours after the smoker finished smoking and then slowly decreased to the background level in 7 days. The experimental data of a large number of (> 165) samples indicated that the inhaled acetonitrile is excreted most likely by facilitated diffusion, instead of simple diffusion reported previously for other volatile compounds.

  19. Electrospray ionization in concentrated acetonitrile vapor improves the performance of mass spectrometry for proteomic analyses.

    Science.gov (United States)

    Chen, Jin; Wang, Fangjun; Liu, Zheyi; Liu, Jing; Zhu, Yixin; Zhang, Yukui; Zou, Hanfa

    2017-02-03

    Suppressing the background interferences and enhancing the analytes signals are long-term goals in high performance electrospray ionization mass spectrometry (ESI-MS) analyses. We observed that performing electrospray in the presence of a concentrated acetonitrile atmosphere suppresses background interferences and enhances peptide signals. An enclosed nanoESI source was utilized to provide a stable atmosphere of concentrated acetonitrile vapor for high performance ESI-MS analyses. The median MS signal intensity increased by 5 times for a set of 23 BSA tryptic peptides in direct ESI-MS analysis. Further, the number of reproducibly and precisely quantified peptides could be improved 67% in six replicate label-free quantitative proteome analyses by this strategy. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Electrospray ionization tandem mass spectrometry for the simultaneous determination of opiates and cocaine in human hair.

    Science.gov (United States)

    Míguez-Framil, Martha; Moreda-Piñeiro, Antonio; Bermejo-Barrera, Pilar; Cocho, José Ángel; Tabernero, María Jesús; Bermejo, Ana María

    2011-10-17

    A fast and highly sensitive electrospray ionization tandem mass spectrometry (ESI-MS/MS) method has been developed for the simultaneous determination of morphine, 6-methylacetylmorphine (6-MAM), codeine, cocaine and benzoylecgonine (BZE) in hair from drug abusers. Pulverized hair samples were subjected to an optimized matrix solid phase dispersion (MSPD) procedure with alumina, followed by diluted hydrochloric acid elution on column solid-phase extraction (SPE) clean-up/pre-concentration. Alternatively, samples were also subjected to an optimized ultrasound assisted enzymatic hydrolysis (USEH) with Pronase E, followed by an off-line SPE clean up/pre-concentration procedure. Positive electrospray ionization and multiple reaction monitoring (MRM) with one precursor ion/product ion transition were used for the identification and quantification (deuterated analogues of each target as internal standards) of each analyte. The chromatographic pump and the autosampler were used for injecting the standards and the hair extracts (20 μL) as a flow injection analysis mode. The highest sensitivity was achieved when delivering the targets with an acetonitrile/water/formic acid (80/19.875/0.125) mixture. The limits of detection of the method were 39.2, 4.4, 6.8, 7.0 and 7.4 ng g(-1) for morphine, 6-MAM, codeine, cocaine and BZE, respectively. Relative standard deviations of intra- and inter-day precision were lower than 9 and 12%, respectively; whereas, analytical recoveries ranged from 96±5 to 106±4%. The developed method (MSPD-ESI-MS/MS) was applied to different hair samples from polydrug abusers, and results were statistically compared to those obtained after a conventional gas chromatography-mass spectrometry (GC-MS) analysis and also after USEH and ESI-MS/MS or GC-MS determinations. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Controlled-Resonant Surface Tapping-Mode Scanning Probe Electrospray Ionization Mass Spectrometry Imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, Matthias [ORNL; Ovchinnikova, Olga S [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL

    2014-01-01

    This paper reports on the advancement of a controlled-resonance surface tapping-mode single capillary liquid junction extraction/ESI emitter for mass spectrometry imaging. The basic instrumental setup and the general operation of the system were discussed and optimized performance metrics were presented. The ability to spot sample, lane scan and chemically image in an automated and controlled fashion were demonstrated. Rapid, automated spot sampling was demonstrated for a variety of compound types including the cationic dye basic blue 7, the oligosaccharide cellopentaose, and the protein equine heart cytochrome c. The system was used for lane scanning and chemical imaging of the cationic dye crystal violet in inked lines on glass and for lipid distributions in mouse brain thin tissue sections. Imaging of the lipids in mouse brain tissue under optimized conditions provided a spatial resolution of approximately 35 m based on the ability to distinguish between features observed both in the optical and mass spectral chemical images. The sampling spatial resolution of this system was comparable to the best resolution that has been reported for other types of atmospheric pressure liquid extraction-based surface sampling/ionization techniques used for mass spectrometry imaging.

  2. Development of electrospray ionization of biomolecules on a magnetic sector mass spectrometer

    CERN Document Server

    Zhang, Y

    2002-01-01

    The initial part of this study involves developments made on an electrospray ionization (ESI) source installed on a large-scale double-focusing reverse-geometry two-sector mass spectrometer. The practical considerations and some basic theory have been given in this thesis for each of the improvements made to the ESI source. The process of partial re-designing the ion optical system showed that the ion beam was affected by both gas dynamics and by the field penetration from the lenses of the ion optical system in the region immediately after second skimmer. More than one order magnitude stronger ion signal intensities at the mass spectrometer final detector and easier ESI source operation conditions and stable ion signals has been achieved. Mass-analyzed ion kinetic energy spectroscopy (MIKES) of different charge-states of relatively small peptides (substance P and bradykinin) for collision-induced dissociation (CID) and the metastable dissociation was carried out successfully. The translational energy losses ...

  3. In situ analysis of corrosion inhibitors using a portable mass spectrometer with paper spray ionization

    KAUST Repository

    Jjunju, Fred Paul Mark

    2013-01-01

    Paper spray (PS) ambient ionization is implemented using a portable mass spectrometer and applied to the detection of alkyl quaternary ammonium salts in a complex oil matrix. These salts are commonly used as active components in the formulation of corrosion inhibitors. They were identified in oil and confirmed by their fragmentation patterns recorded using tandem mass spectrometry (MS/MS). The cations of alkyl and benzyl-substituted quaternary ammonium salts showed characteristic neutral losses of CnH2n (n carbon number of the longest chain) and C7H8, respectively. Individual quaternary ammonium compounds were detected at low concentrations (<1 ng μL-1) and over a dynamic range of ∼5 pg μL-1 to 500 pg μL-1 (ppb). Direct detection of these compounds in complex oil samples without prior sample preparation or pre-concentration was also demonstrated using a home-built miniature mass spectrometer at levels below 1 ng μL-1.© 2013 The Royal Society of Chemistry.

  4. Detection of diethyl phthalate in perfumes by extractive electrospray ionization mass spectrometry.

    Science.gov (United States)

    Chingin, Konstantin; Chen, Huanwen; Gamez, Gerardo; Zhu, Liang; Zenobi, Renato

    2009-01-01

    Recent findings suggest that long-term exposure to diethyl phthalate (DEP), one of the widely used phthalate esters, can lead to serious health problems. Most perfumes contain non-negligible amounts of DEP. Rapid and sensitive detection of DEP in perfumes is thus of increasing importance. A novel procedure based on extractive electrospray ionization mass spectrometry (EESI-MS) has been developed for fast detection and identification of DEP in perfumes without the need for any sample pretreatment. The limit of determination for DEP in perfume was less than 100 ppb using tandem mass spectrometry on a commercial quadrupole time-of-flight mass spectrometer. The dynamic range of this method was about 4 orders of magnitude. A single sample analysis was completed within a few seconds, providing a rapid way to obtain semiquantitative information on the DEP content in perfumes. This study shows that both volatile and nonvolatile analytes (e.g., amino acids) in liquids can be directly sampled by neutral desorption, providing a convenient way for high-throughput screening of target compounds using EESI-MS.

  5. Chemical ionization mass spectrometry using carbon nanotube field emission electron sources.

    Science.gov (United States)

    Radauscher, Erich J; Keil, Adam D; Wells, Mitch; Amsden, Jason J; Piascik, Jeffrey R; Parker, Charles B; Stoner, Brian R; Glass, Jeffrey T

    2015-11-01

    A novel chemical ionization (CI) source has been developed based on a carbon nanotube (CNT) field emission electron source. The CNT-based electron source was evaluated and compared with a standard filament thermionic electron source in a commercial explosives trace detection desktop mass spectrometer. This work demonstrates the first reported use of a CNT-based ion source capable of collecting CI mass spectra. Both positive and negative modes were investigated. Spectra were collected for a standard mass spectrometer calibration compound, perfluorotributylamine (PFTBA), as well as trace explosives including trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol tetranitrate (PETN). The electrical characteristics, lifetime at operating pressure, and power requirements of the CNT-based electron source are reported. The CNT field emission electron sources demonstrated an average lifetime of 320 h when operated in constant emission mode under elevated CI pressures. The ability of the CNT field emission source to cycle on and off can provide enhanced lifetime and reduced power consumption without sacrificing performance and detection capabilities. Graphical Abstract ᅟ.

  6. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    Energy Technology Data Exchange (ETDEWEB)

    Lentz, Nicholas B. [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

  7. Quantitative Caffeine Analysis Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

    2005-01-01

    Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

  8. Atomic xenon recombination laser excited by thermal ionizing radiation from a magnetoplasma compressor and discharge

    Science.gov (United States)

    Kamrukov, A. S.; Kozlov, Nicolay P.; Opekan, A. G.; Protasov, Yuri S.; Rudoi, I. G.; Soroka, A. M.

    1991-09-01

    A description is given and the results are reported of the first photoionization-recombination laser using atomic xenon excited by thermal ionizing radiation from a plasma. The pump source was a multichannel plasmadynamic in magnetoplasma compressors, which was ignited in the active medium of the laser. When the composition of the working mixture was optimal (Xe:Ar equals 1:250) and the total pressure was 1 atm, the output energy was approximately 0.5 in the form of pulses of approximately 10 microsecond(s) duration, and maximum specific output energy represented by laser radiation was 1-2 J/l. The unsaturated gain was 27 m. A kinetic laser scheme was proposed and analyzed. It allowed for the processes of photoionization, ion conversion, dissociative recombination, interaction of excited states with electron and buffer gases, etc. An important role played by heating of the active medium during pumping was demonstrated; it explained the observed characteristics of the spatial and temporal structure of the lasing process, particularly bleaching of large volumes of the active medium. The potential output energy of the laser was considered, and specific constructions were proposed to attain a lasing efficiency amounting to a few percent.

  9. LASERS: Atomic xenon recombination laser excited by thermal ionizing radiation from a magnetoplasma compressor and discharge

    Science.gov (United States)

    Kamrukov, A. S.; Kozlov, N. P.; Opekan, A. G.; Protasov, Yu S.; Rudoĭ, I. G.; Soroka, A. M.

    1989-07-01

    A description is given and the results are reported of the first photoionization-recombination laser using atomic xenon excited by thermal ionizing radiation from a plasma. The pump source was a multichannel plasmadynamic discharge in magnetoplasma compressors, which was ignited in the active medium of the laser. When the composition of the working mixture was optimal (Xe:Ar = 1:250) and the total pressure was 1 atm, the output energy was ~ 0.5 J in the form of pulses of ~ 10 μs duration and the maximum specific output energy represented by laser radiation was 1-2 J/liter. The unsaturated gain was 27 m - 1. A kinetic laser scheme was proposed and analyzed. It allowed for the processes of photoionization, ion conversion, dissociative recombination, interaction of excited states with electron and buffer gases, etc. An important role played by heating of the active medium during pumping was demonstrated and it explained the observed characteristics of the spatial and temporal structure of the lasing process, particularly bleaching of large volumes of the active medium. The potential output energy of the laser was considered and specific constructions were proposed to attain a lasing efficiency amounting to a few percent.

  10. Mass spectrometry studies of the ionization of organic molecules by slow positrons

    Energy Technology Data Exchange (ETDEWEB)

    Hulett, L.D. Jr.; Xu, Jun; Lewis, T.A.; Crawford, O.H.; McLuckey, S.A.

    1994-06-01

    The dissociative ionization of organic molecules, induced by positrons having energies below positronium thresholds (0.5--3 eV), has been studied. The ionization-fragmentation yields increase as positron energies decrease. The energies required for dissociative ionization are supplied by the annihilation processes. Fragmentation occurs by breakage of C-C single bonds in preference to double or triple bonds.

  11. Investigation of naproxen drug using mass spectrometry, thermal analyses and semi-empirical molecular orbital calculation

    Directory of Open Access Journals (Sweden)

    M.A. Zayed

    2017-03-01

    Full Text Available Naproxen (C14H14O3 is a non-steroidal anti-inflammatory drug (NSAID. It is important to investigate its structure to know the active groups and weak bonds responsible for medical activity. In the present study, naproxen was investigated by mass spectrometry (MS, thermal analysis (TA measurements (TG/DTG and DTA and confirmed by semi empirical molecular orbital (MO calculation, using PM3 procedure. These calculations included, bond length, bond order, bond strain, partial charge distribution, ionization energy and heat of formation (ΔHf. The mass spectra and thermal analysis fragmentation pathways were proposed and compared to select the most suitable scheme representing the correct fragmentation pathway of the drug in both techniques. The PM3 procedure reveals that the primary cleavage site of the charged molecule is the rupture of the COOH group (lowest bond order and high strain which followed by CH3 loss of the methoxy group. Thermal analysis of the neutral drug reveals a high response to the temperature variation with very fast rate. It decomposed in several sequential steps in the temperature range 80–400 °C. These mass losses appear as two endothermic and one exothermic peaks which required energy values of 255.42, 10.67 and 371.49 J g−1 respectively. The initial thermal ruptures are similar to that obtained by mass spectral fragmentation (COOH rupture. It was followed by the loss of the methyl group and finally by ethylene loss. Therefore, comparison between MS and TA helps in selection of the proper pathway representing its fragmentation. This comparison is successfully confirmed by MO-calculation.

  12. Direct identification of prohibited substances in cosmetics and foodstuffs using ambient ionization on a miniature mass spectrometry system.

    Science.gov (United States)

    Ma, Qiang; Bai, Hua; Li, Wentao; Wang, Chao; Li, Xinshi; Cooks, R Graham; Ouyang, Zheng

    2016-03-17

    Significantly simplified work flows were developed for rapid analysis of various types of cosmetic and foodstuff samples by employing a miniature mass spectrometry system and ambient ionization methods. A desktop Mini 12 ion trap mass spectrometer was coupled with paper spray ionization, extraction spray ionization and slug-flow microextraction for direct analysis of Sudan Reds, parabens, antibiotics, steroids, bisphenol and plasticizer from raw samples with complex matrices. Limits of detection as low as 5 μg/kg were obtained for target analytes. On-line derivatization was also implemented for analysis of steroid in cosmetics. The developed methods provide potential analytical possibility for outside-the-lab screening of cosmetics and foodstuff products for the presence of illegal substances. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Salicylaldehyde azine cluster formation observed by cold-spray ionization mass spectrometry.

    Science.gov (United States)

    Xu, Xiangyu; Qiao, Jinping; Deng, Xuebin; Na, Na; Ouyang, Jin

    2013-08-01

    We installed a cold-spray ionization (CSI) source on a mass spectrometer to investigate the self-assembly behavior of an aggregation-induced emission enhancement system. Using a CSI source and the three-dimensional platform, a self-assembly system of a salicylaldehyde azine (SAA) was studied in mixture solution. This method permitted the determination of the structural information of the solution state, which cannot be detected by conventional mass spectrometry. In addition to the [M+H](+) ion (M is the SAA molecule), many major ion clusters such as [2M+Na](+) at m/z 503, [3M+Na](+) at m/z 743, [4M+Na](+) at m/z 983 and higher order aggregates were observed in the CSI mass spectra. However, many fragment ions, with the exception of cluster ions, appeared with high abundance when the ESI ion source was used due to the desolvation chamber temperature, suggesting that some aggregation can be detected at low temperatures. To investigate the effect of solvent on the aggregation, the CSI-mass spectrometry (MS) experiments of SAA in absolute ethanol solution and ethanol/water (good/poor solvent) mixture solution were conducted. The most abundant ion peak was protonated SAA (m/z 241) in absolute ethanol, but many cluster ions and some multiple charged ion peaks were observed after adding a small amount of water into the ethanol solution. The results showed good agreement with that inferred by the combinational analysis of scanning electron microscope and fluorescence microscopy, indicating that CSI-MS is capable of providing self-assembly information of labile molecules in the solution state. Copyright © 2013 John Wiley & Sons, Ltd.

  14. Basic poly(propylene glycols) as reference compounds for internal mass calibration in positive-ion matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Gross, Jürgen H

    2017-12-01

    Basic poly(propylene glycols), commercially available under the trade name Jeffamine, are evaluated for their potential use as internal mass calibrants in matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry. Due to their basic amino endgroups Jeffamines are expected to deliver [M+H] + ions in higher yields than neutral poly(propylene glycols) or poly(ethylene glycols). Aiming at accurate mass measurements and molecular formula determinations by matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry, four Jeffamines (M-600, M-2005, D-400, D-230) were thus compared. As a result, Jeffamine M-2005 is introduced as a new mass calibrant for positive-ion matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry in the range of m/z 200-1200 and the reference mass list is provided. While Jeffamine M-2005 is compatible with α-cyano-4-hydroxycinnamic acid, 2,5-dihydroxybenzoic acid, and 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile matrix, its use in combination with 2-[(2 E)-3-(4- tert-butylphenyl)-2-methylprop-2-enylidene]malonitrile provides best results due to low laser fluence requirements. Applications to PEG 300, PEG 600, the ionic liquid trihexyl(tetradecyl)-phosphonium tris(pentafluoroethyl)-trifluorophosphate, and [60]fullerene demonstrate mass accuracies of 2-5 ppm.

  15. Rapid discrimination of fatty acid composition in fats and oils by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Kurata, Shoji; Yamaguchi, Kazutaka; Nagai, Masatoshi

    2005-12-01

    Fatty acids in 42 types of saponified vegetable and animal oils were analyzed by electrospray ionization mass spectrometry (ESI-MS) for the development of their rapid discrimination. The compositions were compared with those analyzed by gas chromatography-mass spectrometry (GC-MS), a more conventional method used in the discrimination of fats and oils. Fatty acids extracted with 2-propanol were-detected as deprotonated molecular ions ([M-H]-) in the ESI-MS spectra of the negative-ion mode. The composition obtained by ESI-MS corresponded to the data of the total ion chromatograms by GC-MS. The ESI-MS analysis discriminated the fats and oils within only one minute after starting the measurement. The detection limit for the analysis was approximately 10(-10) g as a sample amount analyzed for one minute. This result showed that the ESI-MS analysis discriminated the fats and oils much more rapidly and sensitively than the GC-MS analysis, which requires several tens of minutes and approximately 10(-9) g. Accordingly, the ESI-MS analysis was found to be suitable for a screening procedure for the discrimination of fats and oils.

  16. Effects of Different Waveforms on the Performance of Active Capillary Dielectric Barrier Discharge Ionization Mass Spectrometry.

    Science.gov (United States)

    Dumlao, Morphy C; Xiao, Dan; Zhang, Daming; Fletcher, John; Donald, William A

    2017-04-01

    Active capillary dielectric barrier discharge ionization (DBDI) is emerging as a compact, low-cost, and robust method to form intact ions of small molecules for detection in near real time by portable mass spectrometers. Here, we demonstrate that by using a 10 kHz, ~2.5 kV p-p high-voltage square-wave alternating current plasma, active capillary DBDI can consume less than 1 μW of power. In contrast, the power consumed using a sine and triangle alternating current waveform is more than two orders of magnitude higher than that for the square waveform to obtain a similar voltage for plasma generation. Moreover, the plasma obtained using a square waveform can be significantly more homogenous than that obtained using sine and triangle waveforms. Protonated dimethyl methylphosphonate (DMMP) and deprotonated perfluorooctanoic acid (PFOA) can be detected at about the same or higher abundances using square-wave DBDI mass spectrometry compared with the use of sine and triangle waveforms. By use of benzylammonium thermometer ions, the extent of internal energy deposition using square, sine, or triangle waveform excited plasmas are essentially the same at the optimum voltages for ion detection. Using an H-bridge circuit driving a transformer optimized to reduce losses, square-wave active capillary DBDI can be continuously powered for ~50 h by common 9 V-battery (PP3). Graphical Abstract ᅟ.

  17. Towards Better Understanding of Pea Seed Dormancy Using Laser Desorption/Ionization Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Monika Cechová

    2017-10-01

    Full Text Available Seed coats of six pea genotypes contrasting in dormancy were studied by laser desorption/ionization mass spectrometry (LDI-MS. Multivariate statistical analysis discriminated dormant and non-dormant seeds in mature dry state. Separation between dormant and non-dormant types was observed despite important markers of particular dormant genotypes differ from each other. Normalized signals of long-chain hydroxylated fatty acids (HLFA in dormant JI64 genotype seed coats were significantly higher than in other genotypes. These compounds seem to be important markers likely influencing JI64 seed imbibition and germination. HLFA importance was supported by study of recombinant inbred lines (JI64xJI92 contrasting in dormancy but similar in other seed properties. Furthemore HLFA distribution in seed coat was studied by mass spectrometry imaging. HLFA contents in strophiole and hilum are significantly lower compared to other parts indicating their role in water uptake. Results from LDI-MS experiments are useful in understanding (physical dormancy (first phases of germination mechanism and properties related to food processing technologies (e.g., seed treatment by cooking.

  18. Ammonium Bicarbonate Addition Improves the Detection of Proteins by Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Honarvar, Elahe; Venter, Andre R.

    2017-06-01

    The analysis of protein by desorption electrospray ionization mass spectrometry (DESI-MS) is considered impractical due to a mass-dependent loss in sensitivity with increase in protein molecular weights. With the addition of ammonium bicarbonate to the DESI-MS analysis the sensitivity towards proteins by DESI was improved. The signal to noise ratio (S/N) improvement for a variety of proteins increased between 2- to 3-fold relative to solvent systems containing formic acid and more than seven times relative to aqueous methanol spray solvents. Three methods for ammonium bicarbonate addition during DESI-MS were investigated. The additive delivered improvements in S/N whether it was mixed with the analyte prior to sample deposition, applied over pre-prepared samples, or simply added to the desorption spray solvent. The improvement correlated well with protein pI but not with protein size. Other ammonium or bicarbonate salts did not produce similar improvements in S/N, nor was this improvement in S/N observed for ESI of the same samples. As was previously described for ESI, DESI also caused extensive protein unfolding upon the addition of ammonium bicarbonate. [Figure not available: see fulltext.

  19. An Automated Platform for High-Resolution Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Heath, Brandi S.; Liyu, Andrey V.; Thomas, Mathew; Carson, James P.; Laskin, Julia

    2012-10-02

    An automated platform has been developed for acquisition and visualization of mass spectrometry imaging (MSI) data using nanospray desorption electrospray ionization (nano-DESI). The new system enables robust operation of the nano-DESI imaging source over many hours. This is achieved by controlling the distance between the sample and the probe by mounting the sample holder onto an automated XYZ stage and defining the tilt of the sample plane. This approach is useful for imaging of relatively flat samples such as thin tissue sections. Custom software called MSI QuickView was developed for visualization of large data sets generated in imaging experiments. MSI QuickView enables fast visualization of the imaging data during data acquisition and detailed processing after the entire image is acquired. The performance of the system is demonstrated by imaging rat brain tissue sections. High resolution mass analysis combined with MS/MS experiments enabled identification of lipids and metabolites in the tissue section. In addition, high dynamic range and sensitivity of the technique allowed us to generate ion images of low-abundance isobaric lipids. High-spatial resolution image acquired over a small region of the tissue section revealed the spatial distribution of an abundant brain metabolite, creatine, in the white and gray matter that is consistent with the literature data obtained using magnetic resonance spectroscopy.

  20. Ethanol analysis by headspace gas chromatography with simultaneous flame-ionization and mass spectrometry detection.

    Science.gov (United States)

    Tiscione, Nicholas B; Alford, Ilene; Yeatman, Dustin Tate; Shan, Xiaoqin

    2011-09-01

    Ethanol is the most frequently identified compound in forensic toxicology. Although confirmation involving mass spectrometry is desirable, relatively few methods have been published to date. A novel technique utilizing a Dean's Switch to simultaneously quantitate and confirm ethyl alcohol by flame-ionization (FID) and mass spectrometric (MS) detection after headspace sampling and gas chromatographic separation is presented. Using 100 μL of sample, the limits of detection and quantitation were 0.005 and 0.010 g/dL, respectively. The zero-order linear range (r(2) > 0.990) was determined to span the concentrations of 0.010 to 1.000 g/dL. The coefficient of variation of replicate analyses was less than 3.1%. Quantitative accuracy was within ±8%, ±6%, ±3%, and ±1.5% at concentrations of 0.010, 0.025, 0.080, and 0.300 g/dL, respectively. In addition, 1,1-difluoroethane was validated for qualitative identification by this method. The validated FID-MS method provides a procedure for the quantitation of ethyl alcohol in blood by FID with simultaneous confirmation by MS and can also be utilized as an identification method for inhalants such as 1,1-difluoroethane.

  1. In situ metabolic profiling of single cells by laser ablation electrospray ionization mass spectrometry.

    Science.gov (United States)

    Shrestha, Bindesh; Vertes, Akos

    2009-10-15

    Depending on age, phase in the cell cycle, nutrition, and environmental factors, individual cells exhibit large metabolic diversity. To explore metabolic variations in cell populations, laser ablation electrospray ionization (LAESI) mass spectrometry (MS) was used for the in situ analysis of individual cells at atmospheric pressure. Single cell ablation was achieved by delivering mid-IR laser pulses through the etched tip of a GeO(2)-based glass fiber. Metabolic analysis was performed from single cells and small cell populations of Allium cepa and Narcissus pseudonarcissus bulb epidermis, as well as single eggs of Lytechinus pictus. Of the 332 peaks detected for A. cepa, 35 were assigned to metabolites with the help of accurate ion masses and tandem MS. The metabolic profiles from single cells of the two plant species included a large variety of oligosaccharides including possibly fructans in A. cepa, and alkaloids, e.g., lycorine in N. pseudonarcissus. Analysis of adjacent individual cells with a difference in pigmentation showed that, in addition to essential metabolites found in both variants, the pigmented cells contained anthocyanidins, other flavonoids, and their glucosides. Analysis of single epidermal cells from different scale leaves in an A. cepa bulb showed metabolic differences corresponding to their age. Our results indicate the feasibility of using LAESI-MS for the in situ analysis of metabolites in single cells with potential applications in studying cell differentiation, changes due to disease states, and response to xenobiotics.

  2. Chemical Analysis of Complex Organic Mixtures Using Reactive Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Eckert, Peter A.; Roach, Patrick J.; Heath, Brandi S.; Nizkorodov, Sergey A.; Laskin, Alexander

    2012-08-21

    Reactive nanospray desorption electrospray ionization (nano-DESI) combined with high-resolution mass spectrometry was utilized for the analysis of secondary organic aerosol produced through ozonolysis of limonene (LSOA). Previous studies showed that LSOA constituents are multifunctional compounds containing aldehyde and ketone groups. In this study, we used the selectivity of the Girard T (GT) reagent towards carbonyl compounds to examine the utility of reactive nano-DESI for the analysis of complex organic mixtures. In these experiments, 1-100 {micro}M GT solution was used as a working solvent for reactive nano-DESI analysis. Abundant products of a single addition of GT to LSOA constituents were observed at GT concentrations in excess of 10 {micro}M. We found that LSOA compounds with 18-20 carbon atoms (dimers) and 27-30 carbon atoms (trimers) react with GT through a simple addition reaction resulting in formation of the carbinolamine derivative. In contrast, reactions of GT with monomeric species result in formation of both the carbinolamine and the hydrazone derivatives. In addition, several monomers did not react with GT on the timescale of our experiment. These molecules were characterized by relatively high values of the double bond equivalent (DBE) and low oxygen content. Furthermore, because addition of a charged GT tag to a neutral molecule eliminates the discrimination against the low proton affinity compounds in the ionization process, reactive nano-DESI analysis enables quantification of individual compounds in the complex mixture. For example, we were able to estimate for the first time the amounts of dimers and trimers in the LSOA mixture. Specifically, we found that the most abundant LSOA dimer was detected at ca. 0.5 pg level and the total amount of dimers and trimers in the analyzed sample was just around 11 pg. Our results indicate that reactive nano-DESI is a valuable approach for examining the presence of specific functional groups and

  3. Airborne observations of formic acid using a chemical ionization mass spectrometer

    Directory of Open Access Journals (Sweden)

    M. Le Breton

    2012-12-01

    Full Text Available The first airborne measurements of formic acid mixing ratios over the United Kingdom were measured on the FAAM BAe-146 research aircraft on 16 March 2010 with a chemical ionization mass spectrometer using I reagent ions. The I ionization scheme was able to measure formic acid mixing ratios at 1 Hz in the boundary layer.

    In-flight standard addition calibrations from a formic acid source were used to determine the instrument sensitivity of 35 ± 6 ion counts pptv−1 s−1 and a limit of detection of 25 pptv. Routine measurements were made through a scrubbed inlet to determine the instrumental background. Three plumes of formic acid were observed over the UK, originating from London, Humberside and Tyneside. The London plume had the highest formic acid mixing ratio throughout the flight, peaking at 358 pptv. No significant correlations of formic acid with NOx and ozone were found, but a positive correlation was observed between CO and HCOOH within the two plumes where coincident data were recorded.

    A trajectory model was employed to determine the sources of the plumes and compare modelled mixing ratios with measured values. The model underestimated formic acid concentrations by up to a factor of 2. This is explained by missing sources in the model, which were considered to be both primary emissions of formic acid of mainly anthropogenic origin and a lack of precursor emissions, such as isoprene, from biogenic sources, whose oxidation in situ would lead to formic acid formation.

  4. Analysis of triacetone triperoxide (TATP) and TATP synthetic intermediates by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Sigman, Michael E; Clark, C Douglas; Caiano, Tara; Mullen, Rebecca

    2008-01-01

    The explosive triacetone triperoxide (TATP) has been analyzed by electrospray ionization mass spectrometry (ESI-MS) on a linear quadrupole instrument, giving a 62.5 ng limit of detection in full scan positive ion mode. In the ESI interface with no applied fragmentor voltage the m/z 245 [TATP + Na](+) ion was observed along with m/z 215 [TATP + Na - C(2)H(6)](+) and 81 [(CH(3))(2)CO + Na](+). When TATP was ionized by ESI with an applied fragmentor voltage of 75 V, ions at m/z 141 [C(4)H(6)O(4) + Na](+) and 172 [C(5)H(9)O(5) + Na](+) were also observed. When the precipitates formed in the synthesis of TATP were analyzed before the reaction was complete, a new series of ions was observed in which the ions were separated by 74 m/z units, with ions occurring at m/z 205, 279, 353, 427, 501, 575, 649 and 723. The series of evenly spaced ions is accounted for as oligomeric acetone carbonyl oxides terminated as hydroperoxides, [HOOC(CH(3))(2){OOC(CH(3))(2)}(n)OOH + Na](+) (n = 1, 2 ... 8). The ESI-MS spectra for this homologous series of oligoperoxides have previously been observed from the ozonolysis of tetramethylethylene at low temperatures. Precipitates from the incomplete reaction mixture, under an applied fragmentor voltage of 100 V in ESI, produced an additional ion observed at m/z 99 [C(2)H(4)O(3) + Na](+), and a set of ions separated by 74 m/z units occurring at m/z 173, 247, 321, 395, 469 and 543, proposed to correspond to [CH(3)CO{OOC(CH(3))(2)}(n)OOH + Na](+) (n = 1,2 ... 5). Support for the assigned structures was obtained through the analysis of both protiated and perdeuterated TATP samples. Copyright (c) 2007 John Wiley & Sons, Ltd.

  5. Quantum Monte Carlo calculation of point defect thermal and optical ionization levels: application to magnesium oxide and zinc oxide

    Science.gov (United States)

    Ertekin, Elif; Wagner, Lucas; Grossman, Jeffrey

    2013-03-01

    From electronics to optoelectronics to photovoltaics, point defects influence and dominate the properties of semiconducting materials. Quantitative descriptions of the effect of point defects on electronic, optical, and transport properties are critical to enabling point-defect engineering for materials design. However, accurate prediction of point-defect energetics, thermal ionization energies, and optical transition energies from first principles remains a challenge. We present an approach to calculation of point defect optical and thermal ionization energies based on the highly accurate quantum Monte Carlo methods, and demonstrate it for the oxygen vacancy in the binary ionic compound magnesium oxide and the substitutional nitrogen impurity in zinc oxide. The use of quantum Monte Carlo, an inherently many-body theory that directly treats electron correlation, offers many improvements: it can help overcome the band gap problem in density functional theory and obviate the need for ad-hoc corrections. Our computed optical and thermal ionization energies are in excellent agreement with experimental and/or other high-accuracy results.

  6. Thermal mass impact on energy performance of a low, medium and heavy mass building in Belgrade

    Directory of Open Access Journals (Sweden)

    Anđelković Bojan V.

    2012-01-01

    Full Text Available Heavy mass materials used in building structures and architecture can significantly affect building energy performance and occupant comfort. The purpose of this study was to investigate if thermal mass can improve the internal environment of a building, resulting in lower energy requirements from the mechanical systems. The study was focused on passive building energy performance and compared annual space heating and cooling energy requirements for an office building in Belgrade with several different applications of thermal mass. A three-dimensional building model was generated to represent a typical office building. Building shape, orientation, glazing to wall ratio, envelope insulation thickness, and indoor design conditions were held constant while location and thickness of building mass (concrete was varied between cases in a series of energy simulations. The results were compared and discussed in terms of the building space heating and cooling energy and demand affected by thermal mass. The simulation results indicated that with addition of thermal mass to the building envelope and structure: 100% of all simulated cases experienced reduced annual space heating energy requirements, 67% of all simulated cases experienced reduced annual space cooling energy requirements, 83% of all simulated cases experienced reduced peak space heating demand and 50% of all simulated cases experienced reduced peak space cooling demand. The study demonstrated that there exists a potential for reducing space heating and cooling energy requirements with heavy mass construction in the analyzed climate region (Belgrade, Serbia.

  7. Phenotypic identification of Porphyromonas gingivalis validated with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Rams, Thomas E; Sautter, Jacqueline D; Getreu, Adam; van Winkelhoff, Arie J

    OBJECTIVE: Porphyromonas gingivalis is a major bacterial pathogen in human periodontitis. This study used matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry to assess the accuracy of a rapid phenotypic identification scheme for detection of cultivable P.

  8. Single short-column liquid chromatography with atmospheric pressure chemical ionization - (tandem) mass spectrometric detection for trace environmental analysis.

    NARCIS (Netherlands)

    Hogenboom, A.C.; Vreuls, J.J.; Rontree, J.A.; van Baar, B.L.M.; Niessen, W.M.A.; Brinkman, U.A.T.; Slobodník, J.

    1996-01-01

    Single short, i.e. ca 2-cm long, high-pressure-packed columns coupled with mass spectrometric (MS) or tandem MS detection enable rapid trace-level determination and identification of environmental pollutants in water samples. In this study an atmospheric pressure chemical ionization (APCI) interface

  9. Advantages of Atmospheric Pressure Chemical Ionization in Gas Chromatography Tandem Mass Spectrometry: Pyrethroid Insecticides as a Case Study

    NARCIS (Netherlands)

    Portolés, T.; Mol, J.G.J.; Sancho, J.V.; Hernández, F.

    2012-01-01

    Gas chromatography coupled to mass spectrometry (GC/MS) has been extensively applied for determination of volatile, nonpolar, compounds in many applied fields like food safety, environment, or toxicology. The wide majority of methods reported use electron ionization (EI), which may result in

  10. Accurate quantitation of pentaerythritol tetranitrate and its degradation products using liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry

    NARCIS (Netherlands)

    Brust, H.; Asten, A. van; Koeberg, M.; Dalmolen, J.; Heijden, A.E.D.M. van der; Schoenmakers, P.

    2014-01-01

    After an explosion of pentaerythritol tetranitrate (PETN), its degradation products pentaerythritol trinitrate (PETriN), dinitrate (PEDiN) and mononitrate (PEMN) were detected using liquid chromatography-atmospheric-pressure chemical-ionization-mass spectrometry (LC-APCI-MS). Discrimination between

  11. Regioisomers of octanoic acid-containing structured triacylglycerols analyzed by tandem mass spectrometry using ammonia negative ion chemical ionization

    DEFF Research Database (Denmark)

    Kurvinen, J.P.; Mu, Huiling; Kallio, H.

    2001-01-01

    Tandem mass spectrometry based on ammonia negative ion chemical ionization and sample introduction via direct exposure probe was applied to analysis of regioisomeric structures of octanoic acid containing structured triacylglycerols (TAG) of type MML, MLM, MLL, and LML (M, medium-chain fatty acid...

  12. Electrospray ionization quadrupole time-of-flight tandem mass spectrometric analysis of hexamethylenediamine-modified maltodextrin and dextran

    NARCIS (Netherlands)

    Sisu, E.; Bosker, W.T.E.; Norde, W.; Slaghek, T.M.; Timmermans, J.W.; Peter-Katalinić, J.; Cohen-Stuart, M.A.; Zamfir, A.D.

    2006-01-01

    A combined methodology for obtaining at the preparative scale and characterization by nanoelectrospray ionization (nanoESI) quadrupole time-of-flight (QTOF) mass spectrometry (MS) and tandem MS (MS/MS) of linear polysaccharides modified at the reducing end is presented. Two polydisperse

  13. Subtle differences in molecular recognition between modified glycopeptide antibiotics and bacterial receptor peptides identified by electrospray ionization mass spectrometry

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J. D.; Staroske, T; Roepstorff, P

    1999-01-01

    showing that electrospray ionization mass spectrometry (ESI-MS) can be used in the rapid quantitative analysis of mixtures of vancomycin-group antibiotics and their bacterial cell-wall receptors allowing the identification of even subtle differences in binding constants. Differences in affinities...

  14. Determination of BROMATE AT PARTS-PER-TRILLION LEVELS BY GAS CHROMATOGRAPHY-MASS SPECTROMETRY WITH NEGATIVE CHEMICAL IONIZATION

    Science.gov (United States)

    The ozonation of bromide-containing source waters produces bromate as a class 2B carcinogenic disinfection by-product. The present work describes the determination of bromate by gas chromatography-negative chemical ionization mass spectrometry (GC-NCIMS) following a bromate react...

  15. Development of matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) for plant metabolite analysis

    Energy Technology Data Exchange (ETDEWEB)

    Korte, Andrew R [Iowa State Univ., Ames, IA (United States)

    2014-12-01

    This thesis presents efforts to improve the methodology of matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) as a method for analysis of metabolites from plant tissue samples. The first chapter consists of a general introduction to the technique of MALDI-MSI, and the sixth and final chapter provides a brief summary and an outlook on future work.

  16. Determination of Peroxide Explosive TATP and Related Compounds by Dielectric Barrier Discharge Ionization-Mass Spectrometry (DBDI-MS).

    Science.gov (United States)

    Hagenhoff, Sebastian; Franzke, Joachim; Hayen, Heiko

    2017-04-04

    Dielectric barrier discharge ionization-mass spectrometry (DBDI-MS), which is based on the use of a low temperature helium plasma as ionization source, is used for the determination of trace amounts of triacetone triperoxide (TATP) and its homologue diacetone diperoxide (DADP) from surfaces. TATP is observed as [M+NH 4 ] + adduct, whereas DADP is observed as [M+O+NH 4 ] + . Measurement of DADP with varying deuteration degrees (DADP, DADP-d 6 , and DADP-d 12 ) indicates that DADP undergoes oxidation when ionized by DBDI. If acetonitrile is used as deposition solvent, TATP tends to show fragmentation and is not only detected as [M+NH 4 ] + but as [M-CH 4 +NH 4 ] + and [M-C 2 H 4 +NH 4 ] + as well. Quantification of TATP solutions from glass surfaces by DBDI-MS, using TATP-3,6,9- 13 C as internal standard, was done and validated using an LC/APCI-MS method. Achievable limits of detection (LOD) for TATP are equivalent to the deposition of 15 ng TATP and are comparable with other ambient desorption/ionization mass spectrometric techniques like desorption electrospray ionization (DESI).

  17. Coorbital thermal torques on low-mass protoplanets

    Science.gov (United States)

    Masset, Frédéric S.

    2017-12-01

    Using linear perturbation theory, we investigate the torque exerted on a low-mass planet embedded in a gaseous protoplanetary disc with finite thermal diffusivity. When the planet does not release energy into the ambient disc, the main effect of thermal diffusion is the softening of the enthalpy peak near the planet, which results in the appearance of two cold and dense lobes on either side of the orbit, of size smaller than the thickness of the disc. The lobes exert torques of opposite sign on the planet, each comparable in magnitude to the one-sided Lindblad torque. When the planet is offset from corotation, the lobes are asymmetric and the planet experiences a net torque, the `cold' thermal torque, which has a magnitude that depends on the relative value of the distance to corotation to the size of the lobes {˜ }√{χ /Ω _p}, χ being the thermal diffusivity and Ωp the orbital frequency. We believe that this effect corresponds to the phenomenon named `cold finger' recently reported in numerical simulations, and we argue that it constitutes the dominant mode of migration of sub-Earth-mass objects. When the planet is luminous, the heat released into the ambient disc results in an additional disturbance that takes the form of hot, low-density lobes. They give a torque, named heating torque in previous work, that has an expression similar, but of opposite sign, to the cold thermal torque.

  18. Extractive electrospray ionization mass spectrometry toward in situ analysis without sample pretreatment.

    Science.gov (United States)

    Li, Ming; Hu, Bin; Li, Jianqiang; Chen, Rong; Zhang, Xie; Chen, Huanwen

    2009-09-15

    A homemade novel nanoextractive electrospray ionization (nanoEESI) source has been characterized for in situ mass spectrometric analysis of ambient samples without sample pretreatment. The primary ions generated using a nanospray emitter interact with the neutral sample plume created by manually nebulizing liquid samples, allowing production of the analyte ions in the spatial cross section of the nanoEESI source. The performance of nanoEESI is experimentally investigated by coupling the nanoEESI source to a commercial LTQ mass spectrometer for rapid analysis of various ambient samples using positive/negative ion detection modes. Compounds of interest in actual samples such as aerosol drug preparations, beverages, milk suspensions, farmland water, and groundwater were unambiguously detected using tandem nanoEESI ion trap mass spectrometry. The limit of detection was low picogram per milliliter levels for the compounds tested. Acceptable relative standard deviation (RSD) values (5-10%) were obtained for direct measurement of analytes in complex matrixes, providing linear dynamic signal responses using manual sample introduction. A single sample analysis was completed within 1.2 s. Requiring no sheath gas for either primary ion production or neutral sample introduction, the nanoEESI has advantages including readiness for miniaturization and integration, simple maintenance, easy operation, and low cost. The experimental data demonstrate that the nanoEESI is a promising tool for high-throughput, sensitive, quantitative, in situ analysis of ambient complex samples, showing potential applications for in situ analysis in multiple disciplines including but not limited to pharmaceutical analysis, food quality control, pesticides residue detection, and homeland security.

  19. Gaseous composition measured by a chemical ionization mass spectrometer in fresh and aged ship plumes

    Science.gov (United States)

    Faxon, Cameron; Psichoudaki, Magda; Kuuluvainen, Heino; Hallquist, Åsa; Thomson, Erik; Pettersson, Jan; Hallquist, Mattias

    2015-04-01

    The port of Gothenburg is the largest port of the Nordic countries with numerous ships calling the port daily. The ship exhausts contain numerous pollutants including gases such as SO2 and NOx as well as particulate matter and soot. The exhaust also contains numerous organic compounds, a large fraction of which are unidentified. These organics are oxidized in the atmosphere producing more oxygenated and potentially less volatile compounds that may contribute to the secondary organic aerosol (SOA). This work focuses on the characterization of fresh gaseous species present in the exhaust plumes of the passing ships and also on their photochemical aging. Between 26 September and 12 November 2014 measurements were conducted at a sampling site located on a small peninsula at the entrance of Gothenburg's port. The campaign was divided in two periods. During the first period, the fresh plumes of the passing ships were measured through a main inlet. During the second period, the sample passed through the same inlet and was then introduced into a Potential Aerosol Mass (PAM) reactor. The PAM reactor uses UV lamps and high concentrations of oxidants (OH radicals and O3) to oxidize the organic species present in the plumes. The oxidation that takes place within the reactor can be equivalent to up to one week of atmospheric oxidation. Preliminary tests showed that the oxidation employed in the current camping corresponded to 3.4 days in the atmosphere. A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged plumes. Water (positive) and iodide (negative) ionization methods were employed were water was primarily used for fresh plumes (large fraction of non-polar compounds) while iodide was used for the aged plumes (primarily oxidised products). The H2O, O3 and SO2 concentrations inside the PAM chamber were monitored, and an organic tracer for OH exposure determination

  20. Alkaloid profiling of the Chinese herbal medicine Fuzi by combination of matrix-assisted laser desorption ionization mass spectrometry with liquid chromatography-mass spectrometry

    NARCIS (Netherlands)

    Wang, J.; Heijden, R. van der; Spijksma, G.; Reijmers, T.; Wang, M.; Xu, G.; Hankemeier, T.; Greef, J. van der

    2009-01-01

    A matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) method was developed for the high throughput and robust qualitative profiling of alkaloids in Fuzi-the processed lateral roots of the Chinese herbal medicine Aconitum carmichaeli Debx (A. carmichaeli). After optimization,

  1. Comparison of atmospheric pressure chemical ionization and electrospray ionization mass spectrometry for the detection of lignans from sesame seeds

    NARCIS (Netherlands)

    Struijs, K.; Vincken, J.P.; Gruppen, H.

    2008-01-01

    In sesame seeds, high concentrations of lignans are present. When these lignans are fermented in the human colon, a range of structurally different lignans is formed. A good liquid chromatography/mass spectrometry (LC/MS) protocol for the analysis of lignans in complex mixtures is lacking. In order

  2. Rapid identification of regulated organic chemical compounds in toys using ambient ionization and a miniature mass spectrometry system.

    Science.gov (United States)

    Guo, Xiangyu; Bai, Hua; Lv, Yueguang; Xi, Guangcheng; Li, Junfang; Ma, Xiaoxiao; Ren, Yue; Ouyang, Zheng; Ma, Qiang

    2018-04-01

    Rapid, on-site analysis was achieved through significantly simplified operation procedures for a wide variety of toy samples (crayon, temporary tattoo sticker, finger paint, modeling clay, and bubble solution) using a miniature mass spectrometry system with ambient ionization capability. The labor-intensive analytical protocols involving sample workup and chemical separation, traditionally required for MS-based analysis, were replaced by direct sampling analysis using ambient ionization methods. A Mini β ion trap miniature mass spectrometer was coupled with versatile ambient ionization methods, e.g. paper spray, extraction spray and slug-flow microextraction nanoESI for direct identification of prohibited colorants, carcinogenic primary aromatic amines, allergenic fragrances, preservatives and plasticizers from raw toy samples. The use of paper substrates coated with Co 3 O 4 nanoparticles allowed a great increase in sensitivity for paper spray. Limits of detection as low as 5μgkg -1 were obtained for target analytes. The methods being developed based on the integration of ambient ionization with miniature mass spectrometer represent alternatives to current in-lab MS analysis operation, and would enable fast, outside-the-lab screening of toy products to ensure children's safety and health. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Distillation of fermented sugarcane juice: fractions characterized by electrospray ionization mass spectrometry and multivariate data treatment.

    Science.gov (United States)

    Canuto, Marcus H; Rosa, Carlos A; de Moura, Fabiana; Augusti, Rodinei; Siebald, Helmuth G L

    2012-07-01

    Direct infusion electrospray ionization mass spectrometry in the negative ion mode (ESI(-)-MS) was employed to discriminate among fractions arising from the distillation of fermented sugarcane juice during the production of cachaça, a typical Brazilian alcoholic beverage. Aliquots were collected in the course of distillation and their ESI(-)-MS shown to be almost indistinguishable by a simple visual inspection. However, when the ESI(-)-MS data were treated by the principal component analysis (PCA) and hierarchical clustering analysis (HCA) statistical methods, four major groups were clearly determined, the so-called head (two distinct clusters), heart and tail fractions. Furthermore, the recognition of diagnostic ions (and their respective intensities) enabled a more confident establishment of the cutoff position (i.e. the initial and final points of each fraction). In conclusion, ESI-MS, in conjunction with PCA or HCA approaches, proved to be a quite efficient method that allowed for a prompt characterization of each fraction derived from the distillation of brewed sugarcane. The results described herein can, therefore, be useful not only to optimize the production of cachaça but also to improve the quality of the final product. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Gas-phase pesticide measurement using iodide ionization time-of-flight mass spectrometry

    Science.gov (United States)

    Murschell, Trey; Fulgham, S. Ryan; Farmer, Delphine K.

    2017-06-01

    Volatilization and subsequent processing in the atmosphere are an important environmental pathway for the transport and chemical fate of pesticides. However, these processes remain a particularly poorly understood component of pesticide lifecycles due to analytical challenges in measuring pesticides in the atmosphere. Most pesticide measurements require long (hours to days) sampling times coupled with offline analysis, inhibiting observation of meteorologically driven events or investigation of rapid oxidation chemistry. Here, we present chemical ionization time-of-flight mass spectrometry with iodide reagent ions as a fast and sensitive measurement of four current-use pesticides. These semi-volatile pesticides were calibrated with injections of solutions onto a filter and subsequently volatilized to generate gas-phase analytes. Trifluralin and atrazine are detected as iodide-molecule adducts, while permethrin and metolachlor are detected as adducts between iodide and fragments of the parent analyte molecule. Limits of detection (1 s) are 0.37, 0.67, 0.56, and 1.1 µg m-3 for gas-phase trifluralin, metolachlor, atrazine, and permethrin, respectively. The sensitivities of trifluralin and metolachlor depend on relative humidity, changing as much as 70 and 59, respectively, as relative humidity of the sample air varies from 0 to 80 %. This measurement approach is thus appropriate for laboratory experiments and potentially near-source field measurements.

  5. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain); Ferreira, Vicente, E-mail: vferre@unizar.es [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain)

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R{sup 2} > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  6. Rapid screening of clenbuterol in urine samples by desorption electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Lin, Ziqing; Zhang, Sichun; Zhao, Mengxia; Yang, Chengdui; Chen, Depu; Zhang, Xinrong

    2008-06-01

    Rapid screening of clenbuterol in urine was performed by combining desorption electrospray ionization (DESI) and tandem mass spectrometry (MS/MS). Optimization experiments were carried out including the selection of substrates, spray solutions, nebulizing gas pressures, high-voltage power supplies and flow rates of spray solution. The limit of detection (LOD), defined as the lowest quantity that can be detected, was 5.0 pg for the pure compound. Using DESI coupled with solid-phase extraction (SPE), the linear response range was from 10 to 400 ng/mL (R(2) = 0.993) and the concentration LOD for urine sample was 2.0 ng/mL. The analysis for one spiked urine sample was achieved within 4 min. In addition to the fast analysis speed, MS/MS provided structural information for the confirmation of clenbuterol. Urine samples from different people were investigated and the recoveries were within 100 +/- 20%. The developed method can potentially be used for screening of clenbuterol in doping control.

  7. Monitoring structural evolution of organosilicate species during sol-gel processes by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Li, Jun; Chen, Lei

    2016-02-28

    Electrospray ionization mass spectrometry (ESI-MS) has been employed to study species distribution in controlled acid-catalyzed hydrolysis and condensation of (3-chloropropyl)trimethoxysilane (CPTMS), which is frequently used in the synthesis of hybrid silica-based materials. The conditions of analysis for reaction products, i.e. organosilicate oligomers, were optimized by using various capillary temperatures and solute concentrations. The structures of organosilicate oligomers were shown to vary with reaction duration and the molar ratio of water to siloxane (r), with multiple types of oligomers attributed to linear, cyclic and hydroxylated species. The evolution of oligomeric structures was elucidated from the ESI-MS spectra. The number and intensity of cyclic oligomers increase with an increase in the r-value or reaction length, at the expense of linear species, indicating the trend to formation of cross-linked polysiloxane structures. Overall, this work demonstrates that ESI-MS is an indispensable tool for the comprehensive characterization of the correlation between properties and structure of hybrid silica-based materials. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Quantitative profiling and pattern analysis of triacylglycerol species in Arabidopsis seeds by electrospray ionization mass spectrometry.

    Science.gov (United States)

    Li, Maoyin; Baughman, Ethan; Roth, Mary R; Han, Xianlin; Welti, Ruth; Wang, Xuemin

    2014-01-01

    Plant triacylglycerols (TAGs), or vegetable oils, provide approximately 25% of dietary calories to humans and are becoming an increasingly important source of renewable bioenergy and industrial feedstocks. TAGs are assembled by multiple enzymes in the endoplasmic reticulum from building blocks that include an invariable glycerol backbone and variable fatty acyl chains. It remains a challenge to elucidate the mechanism of synthesis of hundreds of different TAG species in planta. One reason is the lack of an efficient analytical approach quantifying individual molecular species. Here we report a rapid and quantitative TAG profiling approach for Arabidopsis seeds based on electrospray ionization tandem mass spectrometry with direct infusion and multiple neutral loss scans. The levels of 93 TAG molecular species, identified by their acyl components, were determined in Arabidopsis seeds. Quantitative TAG pattern analyses revealed that the TAG assembly machinery preferentially produces TAGs with one elongated fatty acid. The importance of the selectivity in oil synthesis was consistent with an observation that an Arabidopsis mutant overexpressing a patatin-like phospholipase had enhanced seed oil content with elongated fatty acids. This quantitative TAG profiling approach should facilitate investigations aimed at understanding the biochemical mechanisms of TAG metabolism in plants. © 2013 The Authors The Plant Journal © 2013 John Wiley & Sons Ltd.

  9. Simultaneous determination of 15 nitroimidazoles in cosmetics by HPLC coupled with electrospray ionization- tandem mass spectrometry.

    Science.gov (United States)

    Meng, Xian-Shuang; Bai, Hua; Zhang, Qing; Lv, Qing; Chen, Yun-Xia; Ma, Hui-Juan; Li, Jing-Rui; Ma, Qiang

    2014-01-01

    A sensitive and reliable analytical method based on HPLC/MSIMS has been developed for the simultaneous determination of 15 nitroimidazoles in cosmetics. A diversity of cosmetic samples, including powder, lotion, shampoo, and cream were collected. The samples were ultrasonically extracted with aqueous methanol, and the extracts were then subjected to cleanup bySPE using an Oasis HLB cartridge followed by filtration with a 0.20 pm membrane filter. Afterwards, chromatographic separation was performed on an XSelect CSH C18 column (2.1 x 150 mm, 3.5 pm) maintained at 30°C within 15 min by a gradient of acetonitrile-0.1% aqueous formic acid solution at a flow rate of 0.25 mL/min. The mass spectrometric detection was carried, out using electrospray positive ionization under the multiple reaction monitoring mode. A good linearity was observed over the concentration range from 0.5 to 500 ng/mL. The intraday and interday precisions, which were investigated by determining all target compounds in cosmetics seven times/day and on 7 consecutive days, were below 5.00%. The mean recoveries at three spiked levels ranged from 80.42 to 100.83% with the RSDs from 0.45 to 9.02%. The LOQs were determined to be between 0.01 and 0.1 mg/kg. The method was sufficiently rapid, reliable, and sensitive for the determination of 15 nitroimidazoles in cosmetics.

  10. Determination of trinexapac in wheat by liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Hiemstra, Maurice; de Kok, André

    2003-09-24

    A quantitative and confirmatory method for the analysis of trinexapac (free acid metabolite of trinexapac-ethyl) in wheat is described. Residues were extracted from wheat with acetonitrile in aqueous phosphate buffer (pH 7) overnight. The extract was directly injected into the HPLC system. Chromatographic separation was achieved on an octadecylsilica column, and detection was performed by negative ion electrospray ionization tandem mass spectrometry. The precursor ion of trinexapac [M - H](-) at m/z 223 was subjected to collisional fragmentation with argon to yield two intense diagnostic product ions at m/z 135 and 179, respectively. Accuracy and specificity for routine analysis of trinexapac were demonstrated. The validated concentration range was 10-200 microg/kg based on a 0.10 g/mL wheat sample extract. Recoveries were within the range of 71-94%, with associated relative standard deviations better than 10%. The limit of detection for trinexapac in wheat was estimated at 5 microg/kg. The method has been applied to a survey of 100 samples of wheat. In 46% of the samples analyzed, a quantifiable amount of trinexapac was detected, ranging from 10 to 110 microg/kg. It has been demonstrated that analyses of trinexapac accurately reflect the total amount of residues of the plant growth regulator, trinexapac-ethyl, in the wheat samples following field application. No residues of the parent compound, trinexapac-ethyl, in wheat were detected.

  11. Performance of a corona ion source for measurement of sulfuric acid by chemical ionization mass spectrometry

    Directory of Open Access Journals (Sweden)

    A. Kürten

    2011-03-01

    Full Text Available The performance of an ion source based on corona discharge has been studied. This source is used for the detection of gaseous sulfuric acid by chemical ionization mass spectrometry (CIMS through the reaction of NO3 ions with H2SO4. The ion source is operated under atmospheric pressure and its design is similar to the one of a radioactive (americium-241 ion source which has been used previously. The results show that the detection limit for the corona ion source is sufficiently good for most applications. For an integration time of 1 min it is ~6 × 104 molecule cm−3 of H2SO4. In addition, only a small cross-sensitivity to SO2 has been observed for concentrations as high as 1 ppmv in the sample gas. This low sensitivity to SO2 is achieved even without the addition of an OH scavenger. When comparing the new corona ion source with the americium ion source for the same provided H2SO4 concentration, both ion sources yield almost identical values. These features make the corona ion source investigated here favorable over the more commonly used radioactive ion sources for most applications where H2SO4 is measured by CIMS.

  12. Calibration of a chemical ionization mass spectrometer for the measurement of gaseous sulfuric acid.

    Science.gov (United States)

    Kürten, Andreas; Rondo, Linda; Ehrhart, Sebastian; Curtius, Joachim

    2012-06-21

    The accurate measurement of the gaseous sulfuric acid concentration is crucial within many fields of atmospheric science. Instruments utilizing chemical ionization mass spectrometry (CIMS) measuring H(2)SO(4), therefore, require a careful calibration. We have set up a calibration source that can provide a stable and adjustable concentration of H(2)SO(4). The calibration system initiates the production of sulfuric acid through the oxidation of SO(2) by OH. The hydroxyl radical is produced by UV photolysis of water vapor. A numerical model calculates the H(2)SO(4) concentration provided at the outlet of the calibration source. From comparison of this concentration and the signals measured by CIMS, a calibration factor is derived. This factor is evaluated to be 1.1 × 10(10) cm(-3), which is in good agreement with values found in the literature for other CIMS instruments measuring H(2)SO(4). The calibration system is described in detail and the results are discussed. Because the setup is external to the CIMS instrument, it offers the possibility for future CIMS intercomparison measurements by providing defined and stable concentrations of sulfuric acid.

  13. Application of Resonance Ionization Mass Spectrometry for Ultratrace Analysis of Technetium.

    Science.gov (United States)

    Schönberg, Pascal; Mokry, Christoph; Runke, Jörg; Schönenbach, Daniela; Stöbener, Nils; Thörle-Pospiech, Petra; Trautmann, Norbert; Reich, Tobias

    2017-09-05

    This work shows the ability of resonance ionization mass spectrometry (RIMS) to determine (99g)Tc at the ultratrace level. The characterization of the prepared samples by X-ray photoelectron spectroscopy (XPS) and optimization of the RIMS setup for this purpose, as well as the application of the RIMS method to a soil sample, are presented in this article. (97)Tc was used as a tracer isotope to determine the amount of (99g)Tc in a soil sample with RIMS. With 8.8 × 10(10) atoms of (97)Tc as the tracer, the concentration of (99g)Tc was found to be 1.5 × 10(9) atoms per gram of dried sample material, demonstrating the sensitivity of the method. Furthermore, it could be shown that the (97)Tc solution contained (98)Tc as well. This is the first time that (97,98,99g)Tc have been simultaneously measured with RIMS.

  14. Quantitative detection of nitric oxide in exhaled human breath by extractive electrospray ionization mass spectrometry

    Science.gov (United States)

    Pan, Susu; Tian, Yong; Li, Ming; Zhao, Jiuyan; Zhu, Lanlan; Zhang, Wei; Gu, Haiwei; Wang, Haidong; Shi, Jianbo; Fang, Xiang; Li, Penghui; Chen, Huanwen

    2015-03-01

    Exhaled nitric oxide (eNO) is a useful biomarker of various physiological conditions, including asthma and other pulmonary diseases. Herein a fast and sensitive analytical method has been developed for the quantitative detection of eNO based on extractive electrospray ionization mass spectrometry (EESI-MS). Exhaled NO molecules selectively reacted with 2-phenyl-4, 4, 5, 5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) reagent, and eNO concentration was derived based on the EESI-MS response of 1-oxyl-2-phenyl-4, 4, 5, 5-tetramethylimidazoline (PTI) product. The method allowed quantification of eNO below ppb level (~0.02 ppbv) with a relative standard deviation (RSD) of 11.6%. In addition, eNO levels of 20 volunteers were monitored by EESI-MS over the time period of 10 hrs. Long-term eNO response to smoking a cigarette was recorded, and the observed time-dependent profile was discussed. This work extends the application of EESI-MS to small molecules (metabolism and clinical diagnosis.

  15. Gas-phase pesticide measurement using iodide ionization time-of-flight mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. Murschell

    2017-06-01

    Full Text Available Volatilization and subsequent processing in the atmosphere are an important environmental pathway for the transport and chemical fate of pesticides. However, these processes remain a particularly poorly understood component of pesticide lifecycles due to analytical challenges in measuring pesticides in the atmosphere. Most pesticide measurements require long (hours to days sampling times coupled with offline analysis, inhibiting observation of meteorologically driven events or investigation of rapid oxidation chemistry. Here, we present chemical ionization time-of-flight mass spectrometry with iodide reagent ions as a fast and sensitive measurement of four current-use pesticides. These semi-volatile pesticides were calibrated with injections of solutions onto a filter and subsequently volatilized to generate gas-phase analytes. Trifluralin and atrazine are detected as iodide–molecule adducts, while permethrin and metolachlor are detected as adducts between iodide and fragments of the parent analyte molecule. Limits of detection (1 s are 0.37, 0.67, 0.56, and 1.1 µg m−3 for gas-phase trifluralin, metolachlor, atrazine, and permethrin, respectively. The sensitivities of trifluralin and metolachlor depend on relative humidity, changing as much as 70 and 59, respectively, as relative humidity of the sample air varies from 0 to 80 %. This measurement approach is thus appropriate for laboratory experiments and potentially near-source field measurements.

  16. Imaging Nicotine in Rat Brain Tissue by Use of Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Thomas, Mathew; Carson, James P.; Smith, Jordan N.; Timchalk, Charles; Laskin, Julia

    2013-01-15

    Imaging mass spectrometry offers simultaneous detection of drugs, drug metabolites and endogenous substances in a single experiment. This is important when evaluating effects of a drug on a complex organ system such as the brain, where there is a need to understand how regional drug distribution impacts function. Nicotine is an addictive drug and its action in the brain is of high interest. Here we use nanospray desorption electrospray ionization, nano-DESI, imaging to discover the localization of nicotine in rat brain tissue after in vivo administration of nicotine. Nano-DESI is a new ambient technique that enables spatially-resolved analysis of tissue samples without special sample pretreatment. We demonstrate high sensitivity of nano-DESI imaging that enables detection of only 0.7 fmole nicotine per pixel in the complex brain matrix. Furthermore, by adding deuterated nicotine to the solvent, we examined how matrix effects, ion suppression, and normalization affect the observed nicotine distribution. Finally, we provide preliminary results suggesting that nicotine localizes to the hippocampal substructure called dentate gyrus.

  17. Plasmonic nanoshells enhanced laser desorption/ionization mass spectrometry for detection of serum metabolites.

    Science.gov (United States)

    Wei, Xiang; Liu, Zhonghui; Jin, Xiulong; Huang, Lin; Gurav, Deepanjali Dattatray; Sun, Xuming; Liu, Baohong; Ye, Jian; Qian, Kun

    2017-01-15

    Laser desorption/ionization mass spectrometry (LDI MS)-based small metabolites detection is fundamentally important for the clinic prognoses and diagnoses. Plasmonic materials have been applied as efficient substrates for LDI MS of these molecules. However, there is no clear understanding of the mechanism of using plasmonic materials for enhanced LDI MS of small metabolites, thus restricting their application for real case serum samples. In this work, we report the use of plasmonic nanoshells for enhanced LDI MS detection of small analytes. The antibonding modes of Au nanoshells provided unique opportunity for the generation of hot carriers in the ultra-violet (UV) optical range. This effect of the Au nanoshells displayed desirable analytical sensitivity and endurance towards small metabolites (e.g. amino acids) in complex protein/mixtures as compared to Au nanorods/nanospheres and conventional organic matrix. Further we achieved LDI MS profiling and detection of small metabolites from complex serum samples by Au nanoshells. Our work not only shed light on the enhancement mechanism of LDI MS detection using plasmonic nanoparticles with hot carriers, but also contributed to the real case application of LDI MS in clinical study. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Metabolic Profiling Directly from the Petri Dish Using Nanospray Desorption Electrospray Ionization Imaging Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Watrous, Jeramie D.; Roach, Patrick J.; Heath, Brandi S.; Alexandrov, Theodore; Laskin, Julia; Dorrestein, Pieter C.

    2013-11-05

    Understanding molecular interaction pathways in complex biological systems constitutes a treasure trove of knowledge that might facilitate the specific, chemical manipulation of the countless microbiological systems that occur throughout our world. However, there is a lack of methodologies that allow the direct investigation of chemical gradients and interactions in living biological systems, in real time. Here, we report the use of nanospray desorption electrospray ionization (nanoDESI) imaging mass spectrometry for in vivo metabolic profiling of living bacterial colonies directly from the Petri dish with absolutely no sample preparation needed. Using this technique, we investigated single colonies of Shewanella oneidensis MR-1, Bacillus subtilis 3610, and Streptomyces coelicolor A3(2) as well as a mixed biofilm of S. oneidensis MR-1 and B. subtilis 3610. Data from B. subtilis 3610 and S. coelicolor A3(2) provided a means of validation for the method while data from S. oneidensis MR-1 and the mixed biofilm showed a wide range of compounds that this bacterium uses for the dissimilatory reduction of extracellular metal oxides, including riboflavin, iron-bound heme and heme biosynthetic intermediates, and the siderophore putrebactin.

  19. Modeling energy flexibility of low energy buildings utilizing thermal mass

    DEFF Research Database (Denmark)

    Foteinaki, Kyriaki; Heller, Alfred; Rode, Carsten

    2016-01-01

    In the future energy system a considerable increase in the penetration of renewable energy is expected, challenging the stability of the system, as both production and consumption will have fluctuating patterns. Hence, the concept of energy flexibility will be necessary in order for the consumption...... to match the production patterns, shifting demand from on-peak hours to off-peak hours. Buildings could act as flexibility suppliers to the energy system, through load shifting potential, provided that the large thermal mass of the building stock could be utilized for energy storage. In the present study...... the load shifting potential of an apartment of a low energy building in Copenhagen is assessed, utilizing the heat storage capacity of the thermal mass when the heating system is switched off for relieving the energy system. It is shown that when using a 4-hour preheating period before switching off...

  20. Mass spectrometry characterization of the thermal decomposition/digestion (TDD) at cysteine in peptides and proteins in the condensed phase.

    Science.gov (United States)

    Basile, Franco; Zhang, Shaofeng; Kandar, Sujit Kumar; Lu, Liang

    2011-11-01

    We report on the characterization by mass spectrometry (MS) of a rapid, reagentless and site-specific cleavage at the N-terminus of the amino acid cysteine (C) in peptides and proteins induced by the thermal decomposition at 220-250 °C for 10 s in solid samples. This thermally induced cleavage at C occurs under the same conditions and simultaneously to our previously reported thermally induced site-specific cleavage at the C-terminus of aspartic acid (D) (Zhang, S.; Basile, F. J. Proteome Res. 2007, 6, (5), 1700-1704). The C cleavage proceeds through cleavage of the nitrogen and α-carbon bond (N-terminus) of cysteine and produces modifications at the cleavage site with an amidation (-1 Da) of the N-terminal thermal decomposition product and a -32 Da mass change of the C-terminal thermal decomposition product, the latter yielding either an alanine or β-alanine residue at the N-terminus site. These modifications were confirmed by off-line thermal decomposition electrospray ionization (ESI)-MS, tandem MS (MS/MS) analyses and accurate mass measurements of standard peptides. Molecular oxygen was found to be required for the thermal decomposition and cleavage at C as it induced an initial cysteine thiol side chain oxidation to sulfinic acid. Similar to the thermally induced D cleavage, missed cleavages at C were also observed. The combined thermally induced digestion process at D and C, termed thermal decomposition/digestion (TDD), was observed on several model proteins tested under ambient conditions and the site-specificity of the method confirmed by MS/MS.

  1. Gaseous and particulate composition of fresh and aged emissions of diesel, RME and CNG buses using Chemical Ionization Mass Spectrometry

    Science.gov (United States)

    Psichoudaki, Magda; Le Breton, Michael; Hallquist, Mattias; Watne, Ågot; Hallquist, Asa

    2016-04-01

    . A Time-of-Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) was employed to monitor the concentration of different organic species present in the fresh and aged emissions. This instrument is capable of identifying the molecular formulas of species in the gas phase. The FIGAERO inlet, also enabled the characterisation of the particle phase, as particles were simultaneously collected on a filter, from which they could then be thermally desorbed and detected. Acetate (negative) ionization was utilised to allow high sensitivity measurements of organic acids, aldehydes, ketones, diols and halogenated species. The H2O, O3 and NOx concentrations inside the PAM flow reactor were monitored, and an organic tracer for OH exposure was also continuously measured. The concentrations of dominant species in both fresh and aged gaseous and particulate bus emissions from the different fuel types will be presented as well as their emission factors, calculated from concurrent CO2 measurements.

  2. Detection of chemical weapon agents and simulants using chemical ionization reaction time-of-flight mass spectrometry.

    Science.gov (United States)

    Cordell, Rebecca L; Willis, Kerry A; Wyche, Kevin P; Blake, Robert S; Ellis, Andrew M; Monks, Paul S

    2007-11-01

    Chemical ionization reaction time-of-flight mass spectrometry (CIR-TOF-MS) has been used for the analysis of prepared mixtures of chemical weapon agents (CWAs) sarin and sulfur mustard. Detection of the CWA simulants 2-chloroethyl ethyl sulfide, triethyl phosphate, and dimethyl methyl phosphonate has also been investigated. Chemical ionization of all the agents and simulants was shown to be possible using the CIR-TOF-MS technique with a variety of reagent ions, and the sensitivity was optimized by variation of instrument parameters. The ionization process was found to be largely unaffected by sample humidity levels, demonstrating the potential suitability of the method to a range of environmental conditions, including the analysis of CWAs in air and in the breath of exposed individuals.

  3. Rapid identification of molecular changes in tulsi (Ocimum sanctum Linn) upon ageing using leaf spray ionization mass spectrometry.

    Science.gov (United States)

    Sarkar, Depanjan; Srimany, Amitava; Pradeep, T

    2012-10-07

    Tulsi or Holy Basil (Ocimum sanctum Linn) is a medicinally important plant. Ursolic acid (UA) and oleanolic acid (OA) are among its major constituents which account for many medicinal activities of the plant. In the present work, we deployed a new ambient ionization method, leaf spray ionization, for rapid detection of UA, OA and their oxidation products from tulsi leaves. Tandem electrospray ionization mass spectrometry (ESI-MS) has been performed on tulsi leaf extracts in methanol to establish the identity of the compounds. We probed changes occurring in the relative amounts of the parent compounds (UA and OA) with their oxidized products and the latter show an increasing trend upon ageing. The findings are verified by ESI-MS analysis of tulsi leaf extracts, which shows the same trend proving the reliability of the leaf spray method.

  4. Analysis of phenolic compounds in rhubarbs using liquid chromatography coupled with electrospray ionization mass spectrometry.

    Science.gov (United States)

    Ye, Min; Han, Jian; Chen, Hubiao; Zheng, Junhua; Guo, Dean

    2007-01-01

    Rhubarb is an important herbal medicine for the treatment of constipation, inflammation, and cancer. In this study, a facile method based on liquid chromatography coupled with electrospray ionization tandem mass spectrometry has been established for the analysis of bioactive phenolic compounds in rhubarbs. From six rhubarb species, official (Rheum officinale, R. palmatum, and R. tanguticum) and unofficial (R. franzenbachii, R. hotaoense, and R. emodi), a total of 107 phenolic compounds were identified or tentatively characterized based on their mass spectra. These compounds include sennosides, anthraquinones, stilbenes, glucose gallates, naphthalenes, and catechins. Ion chromatograms for the identified compounds of different rhubarbs were then compared. Consistent with previous reports, sennosides and rhein were only detected in official rhubarbs. Unexpectedly, we found that R. officinale contained very different phenolic compounds from the other two official species. Sennoside A, which has been considered as the major purgative component of rhubarb, was only detected in R. officinale, while its close isomers were observed in R. palmatum and R. tanguticum. In addition, the predominant anthraquinone glycosides in R. officinale were found to be rhein 8-O-glucoside and emodin 1-O-glucoside, whereas those in R. palmatum and R. tanguticum were rhein 1-O-glucoside and emodin 8-O-glucoside. Stilbenes, which are the major constituents of unofficial rhubarbs, were also different among the species. Our results clarify the chemical composition of rhubarbs comprehensively for the first time. Due to the significant differences in chemical components of rhubarbs, we suggest that different Rheum species be used separately in clinical practice.

  5. Complexation of transition metals by 3-azidopropionitrile. An electrospray ionization mass spectrometry study.

    Science.gov (United States)

    Couto, Narciso; Duarte, M Filomena; Fernandez, M Tereza; Rodrigues, Paula; Barros, M Teresa; Costa, M Lourdes; Cabral, Benedito J Costa

    2007-03-01

    Most complexes of azides and transition metals involve the N(3)(-) azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) in methanol/water. In the case of nickel, other NiX(2) salts were investigated (where X = Br or NO(3)) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2), and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX](+), where X = Cl, Br, NO(3). Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal-nitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono- or a bidentate ligand.

  6. Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

    2017-01-01

    Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

  7. Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

    Science.gov (United States)

    Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

    2015-09-03

    Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

  8. Study of liquid chromatography/electrospray ionization mass spectrometry matrix effect on the example of glyphosate analysis from cereals.

    Science.gov (United States)

    Kruve, Anneli; Auling, Ragne; Herodes, Koit; Leito, Ivo

    2011-11-15

    Glyphosate is one of the most common pesticides used in the pre-harvest treatment of cereals. This paper examines the matrix effect of glyphosate liquid chromatography/electrospray ionization mass spectrometric (LC/ESI-MS) analysis in wheat and rye. The matrix effect (ionization suppression) was found to be dependent on sample particle size taken for the extraction. If samples are ground to very small particles severe ionization suppression occurs. For lower glyphosate contents (matrix effect was found to be dependent on the matrix - rye showed significantly stronger ionization suppression than wheat, although these matrices are not very different. The matrix effect also depends on the concentration of glyphosate in the post-extraction spiked samples. It is demonstrated that the isotope-labelled standard (13)C(2)-glyphosate undergoes different ionization suppression than glyphosate and is therefore not efficient in compensating for matrix effect. At the same time the extrapolative dilution approach allows to efficiently compensate for matrix effect. Copyright © 2011 John Wiley & Sons, Ltd.

  9. Mass Spectrometry in Cosmetic Science: Advanced Ionization Techniques for Detecting Trace Molecules in or on Human Skin

    Science.gov (United States)

    Motoyama, Akira; Kihara, Keishi

    2017-01-01

    To provide safe and effective products to customers in the cosmetic industry, mass spectrometry (MS) is an indispensable analytical tool. In addition to its outstanding sensitivity and specificity, the method is applicable to a wide variety of compounds, which makes it irreplaceable for the development of cosmetics, which requires the analysis of complex systems. Because most cosmetic products are applied directly to the skin and function as they are designed, monitoring the molecular compositions of endogenous or exogenous compounds in or on the skin is crucial to ensure the safety and efficacy of a cosmetic product. Recent advancements in MS and ionization techniques, such as MS imaging and ambient ionization, now provide access to richer and deeper molecular information with less time and effort. This brief review discusses advanced ionization techniques that are currently used in the field of cosmetic science using two examples, namely, the use of desorption electrospray ionization and zero-volt paperspray ionization to detect trace molecules in or on human skin. PMID:28959516

  10. A comparison of the techniques of secondary ion mass spectrometry and resonance ionization mass spectrometry for the analysis of potentially toxic element accumulation in neural tissue.

    Science.gov (United States)

    Jones, O R; Perks, R M; Abraham, C J; Telle, H H; Oakley, A E

    1997-01-01

    A comparison is made of the techniques of secondary ion mass spectrometry (SIMS) and resonance ionization mass spectrometry (RIMS) for the detection of the neuro-toxic element aluminium in cortical tissue. Experiments were performed using a reflectron-type time-of-flight mass spectrometer (TOFMS) in conjunction with an Ar+ source for target sputtering and a pulsed tuneable dye laser system for resonance ionization. It is shown how isobaric interference of species such as CNH and C2H3 in the case of aluminium greatly affect the quantitative accuracy and the detection limit of aluminium in biological samples when analysed using SIMS. In contrast the use of RIMS virtually eliminates this problem, so allowing easier quantification and much lower detection limits to be achieved. Detection limits of approximately 3 ppm for aluminium in brain tissue homogenates were achieved using RIMS, with a spatial resolution of less than 100 microns.

  11. Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

    Science.gov (United States)

    Raina, Renata; Hall, Patricia

    2008-01-01

    A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) with gas chromatography-tandem mass spectrometry (GC-MS/MS) in selected reaction monitoring (SRM) mode with both electron ionization (EI) and negative-ion chemical ionization (NCI) are presented for over 50 pesticides ranging from organochlorines (OCs), organophosphorus pesticides (OPs) and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalfluralin). The developed GC-EI/SIM, GC-NCI/SIM, and GC-NCI/SRM are suitable for the determination of pesticides in air sample extracts at concentrations ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT). PMID:19609395

  12. Determination of short chain carboxylic acids in vegetable oils and fats using ion exclusion chromatography electrospray ionization mass spectrometry.

    Science.gov (United States)

    Viidanoja, Jyrki

    2015-02-27

    A new method for quantification of short chain C1-C6 carboxylic acids in vegetable oils and fats by employing Liquid Chromatography Mass Spectrometry (LC-MS) has been developed. The method requires minor sample preparation and applies non-conventional Electrospray Ionization (ESI) liquid phase chemistry. Samples are first dissolved in chloroform and then extracted using water that has been spiked with stable isotope labeled internal standards that are used for signal normalization and absolute quantification of selected acids. The analytes are separated using Ion Exclusion Chromatography (IEC) and detected with Electrospray Ionization Mass Spectrometry (ESI-MS) as deprotonated molecules. Prior to ionization the eluent that contains hydrochloric acid is modified post-column to ensure good ionization efficiency of the analytes. The averaged within run precision and between run precision were generally lower than 8%. The accuracy was between 85 and 115% for most of the analytes. The Lower Limit of Quantification (LLOQ) ranged from 0.006 to 7mg/kg. It is shown that this method offers good selectivity in cases where UV detection fails to produce reliable results. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. [Determination of acetanilide herbicide residues in tea by gas chromatography-mass spectrometry with two different ionization techniques].

    Science.gov (United States)

    Shen, Weijian; Xu, Jinzhong; Yang, Wenquan; Shen, Chongyu; Zhao, Zengyun; Ding, Tao; Wu, Bin

    2007-09-01

    An analytical method of solid phase extraction-gas chromatography-mass spectrometry with two different ionization techniques was established for simultaneous determination of 12 acetanilide herbicide residues in tea-leaves. Herbicides were extracted from tea-leaf samples with ethyl acetate. The extract was cleaned-up on an active carbon SPE column connected to a Florisil SPE column. Analytical screening was determined by the technique of gas chromatography (GC)-mass spectrometry (MS) in the selected ion monitoring (SIM) mode with either electron impact ionization (EI) or negative chemical ionization (NCI). It is reliable and stable that the recoveries of all herbicides were in the range from 50% to 110% at three spiked levels, 10 microg/kg, 20 microg/kg and 40 microg/kg, and the relative standard deviations (RSDs) were no more than 10.9%. The two different ionization techniques are complementary as more ion fragmentation information can be obtained from the EI mode while more molecular ion information from the NCI mode. By comparison of the two techniques, the selectivity of NCI-SIM was much better than that of EI-SIM method. The sensitivities of the both techniques were high, the limit of quantitative (LOQ) for each herbicide was no more than 2.0 microg/kg, and the limit of detection (LOD) with NCI-SIM technique was much lower than that of EI-SIM when analyzing herbicides with several halogen atoms in the molecule.

  14. Development of soft ionization using direct current pulse glow discharge plasma source in mass spectrometry for volatile organic compounds analysis

    Science.gov (United States)

    Nunome, Yoko; Kodama, Kenji; Ueki, Yasuaki; Yoshiie, Ryo; Naruse, Ichiro; Wagatsuma, Kazuaki

    2018-01-01

    This study describes an ionization source for mass analysis, consisting of glow discharge plasma driven by a pulsed direct-current voltage for soft plasma ionization, to detect toxic volatile organic compounds (VOCs) rapidly and easily. The novelty of this work is that a molecular adduct ion, in which the parent molecule attaches with an NO+ radical, [M + NO]+, can be dominantly detected as a base peak with little or no fragmentation of them in an ambient air plasma at a pressure of several kPa. Use of ambient air as the discharge plasma gas is suitable for practical applications. The higher pressure in an ambient air discharge provided a stable glow discharge plasma, contributing to the soft ionization of organic molecules. Typical mass spectra of VOCs toluene, benzene, o-xylene, chlorobenzene and n-hexane were observed as [M + NO]+ adduct ion whose peaks were detected at m/z 122, 108, 136, 142 and 116, respectively. The NO generation was also confirmed by emission bands of NO γ-system. The ionization reactions were suggested, such that NO+ radical formed in an ambient air discharge could attach with the analyte molecule.

  15. A new matrix assisted ionization method for the analysis of volatile and nonvolatile compounds by atmospheric probe mass spectrometry.

    Science.gov (United States)

    Chakrabarty, Shubhashis; Pagnotti, Vincent S; Inutan, Ellen D; Trimpin, Sarah; McEwen, Charles N

    2013-07-01

    Matrix assisted ionization of nonvolatile compounds is shown not to be limited to vacuum conditions and does not require a laser. Simply placing a solution of analyte dissolved with a suitable matrix such as 3-nitrobenzonitrile (3-NBN) or 2,5-dihydroxyacetophenone on a melting point tube and gently heating the dried sample near the ion entrance aperture of a mass spectrometer using a flow of gas produces abundant ions of peptides, small proteins, drugs, and polar lipids. Fundamental studies point to matrix-mediated ionization occurring prior to the entrance aperture of the mass spectrometer. The method is analytically useful, producing peptide mass fingerprints of bovine serum albumin tryptic digest consuming sub-picomoles of sample. Application of 100 fmol of angiotensin I in 3-NBN matrix produces the doubly and triply protonated molecular ions as the most abundant peaks in the mass spectrum. No carryover is observed for samples containing up to 100 pmol of this peptide. A commercial atmospheric samples analysis probe provides a simple method for sample introduction to an atmospheric pressure ion source for analysis of volatile and nonvolatile compounds without using the corona discharge but using sample preparation similar to matrix-assisted laser desorption/ionization.

  16. The concerted impact of galaxies and QSOs on the ionization and thermal state of the intergalactic medium

    Science.gov (United States)

    Kakiichi, Koki; Graziani, Luca; Ciardi, Benedetta; Meiksin, Avery; Compostella, Michele; Eide, Marius B.; Zaroubi, Saleem

    2017-07-01

    We present a detailed analysis of the ionization and thermal structure of the intergalactic medium (IGM) around a high-redshift (z = 10) QSO, using a large suite of cosmological, multifrequency radiative transfer simulations, exploring the contribution from galaxies as well as the QSO, and the effect of X-rays and secondary ionization. We show that in high-z QSO environments both the central QSO and the surrounding galaxies concertedly control the reionization morphology of hydrogen and helium and have a non-linear impact on the thermal structure of the IGM. A QSO imprints a distinctive morphology on H II regions if its total ionizing photon budget exceeds that of the surrounding galaxies since the onset of hydrogen reionization; otherwise, the morphology shows little difference from that of H II regions produced only by galaxies. In addition, the spectral shape of the collective radiation field from galaxies and QSOs controls the thickness of the I-fronts. While a UV-obscured QSO can broaden the I-front, the contribution from other UV sources, either galaxies or unobscured QSOs, is sufficient to maintain a sharp I-front. X-ray photons from the QSO are responsible for a prominent extended tail of partial ionization ahead of the I-front. QSOs leave a unique imprint on the morphology of He II/He III regions. We suggest that, while the physical state of the IGM is modified by QSOs, the most direct test to understand the role of galaxies and QSOs during reionization is to perform galaxy surveys in a region of sky imaged by 21 cm tomography.

  17. Laser desorption ionization time-of-flight mass spectrometry of Ge-As-Te chalcogenides.

    Science.gov (United States)

    Šútorová, Katarína; Hawlová, Petra; Prokeš, Lubomír; Němec, Petr; Boidin, Rémi; Havel, Josef

    2015-03-15

    Ge(x)As(y)Te(z) glasses have a broad window of optical transparency and high refractive index which make them promising for applications in the infrared region. The aim of this work is to reveal structural motifs which could be present during the fabrication of Ge-As-Te thin films by plasma deposition techniques; such knowledge is important for the optimization of thin film growth. Mass spectra were acquired using a laser desorption ionization time-of-flight (LDI-TOF) mass spectrometer equipped with a nitrogen laser (337 nm) coupled with a quadrupole ion trap, and recorded in positive and negative ion reflectron modes. XRD, SEM (EDX) and Raman spectroscopy were also used for the characterization of Ge-As-Te bulk or powdered samples. Bulk Ge(x)As(y)Te(z) samples (x = 10-20%, y = 20-60%, z = 30-70%) were synthesized. LDI-MS of Ge-As-Te powders provided evidence for the formation of both positively and negatively charged clusters, whose stoichiometry was determined as Te(n)(+/-) (n = 1-4), Te(5)(+), binary AsTe(n)(+/-) (n = 1-3), GeTe(n)(+/-) (n = 1-3), As(2)Te(+/-), As(2)Te(3)(+), As(3)Te(+), AsTe(4) (+), Ge(2)H(6) (+/-), ternary GeAsTe(+), GeAsTe(2)(+/-), GeAsH5 (+), GeAsH(6)(+), GeAsH(12)(+), and tertiary GeAsTeH(5)(-), GeAsTeH(8)(-), GeAsTe(2)H(3) (+/-). The local structure of Gex Asy Tez materials is at least partly different from that of species identified in plasma by mass spectrometry, as deduced from Raman scattering spectroscopy analysis. However, LDI-TOFMS was found to be a suitable technique for the partial structure characterization of Ge-As-Te bulk samples and especially for the identification of the structural motifs present in the plasma during the preparation of the corresponding thin films. Copyright © 2015 John Wiley & Sons, Ltd.

  18. Analysis of rabbit tear proteins by high-pressure liquid chromatography/electrospray ionization mass spectrometry.

    Science.gov (United States)

    Zhou, Lei; Beuerman, Roger W; Barathi, Amutha; Tan, Donald

    2003-01-01

    The aim of this study was to develop a fast and reliable analytical procedure for the display of the protein components of tears that can be used to differentiate the status of the ocular surface. Using this new procedure, we analyzed the tear protein components following a corneal wound in the rabbit. Calibrated 10-microL glass, fire-polished capillary micropipettes were used to collect tears from New Zealand White rabbits prior to and daily for 9 days following a unilateral 6-mm diameter centrally placed anterior keratectomy. Tear proteins were eluted by a reversed-phase high-performance liquid chromatography (RP-HPLC) column and the tear protein profile was monitored by electrospray ionization (ESI) mass spectrometry positive total ion current (TIC) chromatography. Tear proteins were reliably separated into 17 peaks, each of which contained one or a number of protein components. The molecular weight of each protein component was determined by on-line ESI. Major tear protein components, lactoferrin, lysozyme (minimally detectable in rabbit tears), albumin, lipocalin, lipophilin and beta2-microglobulin, were tentatively identified by this method. Based on the mass spectrometric data, beta2-microglobulin was found to be glycosylated with N-acetylhexosamine. ESI-positive TIC chromatograms and mass spectra revealed comparative differences in the tear protein spectra after corneal wounding. One day after wounding, rabbit lysozyme with a molecular weight of 14,717 Da was found to be 8-fold higher in the tears of wounded eyes when compared with tears from unwounded eyes. It dropped back to normal 3 days after wounding. The expression of an unidentified tear protein with the molecular weight of 16,060 Da was also elevated after corneal wounding and returned to normal level by day 5. In this study, LC/ESI-MS was developed as a fast, reproducible and simple method for the identification and analysis of many of the protein components of the tears. Importantly, this

  19. Enhancing carbohydrate ion yield by controlling crystalline structures in matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Lee, Hsun; Lai, Yin-Hung; Ou, Yu-Meng; Tsao, Chien-Wei; Jheng, Ya-Jin; Kuo, Shu-Yun; Chang, Huan-Tsung; Wang, Yi-Sheng

    2017-11-22

    Carbohydrate analysis is challenging due to lack of sensitive detection and efficient separation methods. Although matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is a sensitive tool, the low ionization efficiency of carbohydrates makes mass analyses inefficient. This work systematically examines the correlation between MALDI-MS sensitivity and carbohydrate sample morphology. Depending on the properties of the matrix used, the morphology changes through sample recrystallization after drying or imposition of hydrodynamic flows during droplet drying. Observation shows that amorphous solids and finer crystals offer higher carbohydrate sensitivity and spatial homogeneity than larger crystals. Clear evidences of an inverse correlation between sensitivity and crystal size are obtained when various kinds of carbohydrates are mixed with different matrixes. Similar experiments on proteins and peptides showed a negative or negligible effect. The result serves as a general guideline for improving efficiency in routine carbohydrate analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Preparation and structural elucidation of the picolinyl ester of aldosterone for liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Yamashita, Kouwa; Tadokoro, Yumiko; Takahashi, Madoka; Numazawa, Mitsuteru

    2008-06-01

    Treatment of aldosterone with 35% HCl in EtOH or in MeOH followed by the picolinyl derivatization gave the picolinyl derivative of aldosterone-ethyl ether, 8, or methyl ether, 9, as a single and well-shaped liquid chromatographic peak. Picolinyl derivatization of aldosterone produced 21-picolinyl derivative of 18,20-anhydro-hemiacetal derivatives, 6, with poor chromatographic peak with wide half-width. Further conversion of 6 to 8 required long reaction time (>4 h). Structure of each picolinyl or alkyl ether-picolinyl derivative, was carefully elucidated by nuclear magnetic resonance spectroscopy, electron ionization mass spectrometry and liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Enhancement of sensitivity (approximately 10-fold) in positive-LC-ESI-MS/MS of aldosterone was confirmed by the use of the alkyl ether-picolinyl derivatization when compared to the underivatized molecule.

  1. Quasi-simultaneous acquisition of hard electron ionization and soft single-photon ionization mass spectra during GC/MS analysis by rapid switching between both ionization methods: analytical concept, setup, and application on diesel fuel.

    Science.gov (United States)

    Eschner, Markus S; Gröger, Thomas M; Horvath, Thomas; Gonin, Marc; Zimmermann, Ralf

    2011-05-15

    This work describes the realization of rapid switching between hard electron ionization (EI) and soft single-photon ionization (SPI) integrated in a compact orthogonal acceleration time-of-flight mass spectrometer. Vacuum-ultraviolet (VUV) photons of 9.8 eV (126 nm) emitted from the innovative electron-beam-pumped rare-gas excimer light source (EBEL) filled with argon are focused into the ion chamber by an ellipsoidal mirror optic for accomplishing of SPI. This novel orthogonal acceleration time-of-flight mass spectrometer with switching capability was hyphenated to one-dimensional gas chromatography (GC) and comprehensive two-dimensional (2D) gas chromatography (GC × GC) for the first time. Within this demonstration study, a maximum switching frequency of 80 Hz was applied for investigation of a mineral-oil-type diesel sample. This approach allows the quasi-simultaneous acquisition of complementary information about the fragmentation pattern (EI) as well as the molecular mass (SPI) of compounds within a single analysis. Furthermore, by application of a polar GC column for separation, the SPI data can be displayed in a 2D contour plot, leading to a comprehensive 2D characterization (GC × MS), whereas the typical group-type assignment for diesel is also met.

  2. Fully Automated Laser Ablation Liquid Capture Sample Analysis using NanoElectrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, Matthias [ORNL; Ovchinnikova, Olga S [ORNL; Van Berkel, Gary J [ORNL

    2014-01-01

    RATIONALE: Laser ablation provides for the possibility of sampling a large variety of surfaces with high spatial resolution. This type of sampling when employed in conjunction with liquid capture followed by nanoelectrospray ionization provides the opportunity for sensitive and prolonged interrogation of samples by mass spectrometry as well as the ability to analyze surfaces not amenable to direct liquid extraction. METHODS: A fully automated, reflection geometry, laser ablation liquid capture spot sampling system was achieved by incorporating appropriate laser fiber optics and a focusing lens into a commercially available, liquid extraction surface analysis (LESA ) ready Advion TriVersa NanoMate system. RESULTS: Under optimized conditions about 10% of laser ablated material could be captured in a droplet positioned vertically over the ablation region using the NanoMate robot controlled pipette. The sampling spot size area with this laser ablation liquid capture surface analysis (LA/LCSA) mode of operation (typically about 120 m x 160 m) was approximately 50 times smaller than that achievable by direct liquid extraction using LESA (ca. 1 mm diameter liquid extraction spot). The set-up was successfully applied for the analysis of ink on glass and paper as well as the endogenous components in Alstroemeria Yellow King flower petals. In a second mode of operation with a comparable sampling spot size, termed laser ablation/LESA , the laser system was used to drill through, penetrate, or otherwise expose material beneath a solvent resistant surface. Once drilled, LESA was effective in sampling soluble material exposed at that location on the surface. CONCLUSIONS: Incorporating the capability for different laser ablation liquid capture spot sampling modes of operation into a LESA ready Advion TriVersa NanoMate enhanced the spot sampling spatial resolution of this device and broadened the surface types amenable to analysis to include absorbent and solvent resistant

  3. Screening of Threading Bis-Intercalators Binding to Duplex DNA by Electrospray Ionization Tandem Mass Spectrometry

    Science.gov (United States)

    Mazzitelli, Carolyn L.; Chu, Yongjun; Reczek, Joseph J.; Iverson, Brent L.

    2007-01-01

    The DNA binding of novel threading bis-intercalators V1, trans-D1, and cis-C1, which contain two naphthalene diimide (NDI) intercalation units connected by a scaffold, was evaluated using electrospray ionization mass spectrometry (ESI-MS) and DNAse footprinting techniques. ESI-MS experiments confirmed that V1, the ligand containing the –Gly3-Lys-peptide scaffold, binds to a DNA duplex containing the 5'-GGTACC-3' specific binding site identified in previous NMR-based studies. The ligand formed complexes with a ligand/DNA binding stoichiometry of 1:1, even when there was excess ligand in solution. Trans-D1 and cis-C1 are new ligands containing a rigid spiro-tricyclic scaffold in the trans- and cis- orientations, respectively. Preliminary DNAse footprinting experiments identified possible specific binding sites of 5'-CAGTGA-5' for trans-D1 and 5'-GGTACC-3' for cis-C1. ESI-MS experiments revealed that both ligands bound to DNA duplexes containing the respective specific binding sequences, with cis-C1 exhibiting the most extensive binding based on a higher fraction of bound DNA value. Cis-C1 formed complexes with a dominant 1:1 binding stoichiometry, whereas trans-D1 was able to form 2:1 complexes at ligand/DNA molar ratios ≥ 1 which is suggestive of non-specific binding. Collisional activated dissociation (CAD) experiments indicate that DNA complexes containing V1, trans-D1, and cis-C1 have a unique fragmentation pathway, which was also observed for complexes containing the commercially available bisintercalator echinomycin, as a result of similar binding interactions, marked by intercalation in addition to hydrogen bonding by the scaffold with the DNA major or minor groove. PMID:17098442

  4. Alkaline liquid chromatography/electrospray ionization skimmer collision-induced dissociation mass spectrometry for phosphopeptide screening.

    Science.gov (United States)

    Beck, A; Deeg, M; Moeschel, K; Schmidt, E K; Schleicher, E D; Voelter, W; Häring, H U; Lehmann, R

    2001-01-01

    A rapid on-line method for the identification of phosphorylated peptides in enzymatic protein digests by specific marker ion signals is described. In our study we investigated the use of alkaline conditions together with a previously described method for selective and sensitive detection of phosphopeptide ions combining high-performance capillary liquid chromatography (LC) and electrospray ionization mass spectrometry (ESI-MS). Phosphorylation-specific marker ions (m/z 79, PO(3)(-), and m/z 97, H(2)PO(4)(-)) were generated by skimmer collision-induced dissociation (sCID) in the negative-ion mode. The method was evaluated and validated for mono-phosphorylated synthetic peptides using different alkaline pH values and CID offsets. Alkaline conditions (pH 10.5) enhance the generation of phosphopeptide-specific fragment ions from serine- and tyrosine-phosphorylated peptides, and enable the use of m/z 79 (PO(3)(-)) and m/z 97 (H(2)PO(4)(-)) as phosphorylation-specific marker traces. Note that HPLC separation in trifluoroacetic acid containing solvents impairs the use of m/z 97 (C(2)F(3)O(-) fragment ion at m/z 97) as a phosphorylation-specific marker. The optimized method was applied for the detection of phosphorylated peptides in a tryptic beta-casein digest. The expected mono- and tetra-phosphorylated peptides were detected and rapidly identified by (mu)LC/ESI-sCID-MS and (mu)LC/ESI-MS analysis. Copyright 2001 John Wiley & Sons, Ltd.

  5. Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)

    Energy Technology Data Exchange (ETDEWEB)

    You, Y.; Kanawade, V. P.; de Gouw, J. A.; Guenther, Alex B.; Madronich, Sasha; Sierra-Hernandez, M. R.; Lawler, M.; Smith, James N.; Takahama, S.; Ruggeri, G.; Koss, A.; Olson, K.; Baumann, K.; Weber, R. J.; Nenes, A.; Guo, H.; Edgerton, Eric S.; Porcelli, L.; Brune, W. H.; Goldstein, Allen H.; Lee, S.-H

    2014-11-19

    We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

  6. Nanoparticle-assisted laser desorption/ionization mass spectrometry: Novel sample preparation methods and nanoparticle screening for plant metabolite imaging

    Energy Technology Data Exchange (ETDEWEB)

    Yagnik, Gargey B. [Iowa State Univ., Ames, IA (United States)

    2016-02-19

    The main goal of the presented research is development of nanoparticle based matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS). This dissertation includes the application of previously developed data acquisition methods, development of novel sample preparation methods, application and comparison of novel nanoparticle matrices, and comparison of two nanoparticle matrix application methods for MALDI-MS and MALDI-MS imaging.

  7. Phosphopeptide detection and sequencing by matrix-assisted laser desorption/ionization quadrupole time-of-flight tandem mass spectrometry

    DEFF Research Database (Denmark)

    Bennett, Keiryn L; Stensballe, Allan; Podtelejnikov, Alexandre V

    2002-01-01

    A prototype matrix-assisted laser desorption/ionization quadrupole time-of-flight (MALDI-TOF) tandem mass spectrometer was used to sequence a series of phosphotyrosine-, phosphothreonine- and phosphoserine-containing peptides. The high mass resolution and mass accuracy of the instrument allowed...... ion at m/z 216.04 was observed in these MALDI low-energy CID tandem mass spectra. Elimination of phosphate groups was evident from the triphosphorylated peptide but not from the monophosphorylated species. The main fragmentation pathway for the synthetic phosphothreonine-containing peptide...... the localization of one, three or four phosphorylated amino acid residues in phosphopeptides up to 3.1 kDa. Tandem mass spectra of two different phosphotyrosine peptides permitted amino acid sequence determination and localization of one and three phosphorylation sites, respectively. The phosphotyrosine immonium...

  8. Real-time analysis of self-assembled nucleobases by Venturi easy ambient sonic-spray ionization mass spectrometry.

    Science.gov (United States)

    Na, Na; Shi, Ruixia; Long, Zi; Lu, Xin; Jiang, Fubin; Ouyang, Jin

    2014-10-01

    In this study, the real-time analysis of self-assembled nucleobases was employed by Venturi easy ambient sonic-spray ionization mass spectrometry (V-EASI-MS). With the analysis of three nucleobases including 6-methyluracil (6MU), uracil (U) and thymine (T) as examples, different orders of clusters centered with different metal ions were recorded in both positive and negative modes. Compared with the results obtained by traditional electrospray ionization mass spectrometry (ESI-MS) under the same condition, more clusters with high orders, such as [6MU7+Na](+), [6MU15+2NH4](2+), [6MU10+Na](+), [T7+Na](+), and [T15+2NH4](2+) were detected by V-EASI-MS, which demonstrated the soft ionization ability of V-EASI for studying the non-covalent interaction in a self-assembly process. Furthermore, with the injection of K(+) to the system by a syringe pumping, the real-time monitoring of the formation of nucleobases clusters was achieved by the direct extraction of samples from the system under the Venturi effect. Therefore, the effect of cations on the formation of clusters during self-assembly of nucleobases was demonstrated, which was in accordance with the reports. Free of high voltage, heating or radiation during the ionization, this technique is much soft and suitable for obtaining the real-time information of the self-assembly system, which also makes it quite convenient for extraction samples from the reaction system. This "easy and soft" ionization technique has provided a potential pathway for monitoring and controlling the self-assembly processes. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Identifying the related compounds using electrospray ionization tandem mass spectrometry: bromotyrosine alkaloids from marine sponge Psammaplysilla purpurea

    Digital Repository Service at National Institute of Oceanography (India)

    Tilvi, S.; DeSouza, L.

    erythrocytes, mouse kidney and fetal calf brain were characterized by matrix-assisted laser desorption/ionisation time-of-flight (MALDI-TOF) MS, liquid secondary ionization mass spectrometry (LSIMS) and MS/MS. 22 Recently, MALDI-MS full scan analysis... sepctrom, 15, 2240 (2001). 22. H. Perreault, X.L. Hronowski, O. Koul, J. Street, R.H. McCluer and C.E. Costello, “High sensitivity mass spectral characterization of glycosphingolipids from bovine erythrocytes, mouse kidney and fetal calf brain”, lnt. J...

  10. Analysis of triazines and associated metabolites with electrospray ionization field-asymmetric ion mobility spectrometry/mass spectrometry

    DEFF Research Database (Denmark)

    Mie, Axel; Sandulescu, Madaline; Mathiasson, Lennart

    2008-01-01

    Triazines comprise an important pollutant class owing to continued use in certain countries, and owing to strong environmental persistence that leads to problems even in countries like Sweden where the use of triazines has been prohibited for some years. We investigated mass-selective detection...... for analysis of triazines. More specifically, we studied the background reduction and sensitivity enhancement that result from the use of a new interface technique, field-asymmetric ion mobility spectrometry (FAIMS), in conjunction with electrospray ionization ion-trap mass spectrometry. This technique allows...

  11. Variational approach to thermal masses in compactified models

    Energy Technology Data Exchange (ETDEWEB)

    Dominici, Daniele [Dipartimento di Fisica e Astronomia Università di Firenze and INFN - Sezione di Firenze,Via G. Sansone 1, 50019 Sesto Fiorentino (Italy); Roditi, Itzhak [Centro Brasileiro de Pesquisas Físicas - CBPF/MCT,Rua Dr. Xavier Sigaud 150, 22290-180, Rio de Janeiro, RJ (Brazil)

    2015-08-20

    We investigate by means of a variational approach the effective potential of a 5DU(1) scalar model at finite temperature and compactified on S{sup 1} and S{sup 1}/Z{sub 2} as well as the corresponding 4D model obtained through a trivial dimensional reduction. We are particularly interested in the behavior of the thermal masses of the scalar field with respect to the Wilson line phase and the results obtained are compared with those coming from a one-loop effective potential calculation. We also explore the nature of the phase transition.

  12. Improvement in ionization efficiency of direct analysis in real time-mass spectrometry (DART-MS) by corona discharge.

    Science.gov (United States)

    Sekimoto, Kanako; Sakakura, Motoshi; Kawamukai, Takatomo; Hike, Hiroshi; Shiota, Teruhisa; Usui, Fumihiko; Bando, Yasuhiko; Takayama, Mitsuo

    2016-08-02

    Herein it is shown that a combination of direct analysis in real time (DART) with a corona discharge system consisting of only a needle electrode easily improves DART ionization efficiency. Positive and negative DC corona discharges led to a formation of abundant excited helium atoms as well as the reactant ions H3O(+)(H2O)n and O2˙(-) in the DART analyte ionization area. These phenomena resulted in an increase in the absolute intensities of (de)protonated analytes by a factor of 2-20 over conventional DART. The other analyte ions detected in this corona-DART system (i.e., molecular ions, fragment ions, oxygenated (de)protonated analytes, dehydrogenated deprotonated analytes, and negative ion adducts) were quite similar to those obtained from DART alone. This indicates a lack of side reactions due to the corona discharge. The change in the relative intensities of individual analyte-related ions due to the combination of a corona discharge system with DART suggests that there is no effect of the abundant excited helium in the analyte ionization area on the fragmentation processes or enhancement of oxidation due to hydroxyl radicals HO˙. Furthermore, it was found that the corona-DART combination can be applied to the highly sensitive analysis of n-alkanes, in which the alkanes are ionized as positive ions via hydride abstraction and oxidation, independent of the type of alkane or the mass spectrometer used.

  13. Rate equation model of laser induced bias in uranium isotope ratios measured by resonance ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Isselhardt, B. H.; Prussin, S. G.; Savina, M. R.; Willingham, D. G.; Knight, K. B.; Hutcheon, I. D.

    2016-01-01

    Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the U-235/U-238 ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the U-235/U-238 ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. Development of this model has highlighted several important considerations for properly interpreting experimental results.

  14. Quantitative Profiling of Major Neutral Lipid Classes in Human Meibum by Direct Infusion Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Chen, Jianzhong; Green, Kari B.; Nichols, Kelly K.

    2013-01-01

    Purpose. The purpose of this investigation was to better understand lipid composition in human meibum. Methods. Intact lipids in meibum samples were detected by direct infusion electrospray ionization mass spectrometry (ESI-MS) analysis in positive detection mode using sodium iodide (NaI) as an additive. The peak intensities of all major types of lipid species, that is, wax esters (WEs), cholesteryl esters (CEs), and diesters (DEs) were corrected for peak overlapping and isotopic distribution; an additional ionization efficiency correction was performed for WEs and CEs, which was simplified by the observation that the corresponding ionization efficiency was primarily dependent on the specific lipid class and saturation degree of the lipids while independent of the carbon chain length. A set of WE and CE standards was spiked in meibum samples for ionization efficiency determination and absolute quantitation. Results. The absolute amount (μmol/mg) for each of 51 WEs and 31 CEs in meibum samples was determined. The summed masses for 51 WEs and 31 CEs accounted for 48 ± 4% and 40 ± 2%, respectively, of the total meibum lipids. The mass percentages of saturated and unsaturated species were determined to be 75 ± 2% and 25 ± 1% for CEs and 14 ± 1% and 86 ± 1% for WEs. The profiles for two types of DEs were also obtained, which include 42 α,ω Type II DEs, and 21 ω Type I-St DEs. Conclusions. Major neutral lipid classes in meibum samples were quantitatively profiled by ESI-MS analysis with NaI additive. PMID:23847307

  15. Gas-phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Mustapha, Adetayo M; Pasilis, Sofie P

    2015-01-01

    Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu(2+) and Ag(+) , however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag(+) or Cu(2+) showed a significant increase in signal-to-background ratio over those acquired from solutions containing only the pesticides, with Ag(+) improving detection more effectively than Cu(2+). Addition of Ag(+) to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag(+) was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag(+)-pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Characteristics of glycation and glycation sites of lysozyme by matrix-assisted laser desorption/ionization time of flight/time-of-flight mass spectrometry and Liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Ruan, Eric Dongliang; Wang, Hui; Ruan, Yuanyuan; Juáreza, Manuel

    2014-01-01

    Protein glycation with reducing sugars through the Maillard reaction is regarded as one of the most important reactions in food chem- istry. Amadori rearrangement products [ARPs] are produced at the initial stage of the Maillard reaction and then advanced glycation products may be formed. We report here that using matrix-assisted laser desorption/ionization mass spectrometry with time-of-flight detection [MALDI-TOF-MS] and electrospray ionization mass spectrometry (ESI-MSJ to monitor the glycation process in lysozyme and the D-glucose model system. MALDI-TOF-MS displayed a heterogeneous distribution of glycation via a total mass shift in spectra. However electrospray ionization mass spectrometry [ESI-MS] data showed that a total of four molecules of glucose reacted with Lysozyme at an increase in molecular weight by a 162 Da unit. Further, we identified the glycation sites of lysozyme by using MALDI-TOF/TOF-MS and Liquid chromatography [LC]-ESI-MS/MS. Besides the two glycation sites of Lys1 and Lys97 identified by MALDI-TOF/TOF-MS, the other two glycation sites of Lys13 and Lys116 were characterized unambiguously by LC-ESI-MS/MS. Both MALDI-TOF/TOF-MS and LC-ESI-MS/ MS provided confidence in the study of the glycation by restricting the number of possible residues through (un]modified ions. The study is useful to monitor and characterize glycation in protein systems based on both MALDI-TOF-MS and ESI-MS. Comparatively, LC-ESI-MS/MS provides more fragments with better recovery for the identification of glycation than MALDI-TOF/TOF-MS.

  17. Pigments and proteins in green bacterial chlorosomes studied by matrix-assisted laser desorption ionization mass spectrometry

    DEFF Research Database (Denmark)

    Persson, S; Sönksen, C P; Frigaard, N-U

    2000-01-01

    We have used matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) for mass determination of pigments and proteins in chlorosomes, the light-harvesting organelles from the photosynthetic green sulfur bacterium Chlorobium tepidum. By applying a small volume (1...... microL) of a concentrated suspension of isolated chlorosomes directly to the target of the mass spectrometer we have been able to detect bacteriochlorophyll a and all the major homologs of bacteriochlorophyll c. The peak heights of the different bacteriochlorophyll c homologs in the MALDI spectra were...... homologs in a small amount of green bacterial cells. In addition to information on pigments, the MALDI spectra also contained peaks from chlorosome proteins. Thus we have been able with high precision to confirm the molecular masses of the chlorosome proteins CsmA and CsmE which have been previously...

  18. Turnover rates in microorganisms by laser ablation electrospray ionization mass spectrometry and pulse-chase analysis

    Energy Technology Data Exchange (ETDEWEB)

    Stopka, Sylwia A.; Mansour, Tarek R.; Shrestha, Bindesh [Department of Chemistry, W.M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington, DC 20052 (United States); Maréchal, Éric; Falconet, Denis [Laboratoire de Physiologie Cellulaire et Végétale, UMR 5168, CEA-CNRS-INRA-Univ. Grenoble Alpes, Grenoble (France); Vertes, Akos, E-mail: vertes@gwu.edu [Department of Chemistry, W.M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington, DC 20052 (United States)

    2016-01-01

    Biochemical processes rely on elaborate networks containing thousands of compounds participating in thousands of reaction. Rapid turnover of diverse metabolites and lipids in an organism is an essential part of homeostasis. It affects energy production and storage, two important processes utilized in bioengineering. Conventional approaches to simultaneously quantify a large number of turnover rates in biological systems are currently not feasible. Here we show that pulse-chase analysis followed by laser ablation electrospray ionization mass spectrometry (LAESI-MS) enable the simultaneous and rapid determination of metabolic turnover rates. The incorporation of ion mobility separation (IMS) allowed an additional dimension of analysis, i.e., the detection and identification of isotopologs based on their collision cross sections. We demonstrated these capabilities by determining metabolite, lipid, and peptide turnover in the photosynthetic green algae, Chlamydomonas reinhardtii, in the presence of {sup 15}N-labeled ammonium chloride as the main nitrogen source. Following the reversal of isotope patterns in the chase phase by LAESI-IMS-MS revealed the turnover rates and half-lives for biochemical species with a wide range of natural concentrations, e.g., chlorophyll metabolites, lipids, and peptides. For example, the half-lives of lyso-DGTS(16:0) and DGTS(18:3/16:0), t{sub 1/2} = 43.6 ± 4.5 h and 47.6 ± 2.2 h, respectively, provided insight into lipid synthesis and degradation in this organism. Within the same experiment, half-lives for chlorophyll a, t{sub 1/2} = 24.1 ± 2.2 h, and a 2.8 kDa peptide, t{sub 1/2} = 10.4 ± 3.6 h, were also determined. - Highlights: • High-throughput pulse-chase analysis using direct sampling of biological cells. • Ion mobility separation for the elucidation of isotopologs. • Identification of isotopologs in difference heat plots of DT vs. m/z. • Simultaneous determination of turnover rates for lipids and

  19. Combined chemical and topographic imaging at atmospheric pressure via microprobe laser desorption/ionization mass spectrometry-atomic force microscopy.

    Science.gov (United States)

    Bradshaw, James A; Ovchinnikova, Olga S; Meyer, Kent A; Goeringer, Douglas E

    2009-12-01

    The operational characteristics and imaging performance are described for a new instrument comprising an atomic force microscope coupled with a pulsed laser and a linear ion trap mass spectrometer. The operating mode of the atomic force microscope is used to produce topographic surface images having sub-micrometer spatial and height resolution. Spatially resolved mass spectra of ions, produced from the same surface via microprobe-mode laser desorption/ionization at atmospheric pressure, are also used to create a 100 x 100 microm chemical image. The effective spatial resolution of the image (approximately 2 microm) was constrained by the limit of detection (estimated to be 10(9)-10(10) molecules) rather than by the diameter of the focused laser spot or the step size of the sample stage. The instrument has the potential to be particularly useful for surface analysis scenarios in which chemical analysis of targeted topographic features is desired; consequently, it should have extensive application in a number of scientific areas. Because the number density of desorbed neutral species in laser desorption/ionization is known to be orders-of-magnitude greater than that of ions, it is expected that improvements in imaging performance can be realized by implementation of post-ionization methods.

  20. Characterization of phenolic compounds in coal tar by gas chromatography/negative-ion atmospheric pressure chemical ionization mass spectrometry.

    Science.gov (United States)

    Ma, Sutian; Ma, Chao; Qian, Kejun; Zhou, Yasong; Shi, Quan

    2016-08-15

    Phenolic compounds are commonly found in fossel fuels and bio-oils, and have a detrimental effect on the chemical stability of the fuels. A selective analytical method is needed to characterize the phenolic compounds in complex hydrocarbon mixtures. Gas chromatography/atmospheric pressure chemical ionization mass spectrometry (GC/APCI-MS) was used to characterize the phenolic compounds in a low-temperature coal tar and its narrow distillate fractions. Negative-ion APCI selectively ionized phenolic compounds in the coal tar. The [M-H](-) and [M-H + O](-) ions were derived from monohydric phenols, while [M-H](-) , [M-2H](-) , and [M-2H + O](-) were from benzenediols. Monohydric phenolic compounds with 1-4 aromatic rings and some dihydric phenolic compounds were identified. The results from GC/APCI-MS were validated by those from negative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICRMS). Negative-ion GC/APCI-MS was proposed and successfully used to characterize phenolic compounds in coal tar samples. This technique can potentially be used for the characterization of phenolic compounds in other complex hydrocarbon systems. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Ionization-based detectors for gas chromatography.

    Science.gov (United States)

    Poole, Colin F

    2015-11-20

    The gas phase ionization detectors are the most widely used detectors for gas chromatography. The column and makeup gases commonly used in gas chromatography are near perfect insulators. This facilitates the detection of a minute number of charge carriers facilitating the use of ionization mechanisms of low efficiency while providing high sensitivity. The main ionization mechanism discussed in this report are combustion in a hydrogen diffusion flame (flame ionization detector), surface ionization in a plasma (thermionic ionization detector), photon ionization (photoionization detector and pulsed discharge helium ionization detector), attachment of thermal electrons (electron-capture detector), and ionization by collision with metastable helium species (helium ionization detector). The design, response characteristics, response mechanism, and suitability for fast gas chromatography are the main features summarized in this report. Mass spectrometric detection and atomic emission detection, which could be considered as ionization detectors of a more sophisticated and complex design, are not discussed in this report. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Desorption/Ionization Fluence Thresholds and Improved Mass Spectral Consistency Measured Using a Flattop Laser Profile in the Bioaerosol Mass Spectrometry of Single Bacillus Endospores

    Energy Technology Data Exchange (ETDEWEB)

    Steele, P T; Srivastava, A; Pitesky, M E; Fergenson, D P; Tobias, H J; Gard, E E; Frank, M

    2004-11-30

    Bioaerosol mass spectrometry (BAMS) is being developed to analyze and identify biological aerosols in real-time. Mass spectra of individual Bacillus endospores were measured here with a bipolar aerosol time-of-flight mass spectrometer in which molecular desorption and ionization were produced using a single laser pulse from a Q-switched, frequency-quadrupled Nd:YAG laser that was modified to have an approximately flattop profile. The flattened laser profile allowed the minimum fluence required to desorb and ionize significant numbers of ions from single aerosol particles to be determined. For Bacillus spores this threshold had a mean value of approximately 1 nJ/{micro}m{sup 2} (0.1 J/cm{sup 2}). Thresholds for individual spores, however, could apparently deviate by 20% or more from the mean. Threshold distributions for clumps of MS2 bacteriophage and bovine serum albumin were subsequently determined. Finally, the flattened profile was observed to increase the reproducibility of single spore mass spectra. This is consistent with the general conclusions of our earlier paper on the fluence dependence of single spore mass spectra and is particularly significant because it is expected to enable more robust differentiation and identification of single bioaerosol particles.

  3. Observation of different ceramide species from crude cellular extracts by normal-phase high-performance liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry

    NARCIS (Netherlands)

    Pettus, BJ; Bielawska, A; Kroesen, BJ; Moeller, PDR; Szulc, ZM; Hannun, YA; Busman, M

    2003-01-01

    Normal-phase high-performance liquid chromatography (NP-HPLC) coupled to atmospheric pressure chemical ionization mass spectrometry (APCI-MS) allows qualitative analysis of endogenous ceramide and dihydroceramide species from crude lipid extracts utilizing chromatographic methods readily adaptable

  4. The value of total protein in guiding management of infectious parapneumonic effusion by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    National Research Council Canada - National Science Library

    Chiu, Chih-Yung; Hsieh, Sen-Yung; Wong, Kin-Sun; Lai, Shen-Hao; Chen, Jen-Kun; Huang, Jing-Long

    2015-01-01

    .... The purpose of this study was to investigate the value of total protein analysis in guiding management of infectious PE by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry...

  5. Laser desorption/ionization mass spectrometry for direct profiling and imaging of small molecules from raw biological materials

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Sangwon [Iowa State Univ., Ames, IA (United States)

    2008-01-01

    Matrix-assisted laser desorption/ionization(MALDI) mass spectrometry(MS) has been widely used for analysis of biological molecules, especially macromolecules such as proteins. However, MALDI MS has a problem in small molecule (less than 1 kDa) analysis because of the signal saturation by organic matrixes in the low mass region. In imaging MS (IMS), inhomogeneous surface formation due to the co-crystallization process by organic MALDI matrixes limits the spatial resolution of the mass spectral image. Therefore, to make laser desorption/ionization (LDI) MS more suitable for mass spectral profiling and imaging of small molecules directly from raw biological tissues, LDI MS protocols with various alternative assisting materials were developed and applied to many biological systems of interest. Colloidal graphite was used as a matrix for IMS of small molecules for the first time and methodologies for analyses of small metabolites in rat brain tissues, fruits, and plant tissues were developed. With rat brain tissues, the signal enhancement for cerebroside species by colloidal graphite was observed and images of cerebrosides were successfully generated by IMS. In addition, separation of isobaric lipid ions was performed by imaging tandem MS. Directly from Arabidopsis flowers, flavonoids were successfully profiled and heterogeneous distribution of flavonoids in petals was observed for the first time by graphite-assisted LDI(GALDI) IMS.

  6. Detection of Metastatic Breast and Thyroid Cancer in Lymph Nodes by Desorption Electrospray Ionization Mass Spectrometry Imaging

    Science.gov (United States)

    Zhang, Jialing; Feider, Clara L.; Nagi, Chandandeep; Yu, Wendong; Carter, Stacey A.; Suliburk, James; Cao, Hop S. Tran; Eberlin, Livia S.

    2017-06-01

    Ambient ionization mass spectrometry has been widely applied to image lipids and metabolites in primary cancer tissues with the purpose of detecting and understanding metabolic changes associated with cancer development and progression. Here, we report the use of desorption electrospray ionization mass spectrometry (DESI-MS) to image metastatic breast and thyroid cancer in human lymph node tissues. Our results show clear alterations in lipid and metabolite distributions detected in the mass spectra profiles from 42 samples of metastatic thyroid tumors, metastatic breast tumors, and normal lymph node tissues. 2D DESI-MS ion images of selected molecular species allowed discrimination and visualization of specific histologic features within tissue sections, including regions of metastatic cancer, adjacent normal lymph node, and fibrosis or adipose tissues, which strongly correlated with pathologic findings. In thyroid cancer metastasis, increased relative abundances of ceramides and glycerophosphoinisitols were observed. In breast cancer metastasis, increased relative abundances of various fatty acids and specific glycerophospholipids were seen. Trends in the alterations in fatty acyl chain composition of lipid species were also observed through detailed mass spectra evaluation and chemical identification of molecular species. The results obtained demonstrate DESI-MSI as a potential clinical tool for the detection of breast and thyroid cancer metastasis in lymph nodes, although further validation is needed. [Figure not available: see fulltext.

  7. Rapid on-site detection of explosives on surfaces by ambient pressure laser desorption and direct inlet single photon ionization or chemical ionization mass spectrometry.

    Science.gov (United States)

    Ehlert, S; Hölzer, J; Rittgen, J; Pütz, M; Schulte-Ladbeck, R; Zimmermann, R

    2013-09-01

    Considering current security issues, powerful tools for detection of security-relevant substances such as traces of explosives and drugs/drug precursors related to clandestine laboratories are required. Especially in the field of detection of explosives and improvised explosive devices, several relevant compounds exhibit a very low vapor pressure. Ambient pressure laser desorption is proposed to make these substances available in the gas phase for the detection by adapted mass spectrometers or in the future with ion-mobility spectrometry as well. In contrast to the state-of-the-art thermal desorption approach, by which the sample surface is probed for explosive traces by a wipe pad being transferred to a thermal desorber unit, by the ambient pressure laser desorption approach presented here, the sample is directly shockwave ablated from the surface. The laser-dispersed molecules are sampled by a heated sniffing capillary located in the vicinity of the ablation spot into the mass analyzer. This approach has the advantage that the target molecules are dispersed more gently than in a thermal desorber unit where the analyte molecules may be decomposed by the thermal intake. In the technical realization, the sampling capillary as well as the laser desorption optics are integrated in the tip of an endoscopic probe or a handheld sampling module. Laboratory as well as field test scenarios were performed, partially in cooperation with the Federal Criminal Police Office (Bundeskriminalamt, BKA, Wiesbaden, Germany), in order to demonstrate the applicability for various explosives, drugs, and drug precursors. In this work, we concentrate on the detection of explosives. A wide range of samples and matrices have been investigated successfully.

  8. Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures – Application to the petroleomic analysis of bio-oils

    Energy Technology Data Exchange (ETDEWEB)

    Hertzog, Jasmine [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Carré, Vincent, E-mail: vincent.carre@univ-lorraine.fr [LCP-A2MC, FR 2843 Institut Jean Barriol de Chimie et Physique Moléculaires et Biomoléculaires, FR 3624 Réseau National de Spectrométrie de Masse FT-ICR à très haut champ, Université de Lorraine, ICPM, 1 boulevard Arago, 57078 Metz Cedex 03 (France); Le Brech, Yann [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mackay, Colin Logan [SIRCAMS, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, Scotland (United Kingdom); Dufour, Anthony [LRGP, CNRS, Université de Lorraine, ENSIC, 1, Rue Grandville, 54000 Nancy (France); Mašek, Ondřej [UK Biochar Research Center, School of Geosciences, University of Edinburgh, Kings Buildings, Edinburgh, EH9 3JN (United Kingdom); and others

    2017-05-29

    The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C{sub x}H{sub y}O{sub z} with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. - Highlights: • Non-targeted mass spectrometry by combining electrospray ionization, atmospheric pressure photoionization and laser/desorption ionization. • Exhaustive description of pyrolytic bio-oil components. • Distinction of sugaric derivatives, lignin derivatives and lipids contained in a woody-based pyrolytic bio-oil.

  9. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

    Energy Technology Data Exchange (ETDEWEB)

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.

    2011-04-28

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm{sup 2}V{sup -1}s{sup -1} across the temperature range from 60 to 140 C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

  10. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization.

    Science.gov (United States)

    Ewing, Robert G; Waltman, Melanie J; Atkinson, David A

    2011-06-15

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm(2)V(-1)s(-1) across the temperature range from 60 to 140 °C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 °C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

  11. CEPH family 1362 STR database: an online resource for characterization of PCR products using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Null, Allison P; Muddima, David C

    2002-01-01

    An online database has been established in order to validate electrospray ionization mass spectrometry (ESI-MS) for genotyping and to publicize the procedures developed in our laboratory for the characterization of PCR products by ESI-MS. Genotypes derived from short tandem repeat (STR) loci that were obtained using ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) have been posted for fifteen members of the CEPH family 1362 pedigree. The website provides specific information such as PCR parameters, PCR product cleanup approaches, and ESI solution compositions to enable other laboratories to reproduce our data. Links are provided to related websites in an effort to integrate information regarding the CEPH family, STR genotyping, and mass spectrometry. The database, currently available at http://www.people.vcu.edu/ -dcmuddim/genotype/ will be routinely updated with genotypes from additional STR loci including PCR parameters as well as PCR cleanup strategies as further developments are completed.

  12. Characterization of unknown compounds from stainless steel plates in matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Yang, Hyo-Jik; Park, Kyu Hwan; Kim, Hyun Sik; Kim, Jeongkwon

    2010-12-01

    Peaks originating from unknown compounds on stainless steel plates used in matrix-assisted laser desorption/ionization (MALDI) mass spectrometers are observed around m/z 304.3, 332.3, 360.4, and 388.4 regardless of the matrix and/or solvent, and are even observed with bare plates. These peaks were characterized using three different types of MALDI-MS instrumentation: MALDI-TOF MS, MALDI-TOF/TOF MS, and MALDI-FTMS. The fragmentation data from MALDI-TOF/TOF MS and accurate mass determination by MALDI-FTMS enabled identification of the chemical formulae and structures. The unknown compounds are, in fact, likely benzylalkylmethylammonium salts, as confirmed by closely matching fragmentation patterns with a commercially available benzalkonium chloride. Copyright © 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

  13. High performance electrospray ionization mass spectrometry in the study of the noncovalent associations of proteins and DNA

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R.D.; Hofstadler, S.A.; Bruce, J.A. [Pacific Northwest Lab., Richland, WA (United States)] [and others

    1995-12-01

    The ability to study the non-covalent associations of biopolymers under near physiological conditions using electrospray ionization-mass spectrometry has opened new opportunities for the study of a range of crucial biological processes. The use of new instrumentation based upon Fourier transform ion cyclotron resonance mass spectrometry will also be presented, and shown to open new opportunities and applications based upon improved resolution, sensitivity, and extended multi-dimensional mass spectrometric capabilities. In this presentation, studies showing the broad utility of ESI-MS for studies of binding and stoichiometry of biomolecular structure and interactions will be presented. The conditions under which quantitative data can be obtained in such studies will be discussed. Systems described will include protein quaternary structure, protein-protein complexes of relevance to DNA repair, oligonucleotide duplexes and quadruplexes, and the interaction of smaller molecules with these biopolymers (e.g., protein inhibitors).

  14. Characterization of organic aerosol in Beijing by laser desorption ionization coupled with Fourier Transform Ion Cyclotron Resonance Mass spectrometry

    Science.gov (United States)

    Xue, Jinjuan; Li, Yafeng; Xie, Xiaobo; Xiong, Caiqiao; Liu, Huihui; Chen, Suming; Nie, Zongxiu; Chen, Chuncheng; Zhao, Jincai

    2017-06-01

    In order to resolve the organic compositions in the atmospheric aerosol which is significant for understanding the formation mechanism of particulate matter and their harm for human health, a direct laser desorption ionization (LDI) coupled with Fourier Transform Resonance Mass (FT-ICR MS) was utilized for characterizing the aerosol particles collected in Beijing during winter. A lot of organic compounds can be detected by direct laser desorption ionization of the aerosol particular with different size collected on aluminum foil without complicated sample pretreatment process. In addition, semi quantification of the organic compounds can be achieved with solvent extraction procedure. It was found that the ubiquitous polycyclic aromatic hydrocarbons (PAHs) contaminants in the aerosol could serve as matrix, which helps the detection of many kinds of compounds including highly saturated amphiphilic long alkyl chain compounds (carbon number>16), like aliphatic amines in positive ion mode and organosulfates in negative ion mode. Based on the accurate mass measurement results, elemental compositions of over 1500 peaks in the mass spectrum were derived, and we categorized them into five groups according to their elemental compositions in order to provide helpful information for tracing the pollution source. It is demonstrated that abundant information about the organic components in the atmospheric aerosol can be provided by direct LDI FT-ICR MS method, and these information will largely facilitate further studies on origin and formation process of the aerosol.

  15. Direct Visualization of Neurotransmitters in Rat Brain Slices by Desorption Electrospray Ionization Mass Spectrometry Imaging (DESI - MS)

    Science.gov (United States)

    Fernandes, Anna Maria A. P.; Vendramini, Pedro H.; Galaverna, Renan; Schwab, Nicolas V.; Alberici, Luciane C.; Augusti, Rodinei; Castilho, Roger F.; Eberlin, Marcos N.

    2016-12-01

    Mass spectrometry imaging (MSI) of neurotransmitters has so far been mainly performed by matrix-assisted laser desorption/ionization (MALDI) where derivatization reagents, deuterated matrix and/or high resolution, or tandem MS have been applied to circumvent problems with interfering ion peaks from matrix and from isobaric species. We herein describe the application of desorption electrospray ionization mass spectrometry imaging (DESI)-MSI in rat brain coronal and sagittal slices for direct spatial monitoring of neurotransmitters and choline with no need of derivatization reagents and/or deuterated materials. The amino acids γ-aminobutyric (GABA), glutamate, aspartate, serine, as well as acetylcholine, dopamine, and choline were successfully imaged using a commercial DESI source coupled to a hybrid quadrupole-Orbitrap mass spectrometer. The spatial distribution of the analyzed compounds in different brain regions was determined. We conclude that the ambient matrix-free DESI-MSI is suitable for neurotransmitter imaging and could be applied in studies that involve evaluation of imbalances in neurotransmitters levels.

  16. Preparation of porous n-type silicon sample plates for desorption/ionization on silicon mass spectrometry (DIOS-MS).

    Science.gov (United States)

    Tuomikoski, S; Huikko, K; Grigoras, K; Ostman, P; Kostiainen, R; Baumann, M; Abian, J; Kotiaho, T; Franssila, S

    2002-11-01

    This study focuses on porous silicon (pSi) fabrication methods and properties for desorption ionization on silicon mass spectrometry (DIOS-MS). PSi was prepared using electrochemical etching of n-type silicon in HF-ethanol solution. Porous areas were defined by a double-sided illumination arrangement: front-side porous areas were masked by a stencil mask, eliminating the need for standard photolithography, and backside illumination was used for the backside ohmic contact. Backside illumination improved the uniformity of the porosified areas. Porosification conditions, surface derivatizations and storage conditions were explored to optimize pSi area, pore size and pore depth. Chemical derivatization of the pSi surfaces improved the DIOS-MS performance providing better ionization efficiency and signal stability with lower laser energy. Droplet spreading and drying patterns on pSi were also examined. Pore sizes of 50-200 nm were found to be optimal for droplet evaporation and pore filling with the sample liquid, as measured by DIOS efficiency. With DIOS, significantly better detection sensitivity was obtained (e.g. 150 fmol for midazolam) than with desorption ionization from a standard MALDI steel plate without matrix addition (30 pmol for midazolam). Also the noise that disturbs the detection of low-molecular weight compounds at m/z MS spectra and good detection sensitivity at the 100-150 fmol level for pharmaceutical compounds were achieved with DIOS-MS.

  17. Electrostatic Spray Ionization from 384-Well Microtiter Plates for Mass Spectrometry Analysis-Based Enzyme Assay and Drug Metabolism Screening.

    Science.gov (United States)

    Qiao, Liang; Zhong, Xiaoqin; Belghith, Emna; Deng, Yan; Lin, Tzu-En; Tobolkina, Elena; Liu, Baohong; Girault, Hubert H

    2017-06-06

    We have realized the direct ionization of samples from wells of microtiter plates under atmospheric conditions for mass spectrometry analysis without any liquid delivery system or any additional interface. The microtiter plate is a commercially available 384-well plate without any modification, working as a container and an emitter for electrostatic spray ionization of analytes. The approach provides high throughput for the large batches of reactions and both the qualitative and quantitative analysis of a single compound or mixture. The limits of detection in small drug molecules, peptides, and proteins are similar in comparison with standard direct infusion electrospray ionization. The analysis time per well is only seconds. These analytical merits benefit many microtiter plate-based studies, such as combinatorial chemistry and high throughput screening in enzyme assay or drug metabolism. Herein, we illustrate the application in enzyme assay using tyrosine oxidation catalyzed by tyrosinase in the presence or absence of inhibitors. The potential application in drug development is also demonstrated with cytochrome P450-catalyzed metabolic reactions of two drugs in microtiter plates followed with direct ESTASI-MS/MS-based characterization of the metabolism products.

  18. Ambient mass spectrometry: Direct analysis of dimethoate, tebuconazole, and trifloxystrobin on olive and vine leaves by desorption electrospray ionization interface.

    Science.gov (United States)

    Mainero Rocca, Lucia; Cecca, Juri; L'Episcopo, Nunziata; Fabrizi, Giovanni

    2017-11-01

    A new field of application for a relatively new mass-spectrometric interface such as desorption electrospray ionization was evaluated. For this purpose, its behavior was tested versus quantitative analysis of dimethoate, trifloxystrobin, and tebuconazole directly on olive and vine leaves surface. The goal was workers exposure assessment during field re-entry operations since evidence suggests an association between chronic occupational exposure to some agrochemicals and severe adverse effects. Desorption electrospray ionization gave good response working in positive ionization mode, while numerous test were necessary for the choice of a unique blend of spray solvents suitable for all 3 substances. The best compromise, in terms of signal to noise ratios, was obtained with the CH3 OH/H2 O (80:20) mixture. The obvious difficulties related to the impossibility to use the internal standard were overcome through an accurate validation. Limits of detection and quantitation, dynamic ranges, matrix effects, and intraday precisions were calculated, and a small monitoring campaign was arranged to test method applicability and to evaluate potential dermal exposure. This protocol was developed in work safety field, but after a brief investigation, it was find to be suitable also for food residue evaluation. Copyright © 2017 John Wiley & Sons, Ltd.

  19. Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

    Science.gov (United States)

    van Bavel, Bert; Geng, Dawei; Cherta, Laura; Nácher-Mestre, Jaime; Portolés, Tania; Ábalos, Manuela; Sauló, Jordi; Abad, Esteban; Dunstan, Jody; Jones, Rhys; Kotz, Alexander; Winterhalter, Helmut; Malisch, Rainer; Traag, Wim; Hagberg, Jessika; Ericson Jogsten, Ingrid; Beltran, Joaquim; Hernández, Félix

    2015-09-01

    The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is

  20. Non-thermal near-infrared exposure photobiomodulates cellular responses to ionizing radiation in human full thickness skin models.

    Science.gov (United States)

    König, Anke; Zöller, Nadja; Kippenberger, Stefan; Bernd, August; Kaufmann, Roland; Layer, Paul G; Heselich, Anja

    2018-01-01

    Ionizing and near-infrared radiation are both part of the therapeutic spectrum in cancer treatment. During cancer therapy ionizing radiation is typically used for non-invasive reduction of malignant tissue, while near-infrared photobiomodulation is utilized in palliative medical approaches, e.g. for pain reduction or impairment of wound healing. Furthermore, near-infrared is part of the solar wavelength spectrum. A combined exposure of these two irradiation qualities - either intentionally during medical treatment or unintentionally due to solar exposure - is therefore presumable for cancer patients. Several studies in different model organisms and cell cultures show a strong impact of near-infrared pretreatment on ionizing radiation-induced stress response. To investigate the risks of non-thermal near-infrared (NIR) pretreatment in patients, a human in vitro full thickness skin models (FTSM) was evaluated for radiation research. FTSM were pretreated with therapy-relevant doses of NIR followed by X-radiation, and then examined for DNA-double-strand break (DSB) repair, cell proliferation and apoptosis. Double-treated FTSM revealed a clear influence of NIR on X-radiation-induced stress responses in cells in their typical tissue environment. Furthermore, over a 24h time period, double-treated FTSM presented a significant persistence of DSBs, as compared to samples exclusively irradiated by X-rays. In addition, NIR pretreatment inhibited apoptosis induction of integrated fibroblasts, and counteracted the radiation-induced proliferation inhibition of basal keratinocytes. Our work suggests that cancer patients treated with X-rays should be prevented from uncontrolled NIR irradiation. On the other hand, controlled double-treatment could provide an alternative therapy approach, exposing the patient to less radiation. Copyright © 2017. Published by Elsevier B.V.

  1. New Results from the Search for Low-Mass Weakly Interacting Massive Particles with the CDMS Low Ionization Threshold Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Agnese, R.; Anderson, A. J.; Aramaki, T.; Asai, M.; Baker, W.; Balakishiyeva, D.; Barker, D.; Basu Thakur, R.; Bauer, D. A.; Billard, J.; Borgland, A.; Bowles, M. A.; Brink, P. L.; Bunker, R.; Cabrera, B.; Caldwell, D. O.; Calkins, R.; Cerdeno, D. G.; Chagani, H.; Chen, Y.; Cooley, J.; Cornell, B.; Cushman, P.; Daal, M.; Di Stefano, P. C. F.; Doughty, T.; Esteban, L.; Fallows, S.; Figueroa-Feliciano, E.; Ghaith, M.; Godfrey, G. L.; Golwala, S. R.; Hall, J.; Harris, H. R.; Hofer, T.; Holmgren, D.; Hsu, L.; Huber, M. E.; Jardin, D.; Jastram, A.; Kamaev, O.; Kara, B.; Kelsey, M. H.; Kennedy, A.; Leder, A.; Loer, B.; Lopez Asamar, E.; Lukens, P.; Mahapatra, R.; Mandic, V.; Mast, N.; Mirabolfathi, N.; Moffatt, R. A.; Morales Mendoza, J. D.; Oser, S. M.; Page, K.; Page, W. A.; Partridge, R.; Pepin, M.; Phipps, A.; Prasad, K.; Pyle, M.; Qiu, H.; Rau, W.; Redl, P.; Reisetter, A.; Ricci, Y.; Roberts, A.; Rogers, H. E.; Saab, T.; Sadoulet, B.; Sander, J.; Schneck, K.; Schnee, R. W.; Scorza, S.; Serfass, B.; Shank, B.; Speller, D.; Toback, D.; Underwood, R.; Upadhyayula, S.; Villano, A. N.; Welliver, B.; Wilson, J. S.; Wright, D. H.; Yellin, S.; Yen, J. J.; Young, B. A.; Zhang, J.

    2016-02-01

    The CDMS low ionization threshold experiment (CDMSlite) uses cryogenic germanium detectors operated at a relatively high bias voltage to amplify the phonon signal in the search for weakly interacting massive particles (WIMPs). Results are presented from the second CDMSlite run with an exposure of 70 kg day, which reached an energy threshold for electron recoils as low as 56 eV. A fiducialization cut reduces backgrounds below those previously reported by CDMSlite. New parameter space for the WIMP-nucleon spin-independent cross section is excluded for WIMP masses between 1.6 and 5.5 GeV/c^2.

  2. Detection and mapping of Cannabinoids in single hair samples through rapid derivatization- Matrix-Assisted Laser Desorption Ionization Mass Spectrometry

    OpenAIRE

    Beasley, Emma; Francese, Simona; Bassindale, Thomas

    2016-01-01

    The sample preparation method reported in this work has permitted for the first time the application of Matrix Assisted Laser Desorption Ionization Mass Spectrometry Profiling and Imaging (MALDI-MSP and MALDI-MSI) for the detection and mapping of cannabinoids in a single hair sample. MALDI-MSI analysis of hair samples has recently been suggested as an alternative technique to traditional methods of GC-MS and LC-MS due to simpler sample preparation, the ability to detect a narrower time frame ...

  3. On-chip electromembrane extraction for monitoring drug metabolism in real time by electrospray ionization mass spectrometry

    DEFF Research Database (Denmark)

    Petersen, Nickolaj J.; Pedersen, Jacob Sønderby; Poulsen, Nicklas Nørgård

    2012-01-01

    changes in the reaction chamber were continuously detected 9 seconds later in the MS. Most of this time delay was due to transport of the purified extract towards the ESI source. The EME step effectively removed the enzymatic material, buffer and salts from the reaction mixture, and prevented......A temperature controlled (37 °C) metabolic reaction chamber with a volume of 1 mL was coupled directly to electrospray ionization mass spectrometry (ESI-MS) by the use of a 50 µm deep counter flow micro-chip electromembrane extraction (EME) system. The EME/ESI-MS system was used to study...

  4. Species identification of clinical Prevotella isolates by matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    Science.gov (United States)

    Wybo, Ingrid; Soetens, Oriane; De Bel, Annelies; Echahidi, Fedoua; Vancutsem, Ellen; Vandoorslaer, Kristof; Piérard, Denis

    2012-04-01

    The performance of matrix-assisted laser desorption-ionization time of flight mass spectrometry (MALDI-TOF MS) for species identification of Prevotella was evaluated and compared with 16S rRNA gene sequencing. Using a Bruker database, 62.7% of the 102 clinical isolates were identified to the species level and 73.5% to the genus level. Extension of the commercial database improved these figures to, respectively, 83.3% and 89.2%. MALDI-TOF MS identification of Prevotella is reliable but needs a more extensive database.

  5. Identification of Ceftiofur Oxidation Products by High-Performance Liquid Chromatography/Electrospray Ionization/Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Hye-Sung Cho

    2011-03-01

    Full Text Available Oxidation products of ceftiofur were formed in hydrogen peroxide solution. The structures of the ceftiofur oxidationproducts were characterized by high-performance liquid chromatography/electrospray ionization/tandem mass spectrometry(HPLC/ESI/MS/MS. The products were identified as compounds oxidized at the sulfur of a cephem ring. For further analysis,experiments were performed using O18-labeled hydrogen peroxide. In addition, density-functional calculations were carried out forsix possible oxidation products to support the experimental results.

  6. Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry applied to virus identification

    OpenAIRE

    Calderaro, Adriana; Arcangeletti, Maria-Cristina; Rodighiero, Isabella; Buttrini, Mirko; Gorrini, Chiara; Motta, Federica; Germini, Diego; Medici, Maria-Cristina; Chezzi, Carlo; De Conto, Flora

    2014-01-01

    Virus detection and/or identification traditionally rely on methods based on cell culture, electron microscopy and antigen or nucleic acid detection. These techniques are good, but often expensive and/or time-consuming; furthermore, they not always lead to virus identification at the species and/or type level. In this study, Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS) was tested as an innovative tool to identify human polioviruses and to identif...

  7. Ultratrace analysis and isotope ratio measurements of long-lived radioisotopes by resonance ionization mass spectrometry (RIMS).

    Science.gov (United States)

    Trautmann, N; Passler, G; Wendt, K D A

    2004-01-01

    Resonance Ionization Mass Spectrometry (RIMS) is a sensitive and selective method for ultratrace analysis of long-lived radioisotopes and isotope ratio measurements. It provides extremely high isobaric suppression and good overall efficiency. The experimental limits of detection are as low as 10(6) atoms per sample and isotopic selectivities of 5x10(12) have been obtained. The widespread potential of RIMS, using different experimental arrangements, is demonstrated for the determination of the radiotoxic isotopes Pu-238 to Pu-244 and Sr-89/Sr-90 in various environmental samples as well as for Ca-41 in nuclear reactor components and biomedical samples.

  8. Detection of methamphetamine and amphetamine in a single human hair by gas chromatography/chemical ionization mass spectrometry.

    Science.gov (United States)

    Suzuki, O; Hattori, H; Asano, M

    1984-04-01

    A detailed procedure of an extremely sensitive method for quantitation of methamphetamine and amphetamine in human hair by gas chromatography (GC)/chemical ionization (CI) mass spectrometry (MS) is presented. N-methylbenzylamine was used as an internal standard. The samples, after extraction with an organic solvent, were derivatized with trifluoroacetic anhydride before the GC/MS analysis. Quantitation was made with quasi-molecular ions of the derivatives by selected ion monitoring in the CI mode. The detection limit was about 10 pg in an injected volume. The high sensitivity enabled us to measure both stimulants in a single human hair in actual cases.

  9. Laser desorption ionization mass spectrometry of peptides on a hybrid CHCA organic-inorganic matrix.

    Science.gov (United States)

    Fleith, Clément; Cantel, Sonia; Subra, Gilles; Mehdi, Ahmad; Ciccione, Jeremie; Martinez, Jean; Enjalbal, Christine

    2014-08-07

    We report applications of new hybrid organic-inorganic silica based materials as laser desorption/ionization (LDI)-promoting surfaces for high-throughput identification of peptides. The driving force of our work was to design a new material composed of a conventional MALDI matrix covalently attached to silica with a high organic/inorganic ratio in order to improve the UV absorption by such LDI hybrid matrices. Amorphous CHCA-functionalized silica presenting an organic content up to 1.3 mmol g(-1) (around 40% in weight from TGA and elementary analysis measurements) gave very interesting LDI performances in terms of detection sensitivity as well as relative ionization discrepancy (spectral suppression) through the analyses of small synthetic peptide mixtures (550-1300 Da) taking CHCA and amorphous silica as model matrices for control experiments.

  10. Application of pyrolysis–mass spectrometry and pyrolysis–gas chromatography–mass spectrometry with electron-ionization or resonance-enhanced-multi-photon ionization for characterization of crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Otto, Stefan [Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock (Germany); Streibel, Thorsten, E-mail: thorsten.streibel@uni-rostock.de [Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock (Germany); Joint Mass Spectrometry Centre, Cooperation Group Comprehensive Molecular Analytics, Institute of Ecological Chemistry, Helmholtz Zentrum München-German Research Center of Environmental Health (GmbH), Ingolstädter Landstrasse 1, 85764 Neuherberg (Germany); Erdmann, Sabrina [Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock (Germany); Sklorz, Martin [Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock (Germany); Joint Mass Spectrometry Centre, Cooperation Group Comprehensive Molecular Analytics, Institute of Ecological Chemistry, Helmholtz Zentrum München-German Research Center of Environmental Health (GmbH), Ingolstädter Landstrasse 1, 85764 Neuherberg (Germany); Schulz-Bull, Detlef [Marine Chemistry, Leibniz Institute for Baltic Sea Research, Warnemünde, Seestrasse 15, 18119 Rostock (Germany); Zimmermann, Ralf [Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock (Germany); Joint Mass Spectrometry Centre, Cooperation Group Comprehensive Molecular Analytics, Institute of Ecological Chemistry, Helmholtz Zentrum München-German Research Center of Environmental Health (GmbH), Ingolstädter Landstrasse 1, 85764 Neuherberg (Germany)

    2015-01-15

    Highlights: • Gas chromatography setup with two MS detectors applying different ionization methods. • In parallel structural information and sensitive detection of aromatic species. • Characterization of setup and application for crude oil samples. • Detection of polycyclic aromatic hydrocarbons next to sulfur containing aromatics. - Abstract: A novel analytical system for gas-chromatographic investigation of complex samples has been developed, that combines the advantages of several analytical principles to enhance the analytical information. Decomposition of high molecular weight structures is achieved by pyrolysis and a high separation capacity due to the chromatographic step provides both an universal as well as a selective and sensitive substance detection. The latter is achieved by simultaneously applying electron ionization quadrupole mass spectrometry (EI-QMS) for structural elucidation and [1 + 1]-resonance-enhanced-multi-photon ionization (REMPI) combined with time-of-flight mass spectrometry (ToFMS). The system has been evaluated and tested with polycyclic aromatic hydrocarbon (PAH) standards. It was applied to crude oil samples for the first time. In such highly complex samples several thousands of compounds are present and the identification especially of low concentrated chemical species such as PAH or their polycyclic aromatic sulfur containing heterocyclic (PASH) derivatives is often difficult. Detection of unalkylated and alkylated PAH together with PASH is considerably enhanced by REMPI–ToFMS, at times revealing aromatic structures which are not observable by EI-QMS due to their low abundance. On the other hand, the databased structure proposals of the EI-QMS analysis are needed to confirm structural information and isomers distinction. The technique allows a complex structure analysis as well as selective assessment of aromatic substances in one measurement. Information about the content of sulfur containing compounds plays a

  11. Impact of APCI ionization source in liquid chromatography tandem mass spectrometry based tissue distribution studies.

    Science.gov (United States)

    Khatal, Laxman; Gaur, Ashwani; Naphade, Ashish; Kandikere, Vishwottam; Mookhtiar, Kasim

    2016-10-01

    Measurement of test article concentration in tissue samples has been an important part of pharmacokinetic study and has helped to co-relate pharmacokinetic/pharmacodynamic relationships since the 1950s. Bioanalysis of tissue samples using LC-MS/MS comes with unique challenges in terms of sample handling and inconsistent analyte response owing to nonvolatile matrix components. Matrix effect is a phenomenon where the target analyte response is either suppressed or enhanced in the presence of matrix components. Based on previous reports electrospray ionization (ESI) mode of ionization is believed to be more affected by matrix components than atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization. To explore the impact of ionization source with respect to bioanalysis of tissue samples, five structurally diverse compounds - atenolol, verapamil, diclofenac, propranolol and flufenamic acid - were selected. Quality control standards were spiked into 10 different biological matrices like whole blood, liver, heart, brain, spleen, kidney, skeletal muscle, eye and skin tissue and were quantified against calibration standards prepared in rat plasma. Quantitative bioanalysis was performed utilizing both APCI and ESI mode and results were compared. Quality control standards when analyzed with APCI mode were found to be more consistent in terms of accuracy and precision as compared with ESI mode. Additionally, for some instances, up to 20-fold broader dynamic linearity range was observed with APCI mode as compared with ESI mode. As phospholid interferences have poor response in APCI mode, protein precipitation extraction technique can be used for multimatrix quantitation, which is more amenable to automation. The approach of multiple biological matrix quantitation against a single calibration curve helps bioanalysts to reduce turnaround time. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  12. Comparison of Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry with Electron Ionization and Negative-Ion Chemical Ionization for Analyses of Pesticides at Trace Levels in Atmospheric Samples

    Directory of Open Access Journals (Sweden)

    Renata Raina

    2008-01-01

    Full Text Available A comparison of detection limits of gas chromatography-mass spectrometry (GC-MS in selected ion monitoring (SIM with gas chromatography-tandem mass spectrometry (GC-MS/MS in selected reaction monitoring (SRM mode with both electron ionization (EI and negative-ion chemical ionization (NCI are presented for over 50 pesticides ranging from organochlorines (OCs, organophosphorus pesticides (OPs and pre-emergent herbicides used in the Canadian prairies (triallate, trifluralin, ethalfluralin. The developed GC-EI/SIM, GC-NCI/SIM, and GC-NCI/SRM are suitable for the determination of pesticides in air sample extracts at concentrations <100 pg µL−1 (<100 pg m−3 in air. No one method could be used to analyze the range of pre-emergent herbicides, OPs, and OCs investigated. In general GC-NCI/SIM provided the lowest method detection limits (MDLs commonly 2.5–10 pg µL−1 along with best confirmation (<25% RSD of ion ratio, while GC-NCI/SRM is recommended for use where added selectivity or confirmation is required (such as parathion-ethyl, tokuthion, carbofenothion. GC-EI/SRM at concentration <100 pg µL−1 was not suitable for most pesticides. GC-EI/SIM was more prone to interference issues than NCI methods, but gave good sensitivity (MDLs 1–10 pg µL−1 for pesticides with poor NCI response (OPs: sulfotep, phorate, aspon, ethion, and OCs: alachlor, aldrin, perthane, and DDE, DDD, DDT.

  13. A mechanistic study of fragmentation of deprotonated N,2-diphenyl-acetamides in electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Lu, Zhihua; Chai, Yunfeng; Wang, Jichao; Pan, Yuanjiang; Sun, Cuirong; Zeng, Su

    2014-08-15

    Exploring the fragmentation mechanism of amide ions in mass spectrometry has attracted great interest because of the desire to analyze the amino acid sequences of peptides and proteins. However, the collision-induced dissociation (CID) mechanism of deprotonated small amides has been rarely studied in electrospray ionization mass spectrometry (ESI-MS). The fragmentation of deprotonated N,2-diphenylacetamides exhibited some characteristic fragment ions, which are not derived from the conventional cleavage route. Therefore, clarification of their fragmentation mechanism is very important and useful for structural analysis of related amides and peptides. All CID experiments were carried out using an electrospray ionization ion trap mass spectrometer in negative ion mode. In addition, the accurate masses of fragments were measured on an ESI quadrupole time-of-flight (Q-TOF) mass spectrometer in negative ion mode. Deuterium-labeled 2-phenyl-N-(4-trifluoromethylphenyl)acetamide was synthesized and its ESI fragmentation spectrum had been obtained. Theoretical calculations were carried out by the density functional theory (DFT) method at the B3LYP level of theory with the 6-31G++(d,p) basis set. Deprotonated N,2-diphenylacetamides mainly generate four kinds of ions in CID: benzyl anion, aniline anion, phenyl-ethenone anion and isocyanato-benzene anion bearing respective substituent groups. The benzyl anion and the aniline anion can be generated by direct decomposition. The phenyl-ethenone anion and the isocyanato-benzene anion were proposed to be yielded from proton transfer within an ion-neutral complex, and the intensities of two competitive product ions are well correlated with the substituent constants. The mechanism was also supported by theoretical calculations. The characteristic fragment ions of deprotonated N,2-diphenylacetamides were proposed to be produced via an ion-neutral complex mechanism, which was proved by deuterium-labeling experiments, theoretical

  14. Internal energy distribution in electrospray ionization: towards the evaluation of a thermal-like distribution from the multiple-collision model.

    Science.gov (United States)

    Rondeau, David; Drahos, László; Vékey, Károly

    2014-06-15

    The internal energy deposition in ions that cross the desolvation region of an electrospray ionization (ESI) source affects the mass spectra that are obtained using in-source collision-induced dissociation (CID) or in tandem mass spectrometry (MS/MS) mode. It is thus important to evaluate the internal energy distributions of the ions in different parts of an ESI mass spectrometer. The desolvation region is considered as a collision zone and a partially elastic multiple-collision model is used to account for the accumulation of internal energy in the ions. The ion survival yields (SY(Theo) of the theoretical mass spectra calculated by MassKinetics software are fitted with the experimental ion survival yields (SY(Exp)) of the substituted benzylpyridinium cations that have been obtained with an ESI source interfaced with a quadrupole mass spectrometer. The theoretical parameters used for fitting the calculation data with the experimental results are the center-of-mass collision energy (Ecom ) of the colliding ions and a term related to the pressure of the desolvation area of the ESI interface. In the proposed model, an average number of 'effective' collisions of close to 30 in the desolvation area is employed. The voltages applied to the orifice of this interface are correlated to a theoretical initial kinetic energy (E(init,Kin)) in the laboratory frame of the ions. In the present case, these theoretical initial kinetic energies range from 5.5 to 9 eV. The internal energy distributions evaluated from this model resemble the thermal distributions of ions having 'characteristic temperatures' between 1020 and 1550 K, and the results of calculations show that the mean internal energy of the ions increases linearly with the orifice voltage. The model used in this study can account for the energy build-up of the ions in an ESI interface and allows the change in the internal energy distribution of the electrosprayed ions in different regions of a mass spectrometer to be

  15. Determination of polymer electrolyte membrane (PEM) degradation products in fuel cell water using electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Zedda, Marco; Tuerk, Jochen; Peil, Stefan; Schmidt, Torsten C

    2010-12-30

    Within the scope of research of membrane degradation phenomena during fuel cell operation a reliable analytical procedure for the extraction, detection and quantification of possible membrane oxidation products has been developed. These oxidation products originate from the attack of hydroxyl or peroxyl radicals on the membrane polymer. Such radicals are formed in situ (during fuel cell operation) or ex situ (Fenton test as oxidative stress simulation). The analysis of membrane oxidation products was carried out by electrospray ionization tandem mass spectrometry. Five potential membrane oxidation products (4-hydroxybenzoic acid (4-HBA), 4-hydroxybenzaldehyde (4-HBAD), 4,4-biphenol (4,4-BP), 4-hydroxybenzenesulfonate (4-HBS), and 4,4-sulfonylbiphenol (4,4-SBP)) were selected based on the molecular structure of the sulfonated polyarylether membrane used. In conjunction with the development of a multiple reaction monitoring (MRM) method, the ionization and fragmentation of the selected compounds were investigated. For 4,4-BP a molecular ion (M(+•) ) was observed in the positive ionization mode and used for MRM method development. Reproducible extraction of the model compounds was achieved using a mixed-mode sorbent material with both weak anion-exchange and reversed-phase retention properties. By using the developed analytical procedure, the identities of two membrane degradation products (4-HBA and 4-HBAD) were determined in situ and ex situ. In addition to the investigation of membrane degradation phenomena, the combination of extraction on a mixed-mode sorbent material and tandem mass spectrometric detection is attractive for the analysis of aromatic sulfonic acids, phenolic acids and phenols. Copyright © 2010 John Wiley & Sons, Ltd.

  16. Furoic and mefenamic acids as new matrices for matrix assisted laser desorption/ionization-(MALDI)-mass spectrometry.

    Science.gov (United States)

    Abdelhamid, Hani Nasser; Wu, Hui-Fen

    2013-10-15

    The present study introduces two novel organic matrices for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) for the analysis of small molecules. The first matrix is "2-amino-4,5-diphenylfuran-3-carboxylic acid" (also called furoic acid, FA) which was synthesized and then characterized by ultraviolet (UV), infrared (FTIR), nuclear magnetic resonance NMR ((1)H and (13)C) and mass spectrometry. The compound has organic semiconductor properties and exhibits intense UV-absorption which is suitable for the UV-MALDI laser (N2 laser, 337 nm). The second matrix is mefenamic acid (MA). The two matrices can be successfully applied for various classes of compounds including adenosine-5'-triphosphate (ATP, 0.5 µL(10.0 nmol)), spectinomycin (spect, 0.5 µL(14.0 nmol)), glutathione (GSH, 0.5 µL(9.0 nmol)), sulfamethazole (SMT, 0.5 µL(2.0 nmol)) and mixture of peptides gramicidin D (GD, 0.5µL (9.0 nmol)). The two matrices can effectively absorb the laser energy, resulting in excellent desorption/ionization of small molecules. The new matrices offer a significant enhancement of ionization, less fragmentation, few interferences, nice reproducibility, and excellent stability under vacuum. Theoretical calculations of the physical parameters demonstrated increase in polarizability, molar volume and refractivity than the conventional organic matrices which can effectively enhance the proton transfer reactions between the matrices with the analyte molecules. While the reduction in density, surface tension and index of refraction can enhance homogeneity between the two new matrices with the analytes. Due to the sublimation energy of mefenamic acid is (1.2 times) higher than that of the DHB, it is more stable to be used in the vacuum. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Studying interfacial reactions of cholesterol sulfate in an unsaturated phosphatidylglycerol layer with ozone using field induced droplet ionization mass spectrometry.

    Science.gov (United States)

    Ko, Jae Yoon; Choi, Sun Mi; Rhee, Young Min; Beauchamp, J L; Kim, Hugh I

    2012-01-01

    Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO(4)) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O(3)) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO(4) reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO(4) oxidation in the FIDI-MS spectrum after exposure of the droplet to O(3) for 5 s. The abundance of the epoxide product then decreases with continued O(3) exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO(4) and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO(4) and POPG with O(3) suggest that CholSO(4) is present with POPG as a well-mixed interfacial layer. Compared with CholSO(4) and POPG alone, the overall ozonolysis rates of both CholSO(4) and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO(4) correlate well with experimental observations and provide a detailed picture of the interactions between CholSO(4), lipids, and water molecules in the interfacial region. © American Society for Mass Spectrometry, 2011

  18. Mass Spectrometry of Halopyrazolium Salts

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Egsgaard, Helge; Pande, U. C.

    1983-01-01

    Eleven halogen substituted 1-methyl-2-phenylpyrazolium bromides or chlorides were investigated by field desorption, field ionization, and electron impact mass spectrometry. Dealkylation was found to be the predominant thermal decomposition. An exchange between covalent and ionic halogen prior...

  19. Modelling the thermal behaviour of the low-thermal mass liquid chromatography system.

    Science.gov (United States)

    Verstraeten, Matthias; Pursch, Matthias; Eckerle, Patric; Luong, Jim; Desmet, Gert

    2011-04-22

    We report upon the experimental investigation of the heat transfer in low thermal mass LC (LTMLC) systems, used under temperature gradient conditions. The influence of the temperature ramp, the capillary dimensions, the material selection and the chromatographic conditions on the radial temperature gradients formed when applying a temperature ramp were investigated by a numerical model and verified with experimental temperature measurements. It was found that the radial temperature gradients scale linearly with the heating rate, quadratically with the radius of the capillary and inversely to the thermal diffusivity. Because of the thermal radial gradients in the liquid zone inside the capillary lead to radial viscosity and velocity gradients, they form an additional source of dispersion for the solutes. For a temperature ramp of 1 K/s and a strong temperature dependence of the retention of small molecules, the model predicts that narrow-bore columns (i.d. 2.1 mm) can be used. For a temperature ramp of 10 K/s, the maximal inner diameter is of the order of 1 mm before a substantial increase in dispersion occurs. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. Electrowetting-based microfluidics for analysis of peptides and proteins by matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Wheeler, Aaron R; Moon, Hyejin; Kim, Chang-Jin; Loo, Joseph A; Garrell, Robin L

    2004-08-15

    A new technique for preparing samples for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is reported. The technique relies on electrowetting-on-dielectric (EWOD) to move droplets containing proteins or peptides and matrix to specific locations on an array of electrodes for analysis. Standard MALDI-MS reagents, analytes, concentrations, and recipes are demonstrated to be compatible with the technique. Mass spectra are comparable to those collected by conventional methods. Nonspecific adsorption of analytes to device surfaces is demonstrated to be negligible. The results suggest that EWOD may be a useful tool for automating sample preparation for high-throughput proteomics and other applications of MALDI-MS.

  1. Nanomaterial based affinity matrix-assisted laser desorption/ionization mass spectrometry for biomolecules and pathogenic bacteria.

    Science.gov (United States)

    Chiu, Tai-Chia; Huang, Li-Shing; Lin, Po-Chiao; Chen, Yu-Chie; Chen, Yu-Ju; Lin, Chun-Cheng; Chang, Huan-Tsung

    2007-01-01

    This paper describes mass spectrometry (MS) using nanoparticles (NPs) for the analysis of biomolecules such as aminothiol compounds, drugs, peptides, proteins, and bacteria. Papers and patents dealing with preparation and use of several NPs in MS have been briefly reviewed, including carbon nanotubes, gold NPs, and magnetic NPs. The NPs or bioconjugated NPs were used for selective concentration and/or assisted matrices for desorption and ionization of analytes of interest. When compared to conventional organic matrixes, the NPs provide low MS background in low-mass region and low shot-to-shot variation. MS techniques using NPs and bioconjugated NPs for the analysis of disease-associated biomarkers and bacteria in real samples such as blood and urine are highlighted, showing the advantages of high sensitivity, reproducibility, and simplicity.

  2. Identification of plasmalogen cardiolipins from Pectinatus by liquid chromatography-high resolution electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Řezanka, Tomáš; Matoulková, Dagmar; Kyselová, Lucie; Sigler, Karel

    2013-12-01

    High resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) was used to analyze cardiolipins (Ptd2Gro) including their plasmalogen forms from three species of the anaerobic beer-spoilage bacterial genus Pectinatus. Cardiolipins including their plasmalogens were analyzed by HR-ESI-MS/MS on Orbitrap and almost 100 cardiolipins (i.e. tetra-acyl--Ptd2Gro, plasmenyl-tri-acyl--PlsPtd2Gro, and di-plasmenyl-di-acyl--Pls2Ptd2Gro) of three classes were identified. The structures of the molecular species that consist of various regioisomers and structurally similar compounds were revealed in detail. The high resolution mass spectrometry allowed the unambiguous structural assignment of Ptd2Gro, PlsPtd2Gro, and Pls2Ptd2Gro in the three species of Pectinatus, which contain predominantly odd numbered fatty acids.

  3. Rapid detection of undesired cosmetic ingredients by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Ouyang, Jie; An, Dongli; Chen, Tengteng; Lin, Zhiwei

    2017-10-01

    In recent years, cosmetic industry profits soared due to the widespread use of cosmetics, which resulted in illicit manufacturers and products of poor quality. Therefore, the rapid and accurate detection of the composition of cosmetics has become crucial. At present, numerous methods, such as gas chromatography and liquid chromatography-mass spectrometry, were available for the analysis of cosmetic ingredients. However, these methods present several limitations, such as failure to perform comprehensive and rapid analysis of the samples. Compared with other techniques, matrix-assisted laser desorption ionization time-of-flight mass spectrometry offered the advantages of wide detection range, fast speed and high accuracy. In this article, we briefly summarized how to select a suitable matrix and adjust the appropriate laser energy. We also discussed the rapid identification of undesired ingredients, focusing on antibiotics and hormones in cosmetics.

  4. Unexpected Reduction of Iminoquinone and Quinone Derivatives in Positive Electrospray Ionization Mass Spectrometry and Possible Mechanism Exploration

    Science.gov (United States)

    Pei, Jiying; Hsu, Cheng-Chih; Zhang, Ruijie; Wang, Yinghui; Yu, Kefu; Huang, Guangming

    2017-08-01

    Unexpected reduction of iminoquinone (IQ) and quinone derivatives was first reported during positive electrospray ionization mass spectrometry. Upon increasing spray voltage, the intensities of IQ and quinone derivatives decreased drastically, accompanying the increase of the intensities of the reduction products, amodiaquine (AQ) and phenol derivatives. To gain more insight into the mechanism of such reduction, we explored the experimental factors that are influential to corona discharge (CD). The results show that experimental parameters that favor severe CD, including metal spray emitter, using water as spray solvent, sheath gas with low dielectric strength (e.g., nitrogen), and shorter spray tip-to-mass spectrometer inlet distance, facilitated the reduction of IQ and quinone derivatives, implying that the reduction should be closely related to CD in the gas phase. [Figure not available: see fulltext.

  5. Demand Shifting with Thermal Mass in Light and Heavy Mass Commercial Buildings

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Peng; Zagreus, Leah

    2009-05-01

    The potential for utilizing building thermal mass for load shifting and peak demand reduction has been demonstrated in a number of simulation, laboratory, and field studies. This project studied the potential of pre-cooling and demand limiting in a heavy mass and a light mass building in the Bay Area of California. The conclusion of the work to date is that pre-cooling has the potential to improve the demand responsiveness of commercial buildings while maintaining acceptable comfort conditions. Results indicate that pre-cooling increases the depth (kW) and duration (kWh) of the shed capacity of a given building, all other factors being equal. Due to the time necessary for pre-cooling, it is only applicable to day-ahead demand response programs. Pre-cooling can be very effective if the building mass is relatively heavy. The effectiveness of night pre-cooling under hot weather conditions has not been tested. Further work is required to quantify and demonstrate the effectiveness of pre-cooling in different climates. Research is also needed to develop screening tools that can be used to select suitable buildings and customers, identify the most appropriate pre-cooling strategies, and estimate the benefits to the customer and the utility.

  6. Nanomaterials as Assisted Matrix of Laser Desorption/Ionization Time-of-Flight Mass Spectrometry for the Analysis of Small Molecules

    Science.gov (United States)

    Lu, Minghua; Yang, Xueqing; Yang, Yixin; Qin, Peige; Wu, Xiuru; Cai, Zongwei

    2017-01-01

    Matrix-assisted laser desorption/ionization (MALDI), a soft ionization method, coupling with time-of-flight mass spectrometry (TOF MS) has become an indispensible tool for analyzing macromolecules, such as peptides, proteins, nucleic acids and polymers. However, the application of MALDI for the analysis of small molecules (mass region. To overcome this drawback, more attention has been paid to explore interference-free methods in the past decade. The technique of applying nanomaterials as matrix of laser desorption/ionization (LDI), also called nanomaterial-assisted laser desorption/ionization (nanomaterial-assisted LDI), has attracted considerable attention in the analysis of low-molecular weight compounds in TOF MS. This review mainly summarized the applications of different types of nanomaterials including carbon-based, metal-based and metal-organic frameworks as assisted matrices for LDI in the analysis of small biological molecules, environmental pollutants and other low-molecular weight compounds. PMID:28430138

  7. Quantitation of peptides and proteins by matrix-assisted laser desorption/ionization mass spectrometry using (18)O-labeled internal standards

    DEFF Research Database (Denmark)

    Mirgorodskaya, O A; Kozmin, Y P; Titov, M I

    2000-01-01

    A method for quantitating proteins and peptides in the low picomole and sub-picomole range has been developed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with internal (18)O-labeled standards. A simple procedure is proposed to produce such internal standards for...... inhibitor, were quantified by MALDI-time-of-flight (TOF) mass spectrometry.......A method for quantitating proteins and peptides in the low picomole and sub-picomole range has been developed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with internal (18)O-labeled standards. A simple procedure is proposed to produce such internal standards...

  8. Length and base composition of PCR-amplified nucleic acids using mass measurements from electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Muddiman, D.C.; Anderson, G.A.; Hofstadler, S.A.; Smith, R.D. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-04-15

    A generally applicable algorithm has ben developed to allow base composition of polymerase chain reaction (PCR) products to be determined from mass spectrometrically measured molecular weights and the complementary nature of DNA. Mass measurements of arbitrary precision for single-stranded DNA species are compatible with an increasingly large number of possible base compositions as molecular weight increases. For example, the number of base compositions that are consistent with a molecular weight of 35000 is nearly 6000, based on a mass measurement precision of 0.01%. However, given the low misincorporation rate of standard DNA polymerses, mass measurement of both of the complementary single strands produced in the PCR reduces the number of possibilities to less then 100 at 0.01% mass precision, and the base composition is uniquely defined at 0.001% mass precision. Taking into account the low misincorporation rate of standard DNA polymerases and the fact that the final PCR product also contains primers of known sequence (generally 15-20 mer in size, which flank the targeted region), this reduces the number of possible base combinations to only nearly 3 at MW = 35000. In addition, the number of base pairs (i.e., length of the DNA molecule) is uniquely defined. We show that the use of modified bases in PCR or post-PCR modification chemistry allows unique solutions for the base composition of the PCR product with only modest mass measurement precision. 31 refs., 5 figs., 1 tab.

  9. Rapid sample classification using an open port sampling interface coupled with liquid introduction atmospheric pressure ionization mass spectrometry.

    Science.gov (United States)

    Van Berkel, Gary J; Kertesz, Vilmos

    2017-02-15

    An "Open Access"-like mass spectrometric platform to fully utilize the simplicity of the manual open port sampling interface for rapid characterization of unprocessed samples by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The in-house developed integrated software with a simple, small and relatively low-cost mass spectrometry system introduced here fills this void. Software was developed to operate the mass spectrometer, to collect and process mass spectrometric data files, to build a database and to classify samples using such a database. These tasks were accomplished via the vendor-provided software libraries. Sample classification based on spectral comparison utilized the spectral contrast angle method. Using the developed software platform near real-time sample classification is exemplified using a series of commercially available blue ink rollerball pens and vegetable oils. In the case of the inks, full scan positive and negative ion ESI mass spectra were both used for database generation and sample classification. For the vegetable oils, full scan positive ion mode APCI mass spectra were recorded. The overall accuracy of the employed spectral contrast angle statistical model was 95.3% and 98% in case of the inks and oils, respectively, using leave-one-out cross-validation. This work illustrates that an open port sampling interface/mass spectrometer combination, with appropriate instrument control and data processing software, is a viable direct liquid extraction sampling and analysis system suitable for the non-expert user and near real-time sample classification via database matching. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

  10. Benefits of 2.94 μm infrared matrix-assisted laser desorption/ionization for analysis of labile molecules by Fourier transform mass spectrometry

    DEFF Research Database (Denmark)

    Budnik, Bogdan A.; Jensen, Kenneth Bendix; Jørgensen, Thomas J. D.

    2000-01-01

    A 2.94 microm Er:YAG laser was used together with a commercial Fourier transform mass spectrometer to study labile biomolecules. The combination has shown superior performance over conventional 337 nm ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) Fourier transform mass...

  11. A SIMPLE AND RAPID MATRIX-ASSISTED LASER DESORPTION/IONIZATION TIME OF FLIGHT MASS SPECTROMETRY METHOD TO SCREEN FISH PLASMA SAMPLES FOR ESTROGEN-RESPONSIVE BIOMARKERS

    Science.gov (United States)

    In this study, we describe and evaluate the performance of a simple and rapid mass spectral method for screening fish plasma for estrogen-responsive biomarkers using matrix assisted laster desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) couopled with a short...

  12. Development of a method for quantitation of retinol and retinyl palmitate in human serum using high-performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry.

    NARCIS (Netherlands)

    Breemen, van R.B.; Nikolic, D.; Xu, X.Y.; Xiong, Y.S.; Lieshout, van M.; West, C.E.; Schilling, A.B.

    1998-01-01

    A method for the quantitative analysis of the vitamin A compounds all-trans-retinol and all-trans-retinyl palmitate was developed using high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (APCI-LC-MS). Unlike previous quantitative mass spectrometric

  13. Control of Strobilurin Fungicides in Wheat Using Direct Analysis in Real Time Accurate Time-of-Flight and Desorption Electrospray Ionization Linear Ion Trap Mass Spectrometry

    NARCIS (Netherlands)

    Schurek, J.; Vaclavik, L.; Hooijerink, H.; Lacina, O.; Poustka, J.; Sharman, M.; Caldow, M.; Nielen, M.W.F.; Hajslova, J.

    2008-01-01

    Ambient mass spectrometry has been used for the analysis of strobilurin residues in wheat. The use of this novel, challenging technique, employing a direct analysis in a real time (DART) ion-source coupled with a time-of-flight mass spectrometer (TOF MS) and a desorption electrospray ionization

  14. Identification of multiple target sites for a glutathione conjugate on glutathione-S-transferase by matrix-assisted laser desorption/ionization mass spectrometry

    NARCIS (Netherlands)

    Jespersen, S.; Ploemen, J.H.T.M.; Bladeren, P.J.; Niessen, W.M.A.; Tjaden, U.R.; Greef, J. van der

    1996-01-01

    A mass spectrometric method providing qualitative site-specific information regarding covalent modification of proteins is described. The method involves comparison of unmodified and modified proteins by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) peptide mapping in

  15. Probing the dynamics of polyatomic multichannel elementary reactions by crossed molecular beam experiments with soft electron-ionization mass spectrometric detection.

    Science.gov (United States)

    Casavecchia, Piergiorgio; Leonori, Francesca; Balucani, Nadia; Petrucci, Raffaele; Capozza, Giovanni; Segoloni, Enrico

    2009-01-07

    In this Perspective we highlight developments in the field of chemical reaction dynamics. Focus is on the advances recently made in the investigation of the dynamics of elementary multichannel radical-molecule and radical-radical reactions, as they have become possible using an improved crossed molecular beam scattering apparatus with universal electron-ionization mass spectrometric detection and time-of-flight analysis. These improvements consist in the implementation of (a) soft ionization detection by tunable low-energy electrons which has permitted us to reduce interfering signals originating from dissociative ionization processes, usually representing a major complication, (b) different beam crossing-angle set-ups which have permitted us to extend the range of collision energies over which a reaction can be studied, from very low (a few kJ mol(-1), as of interest in astrochemistry or planetary atmospheric chemistry) to quite high energies (several tens of kJ mol(-1), as of interest in high temperature combustion systems), and (c) continuous supersonic sources for producing a wide variety of atomic and molecular radical reactant beams. Exploiting these new features it has become possible to tackle the dynamics of a variety of polyatomic multichannel reactions, such as those occurring in many environments ranging from combustion and plasmas to terrestrial/planetary atmospheres and interstellar clouds. By measuring product angular and velocity distributions, after having suppressed or mitigated, when needed, the problem of dissociative ionization of interfering species (reactants, products, background gases) by soft ionization detection, essentially all primary reaction products can be identified, the dynamics of each reaction channel characterized, and the branching ratios determined as a function of collision energy. In general this information, besides being of fundamental relevance, is required for a predictive description of the chemistry of these

  16. 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.

  17. Characterization of Nitrated Sugar Alcohols by Atmospheric-Pressure Chemical-Ionization Mass Spectrometry

    Science.gov (United States)

    2016-07-27

    mass spectrometry (APCI-MS) was used to detect ions characteristic of nitrated sugar alcohols. Time-of- flight APCI mass spectrometry (TOF APCI-MS...disclosed here will benefit the area of explosives trace detection for counterterrorism and forensics. INTRODUCTION The military-grade...with an Agilent 6520 QTOF quadrupole time-of- flight (TOF) mass spectrometer (Agilent technologies, Santa Clara, CA, USA) equipped with an APCI source

  18. Enzyme-coupled nanoparticles-assisted laser desorption ionization mass spectrometry for searching for low-mass inhibitors of enzymes in complex mixtures.

    Science.gov (United States)

    Salwiński, Aleksander; Da Silva, David; Delépée, Raphaël; Maunit, Benoît

    2014-04-01

    In this report, enzyme-coupled magnetic nanoparticles (EMPs) were shown to be an effective affinity-based tool for finding specific interactions between enzymatic targets and the low-mass molecules in complex mixtures using classic MALDI-TOF apparatus. EMPs used in this work act as nonorganic matrix enabling ionization of small molecules without any interference in the low-mass range (enzyme-coupled nanoparticles-assisted laser desorption ionization MS, ENALDI MS) and simultaneously carry the superficial specific binding sites to capture inhibitors present in a studied mixture. We evaluated ENALDI approach in two complementary variations: 'ion fading' (IF-ENALDI), based on superficial adsorption of inhibitors and 'ion hunting' (IH-ENALDI), based on selective pre-concentration of inhibitors. IF-ENALDI was applied for two sets of enzyme-inhibitor pairs: tyrosinase-glabridin and trypsin-leupeptin and for the real plant sample: Sparrmannia discolor leaf and stem methanol extract. The efficacy of IH-ENALDI was shown for the pair of trypsin-leupeptin. Both ENALDI approaches pose an alternative for bioassay-guided fractionation, the common method for finding inhibitors in the complex mixtures.

  19. High-Spatial and High-Mass Resolution Imaging of Surface Metabolites of Arabidopsis thaliana by Laser Desorption-Ionization Mass Spectrometry Using Colloidal Silver

    Energy Technology Data Exchange (ETDEWEB)

    Jun, Ji Hyun; Song, Zhihong; Liu, Zhenjiu; Nikolau, Basil J.; Yeung, Edward S.; and Lee, Young Jin

    2010-03-17

    High-spatial resolution and high-mass resolution techniques are developed and adopted for the mass spectrometric imaging of epicuticular lipids on the surface of Arabidopsis thaliana. Single cell level spatial resolution of {approx}12 {micro}m was achieved by reducing the laser beam size by using an optical fiber with 25 {micro}m core diameter in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer and improved matrix application using an oscillating capillary nebulizer. Fine chemical images of a whole flower were visualized in this high spatial resolution showing substructure of an anther and single pollen grains at the stigma and anthers. The LTQ-Orbitrap with a MALDI ion source was adopted to achieve MS imaging in high mass resolution. Specifically, isobaric silver ion adducts of C29 alkane (m/z 515.3741) and C28 aldehyde (m/z 515.3377), indistinguishable in low-resolution LTQ, can now be clearly distinguished and their chemical images could be separately constructed. In the application to roots, the high spatial resolution allowed molecular MS imaging of secondary roots and the high mass resolution allowed direct identification of lipid metabolites on root surfaces.

  20. Trapping, detection, and mass determination of coliphage T4 DNA ions of 10{sup 8} Da by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Chen, R.; Cheng, X.; Mitchell, D.W.; Hofstadler, S.A.; Wu, Q.; Rockwood, A.L.; Sherman, M.G.; Smith, R.D. [Pacific Northwest Lab., Richland, WA (United States)

    1995-04-01

    The trapping, detection, and mass measurement of individual T4 DNA ions (nominal molecular weight, M{sub r} = 1.1 x 10{sup 8} Da) have been performed with a 7 T electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometer. The ionic mass was obtained by direct measurement of the number of charges carried by individual T4 DNA ions. The ions detected are a factor of approximately 20 larger than any molecule previously studied by mass spectrometry. These gas-phase macroions demonstrate a high degree of stability, which allows the acquisition of long transients (>476 s) from individual ions and the study of relatively slow reactions or dissociation processes. These results show the potential utility of ESI-FTICR mass spectrometry for the analysis of very large biomolecules and microparticles and indicate that it is possible to transfer ions of 110 MDa size to the gas phase substantially intact. The potential applications of the FTICR analysis of such highly charged ions are briefly discussed. 33 refs., 3 figs., 1 tab.

  1. Proof of Concept Coded Aperture Miniature Mass Spectrometer Using a Cycloidal Sector Mass Analyzer, a Carbon Nanotube (CNT) Field Emission Electron Ionization Source, and an Array Detector

    Science.gov (United States)

    Amsden, Jason J.; Herr, Philip J.; Landry, David M. W.; Kim, William; Vyas, Raul; Parker, Charles B.; Kirley, Matthew P.; Keil, Adam D.; Gilchrist, Kristin H.; Radauscher, Erich J.; Hall, Stephen D.; Carlson, James B.; Baldasaro, Nicholas; Stokes, David; Di Dona, Shane T.; Russell, Zachary E.; Grego, Sonia; Edwards, Steven J.; Sperline, Roger P.; Denton, M. Bonner; Stoner, Brian R.; Gehm, Michael E.; Glass, Jeffrey T.

    2017-10-01

    Despite many potential applications, miniature mass spectrometers have had limited adoption in the field due to the tradeoff between throughput and resolution that limits their performance relative to laboratory instruments. Recently, a solution to this tradeoff has been demonstrated by using spatially coded apertures in magnetic sector mass spectrometers, enabling throughput and signal-to-background improvements of greater than an order of magnitude with no loss of resolution. This paper describes a proof of concept demonstration of a cycloidal coded aperture miniature mass spectrometer (C-CAMMS) demonstrating use of spatially coded apertures in a cycloidal sector mass analyzer for the first time. C-CAMMS also incorporates a miniature carbon nanotube (CNT) field emission electron ionization source and a capacitive transimpedance amplifier (CTIA) ion array detector. Results confirm the cycloidal mass analyzer's compatibility with aperture coding. A >10× increase in throughput was achieved without loss of resolution compared with a single slit instrument. Several areas where additional improvement can be realized are identified. [Figure not available: see fulltext.

  2. Established and emerging atmospheric pressure surface sampling/ionization techniques for mass spectrometry.

    Science.gov (United States)

    Van Berkel, Gary J; Pasilis, Sofie P; Ovchinnikova, Olga

    2008-09-01

    The number and type of atmospheric pressure techniques suitable for sampling analytes from surfaces, forming ions from these analytes, and subsequently transporting these ions into vacuum for interrogation by MS have rapidly expanded over the last several years. Moreover, the literature in this area is complicated by an explosion in acronyms for these techniques, many of which provide no information relating to the chemical or physical processes involved. In this tutorial article, we sort this vast array of techniques into relatively few categories on the basis of the approaches used for surface sampling and ionization. For each technique, we explain, as best known, many of the underlying principles of operation, describe representative applications, and in some cases, discuss needed research or advancements and attempt to forecast their future analytical utility.

  3. Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

    Science.gov (United States)

    Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

    2017-04-01

    Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (instrument response for isoprene and a wide range of monoterpenes and sesquiterpenes. To gain mechanistic insight into the ion-molecule reactions and the role of water vapor and oxygen, we compare our measured sensitivities with a computational analysis of the charge distribution between the analyte, reagent ion and water molecules in the gas phase. These parameters provide insight on the ionization mechanism and provide parameters for quantification of organic molecules measured during field campaigns. References Kim, M. J., M. C. Zoerb, N. R. Campbell, K. J. Zimmermann, B. W. Blomquist, B. J. Huebert, and T. H. Bertram (2016), Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

  4. Newborn screening by matrix-assisted laser desorption/ionization mass spectrometry based on parylene-matrix chip.

    Science.gov (United States)

    Kim, Jo-Il; Noh, Joo-Yoon; Kim, Mira; Park, Jong-Min; Song, Hyun-Woo; Kang, Min-Jung; Pyun, Jae-Chul

    2017-08-01

    Newborn screening for diagnosis of phenylketonuria, homocystinuria, and maple syrup urine disease have been conducted by analyzing the concentration of target amino acids using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF MS) based on parylene-matrix chip. Parylene-matrix chip was applied to MALDI-ToF MS analysis reducing the matrix peaks significantly at low mass-to-charge ratio range (m/z mass spectrometric analysis showing 13.3 to 45% of extraction efficiency. Calibration curves for diagnosis of neonatal metabolic disorders were obtained by analyzing methanol-extracted serum spiked with target amino acids using MALDI-ToF MS. They showed good linearity (R2 > 0.98) and the LODs were ranging from 9.0 to 22.9 μg/mL. Effect of proteins in serum was estimated by comparing MALDI-ToF mass spectra of amino acids-spiked serum before and after the methanol extraction. Interference of other amino acids on analysis of target analyte was determined to be insignificant. From these results, MALDI-ToF MS based on parylene-matrix chip could be applicable to medical diagnosis of neonatal metabolic disorders. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Principles of hydrogen radical mediated peptide/protein fragmentation during matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Asakawa, Daiki

    2016-07-01

    Matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) is a very easy way to obtain large sequence tags and, thereby, reliable identification of peptides and proteins. Recently discovered new matrices have enhanced the MALDI-ISD yield and opened new research avenues. The use of reducing and oxidizing matrices for MALDI-ISD of peptides and proteins favors the production of fragmentation pathways involving "hydrogen-abundant" and "hydrogen-deficient" radical precursors, respectively. Since an oxidizing matrix provides information on peptide/protein sequences complementary to that obtained with a reducing matrix, MALDI-ISD employing both reducing and oxidizing matrices is a potentially useful strategy for de novo peptide sequencing. Moreover, a pseudo-MS(3) method provides sequence information about N- and C-terminus extremities in proteins and allows N- and C-terminal side fragments to be discriminated within the complex MALDI-ISD mass spectrum. The combination of high mass resolution of a Fourier transform-ion cyclotron resonance (FTICR) analyzer and the software suitable for MALDI-ISD facilitates the interpretation of MALDI-ISD mass spectra. A deeper understanding of the MALDI-ISD process is necessary to fully exploit this method. Thus, this review focuses first on the mechanisms underlying MALDI-ISD processes, followed by a discussion of MALDI-ISD applications in the field of proteomics. © 2014 Wiley Periodicals, Inc., Mass Spec Rev 35:535-556, 2016. © 2014 Wiley Periodicals, Inc.

  6. Capillary electrophoresis-electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for direct analysis of cellular proteins

    Energy Technology Data Exchange (ETDEWEB)

    Hofstadler, S.A.; Gale, D.C.; Smith, R.D. [Pacific Northwest Lab., Richland, WA (United States); Swanek, F.D.; Ewing, A.G. [Pennsylvania State Univ., University Park, PA (United States)

    1995-04-15

    The combination of capillary electrophoresis (CE) with electrospray ionization (ESI) mass spectrometry has proven to be broadly applicable to a wide range of biologically important compounds. When combined with Fourier transform ion cyclotron resonance (FTICR) mass spectrometry, the combined method, in addition to high-resolution separations, affords high-resolution precision mass measurements for analytes separated from complex mixtures. Direct chemical analysis of single cells has received considerable attention in recent years; the single cell approach provides a major step toward answering important questions in the field of cellular biochemistry. In this work we present preliminary results which demonstrate the feasibility of using the CE-ESI-FTICR combination as a high-performance detection scheme for the analysis of cellular proteins acquired directly from small populations (i.e., 5-10) of intact living cells. The human erythrocyte was chosen as a model system owing to its availability, relatively homogeneous composition, and thorough documentation of contents by previous researchers. In this work we demonstrate the on-line acquisition of high-resolution mass spectra (average resolution >45 000 fwhm) of both the {alpha} and the {beta} chains of hemoglobin acquired from the injection of 10 human erythrocytes. 33 refs., 3 figs.

  7. Desorption electrospray ionization-high resolution mass spectrometry for the screening of veterinary drugs in cross-contaminated feedstuffs.

    Science.gov (United States)

    Seró, Raquel; Núñez, Oscar; Bosch, Jaume; Grases, José M; Rodríguez, Pilar; Moyano, Encarnacion; Galceran, Martia Teresa

    2015-09-01

    In this study, a desorption electrospray ionization-high resolution mass spectrometry (DESI-HRMS) screening method was developed for fast identification of veterinary drugs in cross-contaminated feedstuffs. The reliable detection was performed working at high resolution (70,000 full width half maximum, FWHM) using an orbitrap mass analyzer. Among the optimized DESI parameters, the solvent (acetonitrile/water, 80:20, v/v) and the sample substrate (poly-tetrafluoroethylene, PTFE) were critical to obtain the best sensitivity. To analyze the solid feed samples, different approaches were tested and a simple solid-liquid extraction and the direct analysis of an aliquot (2 μL) of the extract after letting it dry on the PTFE printed spot provided the best results. The identification of the veterinary drugs (target and non-target) in the cross-contaminated feedstuffs based on the accurate mass measurement and the isotopic pattern fit was performed automatically using a custom-made database. The positive cross-contaminated feed samples were quantified by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The results obtained demonstrate that DESI-HRMS can be proposed as a fast and suitable screening method to identify positive cross-contaminated feedstuffs reducing the number of samples to be subsequently quantified by UHPLC-MS/MS, thus improving the productivity in quality control laboratories.

  8. Sensitive and simple analysis of sorbic acid using liquid chromatography with electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Horiyama, Shizuyo; Honda, Chie; Suwa, Kiyoko; Umemoto, Yuko; Okada, Yasuyo; Semma, Masanori; Ichikawa, Atsushi; Takayama, Mitsuo

    2008-04-01

    Sorbic acid (SA: CH(3)-CH=CH-CH=CH-COOH) and its salts are widely used as preservatives in foodstuff because of their growth inhibitory effects on mold, yeast and a wide range of bacteria. However, it is still unclear whether SA and its salts are actually incorporated in these organisms and a higher organisms like mammalian cells. Acidic compounds such as SA are usually analyzed by HPLC with eluents containing acetic acid, formic acid and their ammonium acetates, but such acidic buffers may suppress the ionization efficiency of the acidic compounds in negative-mode electrospray ionization (ESI). In this study, we present a sensitive and simple method for analysis of SA by HPLC with non-acidic solvents such as CH(3)CN/CH(3)OH-H(2)O by negative ion mode ESI-LC/MS. As a result, SA at less as 30 fmol was selectively determined by the selected reaction monitoring (SRM) mode. It was defined as the peak area with a signal-to-noise ratio (S/N) of 3. Good linearity was obtained in the range from 55 fmol (S/N 3) to 500 fmol (r(2)=0.9968) for SA by using LC/MS with the SRM mode. We also show that the method is useful to analyze SA level in the cytosol of mastocytoma cells, which were pretreated with SA. These results suggest the applicability of this method for the highly sensitive determination of SA in the mammalian tissues and cells.

  9. The yeast metabolome addressed by electrospray ionization mass spectrometry: Initiation of a mass spectral library and its applications for metabolic footprinting by direct infusion mass spectrometry

    DEFF Research Database (Denmark)

    Højer-Pedersen, Jesper Juul; Smedsgaard, Jørn; Nielsen, Jens

    2008-01-01

    for ionization of microbial metabolites without any previous derivatization needed. To address the capabilities of ESI-MS in detecting the metabolome of Saccharomyces cerevisiae, the in silico metabolome of this organism was used as a template to present a theoretical metabolome. This showed that in combination...... into the ionization and fragmentation characteristics of the different metabolites. With this insight, a small study of metabolic footprinting with ESI-MS demonstrated that biological information can be extracted from footprinting spectra. Statistical analysis of the footprinting data revealed discriminating ions...

  10. Application of pyrolysis-mass spectrometry and pyrolysis-gas chromatography-mass spectrometry with electron-ionization or resonance-enhanced-multi-photon ionization for characterization of crude oils.

    Science.gov (United States)

    Otto, Stefan; Streibel, Thorsten; Erdmann, Sabrina; Sklorz, Martin; Schulz-Bull, Detlef; Zimmermann, Ralf

    2015-01-15

    A novel analytical system for gas-chromatographic investigation of complex samples has been developed, that combines the advantages of several analytical principles to enhance the analytical information. Decomposition of high molecular weight structures is achieved by pyrolysis and a high separation capacity due to the chromatographic step provides both an universal as well as a selective and sensitive substance detection. The latter is achieved by simultaneously applying electron ionization quadrupole mass spectrometry (EI-QMS) for structural elucidation and [1+1]-resonance-enhanced-multi-photon ionization (REMPI) combined with time-of-flight mass spectrometry (ToFMS). The system has been evaluated and tested with polycyclic aromatic hydrocarbon (PAH) standards. It was applied to crude oil samples for the first time. In such highly complex samples several thousands of compounds are present and the identification especially of low concentrated chemical species such as PAH or their polycyclic aromatic sulfur containing heterocyclic (PASH) derivatives is often difficult. Detection of unalkylated and alkylated PAH together with PASH is considerably enhanced by REMPI-ToFMS, at times revealing aromatic structures which are not observable by EI-QMS due to their low abundance. On the other hand, the databased structure proposals of the EI-QMS analysis are needed to confirm structural information and isomers distinction. The technique allows a complex structure analysis as well as selective assessment of aromatic substances in one measurement. Information about the content of sulfur containing compounds plays a significant role for the increase of efficiency in the processing of petroleum. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Studies on thermal decomposition mechanism of CL-20 by pyrolysis gas chromatography-mass spectrometry (Py-GC/MS)

    Energy Technology Data Exchange (ETDEWEB)

    Naik, N.H.; Gore, G.M. [High Energy Materials Research Laboratory, Sutarwadi, Pune 411021 (India); Gandhe, B.R. [Directorate of Armament, DRDO Bhavan, New Delhi 110011 (India); Sikder, A.K. [High Energy Materials Research Laboratory, Sutarwadi, Pune 411021 (India)], E-mail: ak_sikder@yahoo.com

    2008-11-30

    The thermal decomposition study of CL-20 (hexanitrohexaazaisowurtzitane) using pyrolysis GC/MS was carried out mainly by electron impact (EI) mode. Chemical ionization (CI) mode was used for further confirmation of identified species. Mass spectrum of CL-20 decomposition products predominantly revealed fragments with m/z 81 and 96 corresponding to C{sub 4}H{sub 5}N{sub 2}{sup +} and C{sub 4}H{sub 4}N{sub 2}O{sup +} ions, respectively. The total ion chromatogram (TIC) of CL-20 pyrolysis shows peak within first 2 min due to the presence of low molecular weight gases. Peaks corresponding to several other products were also observed including the atmospheric gases. Cyanogen formation (C{sub 2}N{sub 2}, m/z 52) observed to be enriched at the scan number 300-500. The low molecular mass range decomposition products formed by cleavage of C-N ring structure were found in majority. Additional structural information was sought by employing chemical ionization mode. The data generated during this study was instrumented in determining decomposition pathways of CL-20.

  12. Efficacy of thermal treatment and copper-silver ionization for controlling Legionella pneumophila in high-volume hot water plumbing systems in hospitals.

    Science.gov (United States)

    Mietzner, S; Schwille, R C; Farley, A; Wald, E R; Ge, J H; States, S J; Libert, T; Wadowsky, R M; Miuetzner, S

    1997-12-01

    Thermal treatment and copper-silver ionization are often used for controlling Legionella pneumophila in high-volume hospital plumbing systems, although the comparative efficacies of these measures in high-volume systems are unknown. Thermal treatment of a hot water circuit was accomplished by flushing hot water (> 60 degrees C) through distal fixtures for 10 minutes. Copper-silver ionization was conducted in three circuits by installing units into return lines immediately upstream from hot water tanks. Recovery rates of L. pneumophila were monitored by culturing swab samples from faucets. Concentrations of copper and silver in water samples were determined by atomic absorption spectrophotometry. Four heat-flush treatments failed to provide long-term control of L. pneumophila. In contrast, ionization treatment reduced the rate of recovery of L. pneumophila from 108 faucets from 72% to 2% within 1 month and maintained effective control for at least 22 months. Only three samples (1.9%) of hot water from faucets exceeded Environmental Protection Agency standards for silver, and none exceeded the standards for copper. Of 24 samples obtained from hot water tanks, 42% and 50% exceeded the silver and copper standards, respectively. Copper-silver ionization effectively controls L. pneumophila in high-volume plumbing systems and is superior to thermal treatment; however, high concentrations of copper and silver can accumulate at the bottom of hot water tanks.

  13. Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

    Science.gov (United States)

    Liao, Wenta; Draper, William M

    2013-02-21

    The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of Search Engine and details performance testing with over 50 model compounds.

  14. Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

    Science.gov (United States)

    Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

    2011-05-15

    In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone. Copyright © 2011 John Wiley & Sons, Ltd.

  15. Alternative two-step matrix application method for imaging mass spectrometry to avoid tissue shrinkage and improve ionization efficiency.

    Science.gov (United States)

    Shimma, Shuichi; Takashima, Yuki; Hashimoto, Jun; Yonemori, Kan; Tamura, Kenji; Hamada, Akinobu

    2013-12-01

    Mass spectrometry (MS) was used to measure the concentrations of drug and biological compounds in plasma and tissues. Matrix-assisted laser desorption/ionization (MALDI) imaging MS (IMS) has recently been applied to the analysis of localized drugs on biological tissue surfaces. In MALDI-IMS, matrix application process is crucial for successful results. However, it is difficult to obtain homogeneous matrix crystals on the tissue surface due to endogenous salts and tissue surface heterogeneity. Consequently, the non-uniform crystals degrade the quality of the spectrum and likely cause surface imaging artifacts. Furthermore, the direct application of matrix solution can cause tissue shrinkage due to the organic solvents. Here, we report an alternative two-step matrix application protocol which combines the vacuum deposition of matrix crystals and the spraying of matrix solution to produce a homogeneous matrix layer on the tissue surface. Our proposed technique can also prevent cracking or shrinking of the tissue samples and improve the ionization efficiency of the distributed exogenous material. Copyright © 2013 John Wiley & Sons, Ltd.

  16. Fluctuating feedback-regulated escape fraction of ionizing radiation in low-mass, high-redshift galaxies

    Science.gov (United States)

    Trebitsch, Maxime; Blaizot, Jérémy; Rosdahl, Joakim; Devriendt, Julien; Slyz, Adrianne

    2017-09-01

    Low-mass galaxies are thought to provide the bulk of the ionizing radiation necessary to reionize the Universe. The amount of photons escaping the galaxies is poorly constrained theoretically, and difficult to measure observationally. Yet it is an essential parameter of reionization models. We study in detail how ionizing radiation can leak from high-redshift galaxies. For this purpose, we use a series of high-resolution radiation hydrodynamics simulations, zooming on three dwarf galaxies in a cosmological context. We find that the energy and momentum input from the supernova explosions has a pivotal role in regulating the escape fraction by disrupting dense star-forming clumps, and clearing sightlines in the halo. In the absence of supernovae, photons are absorbed very locally, within the birth clouds of massive stars. We follow the time evolution of the escape fraction and find that it can vary by more than six orders of magnitude. This explains the large scatter in the value of the escape fraction found by previous studies. This fast variability also impacts the observability of the sources of reionization: a survey even as deep as M1500 = -14 would miss about half of the underlying population of Lyman-continuum emitters.

  17. Imaging of Phospholipids in Formalin Fixed Rat Brain Sections by Matrix Assisted Laser Desorption/Ionization Mass Spectrometry

    Science.gov (United States)

    Carter, Claire L.; McLeod, Cameron W.; Bunch, Josephine

    2011-11-01

    Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a valuable tool for the analysis of molecules directly from tissue. Imaging of phospholipids is gaining widespread interest, particularly as these lipids have been implicated in a variety of pathologic processes. Formalin fixation (FF) is the standard protocol used in histology laboratories worldwide to preserve tissue for analysis, in order to aid in the diagnosis and prognosis of diseases. This study assesses MALDI imaging of phospholipids directly in formalin fixed tissue, with a view to future analysis of archival tissue. This investigation proves the viability of MALDI-MSI for studying the distribution of lipids directly in formalin fixed tissue, without any pretreatment protocols. High quality molecular images for several phosphatidylcholine (PC) and sphingomyelin (SM) species are presented. Images correspond well with previously published data for the analysis of lipids directly from freshly prepared tissue. Different ionization pathways are observed when analyzing fixed tissue compared with fresh, and this change was found to be associated with formalin buffers employed in fixation protocols. The ability to analyze lipids directly from formalin fixed tissue opens up new doors in the investigation of disease profiles. Pathologic specimens taken for histologic investigation can be analyzed by MALDI-MS to provide greater information on the involvement of lipids in diseased tissue.

  18. Application of difference NOE-pumping NMR technique and cold-spray ionization mass spectrometry to identify a ligand binding with a protein receptor.

    Science.gov (United States)

    Seki, Hiroko; Sei, Yoshihisa; Shikii, Kazuaki; Shimotakahara, Sakurako; Utsumi, Hiroaki; Yamaguchi, Kentaro; Tashiro, Mitsuru

    2004-10-01

    A difference diffusion-based NMR technique and cold-spray ionization mass spectrometry were employed as a solution-based approach for identifying a ligand binding with a protein receptor. The difference diffusion-based NMR technique, called difference NOE-pumping, can directly detect the ligand interacting with a protein receptor. This technique uses a simple pulse sequence and the diffusion filter can easily be optimized. The cold-spray ionization mass spectrometry (CSI-MS), a variant of electrospray ionization mass spectrometry (ESI-MS) operating at low temperature, has been applied to detect the ligand-receptor complex. The efficiency of these techniques for identifying binding ligands is demonstrated with the human serum albumin (HSA)-drug system.

  19. Laser diode thermal desorption mass spectrometry for the analysis of quinolone antibiotic residues in aquacultured seafood.

    Science.gov (United States)

    Lohne, Jack J; Andersen, Wendy C; Clark, Susan B; Turnipseed, Sherri B; Madson, Mark R

    2012-12-30

    Veterinary drug residue analysis of meat and seafood products is an important part of national regulatory agency food safety programs to ensure that consumers are not exposed to potentially dangerous substances. Complex tissue matrices often require lengthy extraction and analysis procedures to identify improper animal drug treatment. Direct and rapid analysis mass spectrometry techniques have the potential to increase regulatory sample analysis speed by eliminating liquid chromatographic separation. Flumequine, oxolinic acid, and nalidixic acid were extracted from catfish, shrimp, and salmon using acidified acetonitrile. Extracts were concentrated, dried onto metal sample wells, then rapidly desorbed (6 s) with an infrared diode laser for analysis by laser diode thermal desorption atmospheric pressure chemical ionization with tandem mass spectrometry (LDTD-MS/MS). Analysis was conducted in selected reaction monitoring mode using piromidic acid as internal standard. Six-point calibration curves for each compound in extracted matrix were linear with r(2) correlation greater than 0.99. The method was validated by analyzing 23 negative samples and 116 fortified samples at concentrations of 10, 20, 50, 100, and 600 ng/g. Average recoveries of fortified samples were greater than 77% with method detection levels ranging from 2 to 7 /g. Three product ion transitions were acquired per analyte to identify each residue. A rapid method for quinolone analysis in fish muscle was developed using LDTD-MS/MS. The total analysis time was less than 30 s per sample; quinolone residues were detected below 10 ng/g and in most cases residue identity was confirmed. This represents the first application of LDTD to tissue extract analysis. Published 2012. This article is a US Government work and is in the public domain in the USA. Published 2012. This article is a US Government work and is in the public domain in the USA.

  20. High resolution detection of high mass proteins up to 80,000 Da via multifunctional CdS quantum dots in laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Ke, Yaotang; Kailasa, Suresh Kumar; Wu, Hui-Fen; Chen, Zhen-Yu

    2010-11-15

    CdS quantum dots (∼ 5 nm) are used as multifunctional nanoprobes as an effective matrix for large proteins, peptides and as affinity probes for the enrichment of tryptic digest proteins (lysozyme, myoglobin and cytochrome c) in laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). The use of CdS quantum dots (CdS QDs) as the matrix allows acquisition of high resolution LDI mass spectra for large proteins (5000-80,000 Da). The enhancement of mass resolution is especially notable for large proteins such as BSA, HSA and transferrin (34-49 times) when compared with those obtained by using SA as the matrix. This technique demonstrates the potentiality of LDI-TOF-MS as an appropriate analytical tool for the analysis of high-molecular-weight biomolecules with high mass resolution. In addition, CdS QDs are also used as matrices for background-free detection of small biomolecules (peptides) and as affinity probes for the enrichment of tryptic digest proteins in LDI-TOF-MS. Copyright © 2010 Elsevier B.V. All rights reserved.

  1. Mass fingerprint analysis of spider mites (Acari) by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for rapid discrimination.

    Science.gov (United States)

    Kajiwara, Hideyuki; Hinomoto, Norihide; Gotoh, Tetsuo

    2016-04-30

    Discrimination of spider mite species is still performed using morphological information, although DNA and other biological approaches have been attempted for identification purposes. These techniques need much time, are expensive, and require specialist staff. As an alternative, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis is applied for rapid discrimination of spider mite species. Spider mites were analyzed using MALDI-TOFMS after extraction with 70% formic acid and acetonitrile. A single spider mite was also analyzed directly on double-sided carbon tape. A dendrogram was compiled from the MS data. Evolutionarily close and morphologically similar spider mites, the Kanzawa (Tetranychus kanzawai) and the two-spotted (T. urticae) spider mites, as well as three other related species of spider mites, could be discriminated by mass fingerprints. Although female adults were mainly used in this report, male adults and nymphs showed almost the same mass fingerprints and were not considered to affect discrimination capability. A single spider mite on double-sided carbon tape was analyzed directly by MALDI-TOFMS. Spider mites could be analyzed directly by MALDI-TOFMS, with evolutionarily and morphologically closely related spider mites showing different mass fingerprints, allowing for their identification. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Quantitative analysis of methadone in biological fluids using deuterium-labeled methadone and GLC-chemical-ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Hackey, D.L. (Argonne National Lab., IL); Kreek, M.J.; Mattson, D.H.

    1977-11-01

    The (+)-, (-)-, and (+-)-/sup 2/H/sub 5/-methadones, which contained five deuterium atoms in one aromatic ring, were synthesized for use in clinical pharmacological studies and as internal standards. GLC--chemical-ionization mass spectrometry was used to determine plasma and urinary methadone levels by an inverse isotope dilution assay. Plasma drug levels could be determined to 10 pmoles/ml, and urine levels could be measured to 5 pmoles/ml. Plasma methadone levels were examined in several patients undergoing methadone maintenance therapy. These levels generally ranged between 100 and 400 ng/ml (320 to 1300 pmoles/ml) after an average oral dose of 1 mg/kg/day. The methadone half-life was 28.8 +- 4.8 hr.

  3. Probing regA/RNA interactions using electrospray ionization-Fourier transform ion cyclotron resonance-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C.; Tolic, L.P.; Hofstadler, S.A.; Harms, A.C.; Smith, R.D. [Pacific Northwest National Lab., Richland, WA (United States). Environmental Molecular Sciences Lab.; Kang, C.H. [Washington State Univ., Pullman, WA (United States). Dept. of Biochemistry and Biophysics; Sinha, N. [Boston Biosystems, Inc., Bedford, MA (United States)

    1998-08-15

    The interactions of bacteriophage T4 regA protein, a unique translational regulator, with RNAs of various size and sequence were studied using electrospray ionization-Fourier transform ion cyclotron resonance-mass spectrometry. Using very gentle interface conditions, regA/RNA complexes with a 1:1 binding stoichiometry were observed for all four target RNAs studied, consistent with solution binding studies. Competitive binding of target RNAs and their degradation products with regA demonstrated that the loss of a single nucleotide resulted in a dramatic change in binding affinity in some cases. Competitive binding of regA with four target RNAs revealed similar relative binding affinity order to that suggested by previous in vitro repression experiments. The use of sustained off-resonance irradiation for collisionally induced dissociation of a regA/RNA complex suggested the potential for directly obtaining information regarding the regA binding domain.

  4. Perfume fingerprinting by easy ambient sonic-spray ionization mass spectrometry: nearly instantaneous typification and counterfeit detection.

    Science.gov (United States)

    Haddad, Renato; Catharino, Rodrigo Ramos; Marques, Lygia Azevedo; Eberlin, Marcos Nogueira

    2008-11-01

    Perfume counterfeiting is an illegal worldwide practice that involves huge economic losses and potential consumer risk. EASI is a simple, easily performed and rapidly implemented desorption/ionization technique for ambient mass spectrometry (MS). Herein we demonstrate that EASI-MS allows nearly instantaneous perfume typification and counterfeit detection. Samples are simply sprayed onto a glass rod or paper surface and, after a few seconds of ambient drying, a profile of the most polar components of the perfume is acquired. These components provide unique and reproducible chemical signatures for authentic perfume samples. Counterfeiting is readily recognized since the exact set and relative proportions of the more polar chemicals, sometimes at low concentrations, are unknown or hard to reproduce by the counterfeiters and hence very distinct and variable EASI-MS profiles are observed for the counterfeit samples.

  5. Rapid discrimination of environmental Vibrio by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Eddabra, Rkia; Prévost, Gilles; Scheftel, Jean-Michel

    2012-04-20

    The aim of this study was to discriminate 30 Vibrio strains isolated from two wastewater treatment plants from Agadir, Morocco by two molecular typing methods, pulsed-field gel electrophoresis (PFGE) and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Out of the 30 strains of Vibrio examined in this study, 5 isolates could not be typed by PFGE and consistently appeared as a smear on the gel. In general, high genetic biodiversity among the Vibrio strains was found regardless to the isolation source. The results of MALDI TOF analysis show a high congruence of strain grouping demonstrating the accuracy and reliability of MALDI-TOF MS. Copyright © 2011 Elsevier GmbH. All rights reserved.

  6. Use of novel picolinoyl derivatization for simultaneous quantification of six corticosteroids by liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Yamashita, Kouwa; Takahashi, Madoka; Tsukamoto, Satoshi; Numazawa, Mitsuteru; Okuyama, Mitsunobu; Honma, Seijiro

    2007-11-30

    Simultaneous quantification method of six corticosteroids, cortisone, cortisol, cortexolone, corticosterone, dehydrocorticosterone and deoxycorticosterone, by LC-electrospray ionization (ESI)-MS in a positive mode using novel picolinoyl derivatization was investigated. Conversion of each corticosteroid into the corresponding picolinoyl derivative was performed by mixed anhydride method using picolinic acids and 2-methyl-6-nitrobenzoic anhydride. Derivatization proceeded smoothly to afford the corresponding 21-monopicolinoyl derivatives. Positive ion-ESI mass spectra of the picolinoyl derivatives were dominated by the appearance of [M+H](+) as base peaks. The picolinoyl derivatives provided 5-10 times higher ESI response in the LC-ESI-MS-selected reaction monitoring (SRM) when compared to those of underivatized molecules in a positive LC-ESI-MS mode. The use of the picolinoyl ester, solid-phase extraction, and deuterium labeled internal standards enabled to determine the concentrations of these corticosteroids in human saliva simultaneously by LC-ESI-MS-SRM.

  7. 5-Methoxysalicylic Acid Matrix for Ganglioside Analysis with Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

    Science.gov (United States)

    Lee, Dongkun; Cha, Sangwon

    2015-03-01

    In this note, we report that high quality ganglioside profiles with minimal loss of sialic acid residues can be obtained in the positive ion mode by using a 5-methoxysalicylic acid (MSA) matrix for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Our results showed that MSA produced much less sialic acid losses from gangliosides than DHB, although MSA and DHB are differ only by their functional groups at their 5-positions (-OH for DHB and -OCH3 for MSA). Furthermore, our data also demonstrated that addition of an alkali metal additive was effective for simplifying ganglioside profiles, but not necessary for stabilizing glycosidic bonds of gangliosides if MSA was used as a matrix. This suggests that MALDI MS with MSA has a potential to gain additional benefits from the positive-ion mode analyses without losing performance in ganglioside profiling.

  8. A highly sensitive carbapenemase assay using laser desorption/ionization mass spectrometry based on a parylene-matrix chip.

    Science.gov (United States)

    Park, Jong-Min; Kim, Jo-Il; Noh, Joo-Yoon; Kim, Mira; Kang, Min-Jung; Pyun, Jae-Chul

    2017-09-01

    A quantitative carbapenemase assay was developed using laser desorption/ionization mass spectrometry (LDI-MS) based on a parylene-matrix chip. As a first step, the reproducibility (spot-to-spot, shot-to-shot, and day-to-day) of LDI-MS based on a parylene-matrix chip and the quantification ranges for four carbapenem antibiotics (doripenem, ertapenem, imipenem, and meropenem) were determined. A carbapenem-susceptibility test was performed using the four carbapenems and 51 bacterial strains that displayed (1) carbapenem resistance with carbapenemase, (2) carbapenem resistance without carbapenemase, or (3) carbapenem susceptibility. The susceptibility test results showed that LDI-MS based on a parylene-matrix chip was more sensitive and selective for detecting the carbapenemase reaction than conventional MALDI-TOF MS based on a 2,5-dihydroxybenzoic acid matrix. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Compact ultrafast orthogonal acceleration time-of-flight mass spectrometer for on-line gas analysis by electron impact ionization and soft single photon ionization using an electron beam pumped rare gas excimer lamp as VUV-light source.

    Science.gov (United States)

    Mühlberger, F; Saraji-Bozorgzad, M; Gonin, M; Fuhrer, K; Zimmermann, R

    2007-11-01

    Orthogonal acceleration time-of-flight mass spectrometers (oaTOFMS), which are exhibiting a pulsed orthogonal extraction of ion bunches into the TOF mass analyzer from a continuous primary ion beam, are well-suited for continuous ionization methods such as electron impact ionization (EI). Recently an electron beam pumped rare gas excimer lamp (EBEL) was introduced, which emits intensive vacuum UV (VUV) radiation at, e.g., 126 nm (argon excimer) and is well suited as the light source for soft single photon ionization (SPI) of organic molecules. In this paper, a new compact oaTOFMS system which allows switching between SPI, using VUV-light from an EBEL-light source, and conventional EI is described. With the oaTOFMS system, EBEL-SPI and EI mass spectral transients can be recorded at very high repetition rates (up to 100 kHz), enabling high duty cycles and therefore good detection efficiencies. By using a transient recorder card with the capability to perform on-board accumulation of the oaTOF transients, final mass spectra with a dynamic range of 106 can be saved to the hard disk at a rate of 10 Hz. As it is possible to change the ionization modes (EI and SPI) rapidly, a comprehensive monitoring of complex gases with highly dynamic compositions, such as cigarette smoke, is possible. In this context, the EI based mass spectra address the bulk composition (compounds such as water, oxygen, carbon dioxide, etc. in the up to percentage concentration range) as well as some inorganic trace gases such as argon, sulfur dioxide, etc. down to the low ppm level. The EBEL-SPI mass spectra on the other hand are revealing the organic composition down to the lower ppb concentration range.

  10. Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis

    Science.gov (United States)

    Nahan, Keaton S.; Alvarez, Noe; Shanov, Vesselin; Vonderheide, Anne

    2017-09-01

    Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R2) of three target PAHs with phenanthrene internal standard. [Figure not available: see fulltext.

  11. Chemical analysis of raw and processed Fructus arctii by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry

    Science.gov (United States)

    Qin, Kunming; Liu, Qidi; Cai, Hao; Cao, Gang; Lu, Tulin; Shen, Baojia; Shu, Yachun; Cai, Baochang

    2014-01-01

    Background: In traditional Chinese medicine (TCM), raw and processed herbs are used to treat the different diseases. Fructus Arctii, the dried fruits of Arctium lappa l. (Compositae), is widely used in the TCM. Stir-frying is the most common processing method, which might modify the chemical compositions in Fructus Arctii. Materials and Methods: To test this hypothesis, we focused on analysis and identification of the main chemical constituents in raw and processed Fructus Arctii (PFA) by high-performance liquid chromatography/diode array detection-electrospray ionization-mass spectrometry. Results: The results indicated that there was less arctiin in stir-fried materials than in raw materials. however, there were higher levels of arctigenin in stir-fried materials than in raw materials. Conclusion: We suggest that arctiin reduced significantly following the thermal conversion of arctiin to arctigenin. In conclusion, this finding may shed some light on understanding the differences in the therapeutic values of raw versus PFA in TCM. PMID:25422559

  12. Development of a liquid chromatography-electrospray ionization-tandem mass spectrometry method for the simultaneous analysis of intact glucosinolates and isothiocyanates in Brassicaceae seeds and functional foods.

    Science.gov (United States)

    Franco, P; Spinozzi, S; Pagnotta, E; Lazzeri, L; Ugolini, L; Camborata, C; Roda, A

    2016-01-08

    A new high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry method for the simultaneous determination of glucosinolates, as glucoraphanin and glucoerucin, and the corresponding isothiocyanates, as sulforaphane and erucin, was developed and applied to quantify these compounds in Eruca sativa defatted seed meals and enriched functional foods. The method involved solvent extraction, separation was achieved in gradient mode using water with 0.5% formic acid and acetonitrile with 0.5% formic acid and using a reverse phase C18 column. The electrospray ion source operated in negative and positive mode for the detection of glucosinolates and isothiocyanates, respectively, and the multiple reaction monitoring (MRM) was selected as acquisition mode. The method was validated following the ICH guidelines. Replicate experiments demonstrated a good accuracy (bias%glucosinolates and isothiocyanates determination both in biomasses and in complex matrices such as food products enriched with glucosinolates, or nutraceutical bakery products. In addition, the developed method was applied to the simultaneous determination of glucosinolates and isothiocyanates in bakery product enriched with glucosinolates, to evaluate their thermal stability after different industrial processes from cultivation phases to consumer processing. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Efficient mass-selective three-photon ionization of zirconium atoms

    Science.gov (United States)

    Page, Ralph H.

    1994-01-01

    In an AVLIS process, .sup.91 Zr is selectively removed from natural zirconium by a three-step photoionization wherein Zr atoms are irradiated by a laser beam having a wavelength .lambda..sub.1, selectively raising .sup.91 Zr atoms to an odd-parity E.sub.1 energy level in the range of 16000-19000 cm.sup.-1, are irradiated by a laser beam having a wavelength .lambda..sub.2 to raise the atoms from an E.sub.l level to an even-parity E.sub.2 energy level in the range of 35000-37000 cm.sup.-1 and are irradiated by a laser beam having a wavelength .lambda..sub.3 to cause a resonant transition of atoms from an E.sub.2 level to an autoionizing level above 53506 cm.sup.-1. .lambda..sub.3 wavelengths of 5607, 6511 or 5756 .ANG. will excite a zirconium atom from an E.sub.2 energy state of 36344 cm.sup.-1 to an autoionizing level; a .lambda..sub.3 wavelength of 5666 .ANG. will cause an autoionizing transition from an E.sub.2 level of 36068 cm.sup.-1 ; and a .lambda. .sub.3 wavelength of 5662 .ANG. will cause an ionizing resonance of an atom at an E.sub.2 level of 35904 cm.sup.-1.

  14. Laser Desorption/Ionization Mass Spectrometry (LDI-MS) of Lipids with Iron Oxide Nanoparticle-Coated Targets.

    Science.gov (United States)

    Kusano, Maiko; Kawabata, Shin-Ichirou; Tamura, Yusuke; Mizoguchi, Daigou; Murouchi, Masato; Kawasaki, Hideya; Arakawa, Ryuichi; Tanaka, Koichi

    2014-01-01

    Iron oxide nanoparticle (NP)-coated target plates were employed for the direct detection and analysis of low molecular weight lipids by laser desorption/ionization (LDI) mass spectrometry (MS). We have demonstrated that the use of the iron oxide NP-coated target provides a simple, direct, and rapid detection method for lipid standards and epidermal surface lipids without any cumbersome sample pretreatment as well as mass spectra that are free of background matrix peaks. Lipid standards (1-stearoyl-sn-glycero-3-phosphocholine, 1,2-dioleoyl-sn-glycerol, 1-palmitoyl-2-oleoyl-3-linoleoyl-rac-glycerol, 1,2-distearoyl-sn-glycero-3-phosphocholine) were detected as either protonated or cationated species. Clean MS/MS spectra for each lipid were also successfully obtained. Pre-MS surface cleaning of the target plates with UV-ozone treatment successfully removed organic contaminants that would interfere with the mass spectra especially in the low molecular weight region. Preliminary application of the presented target plate to the detection of endogenous lipids in latent fingerprints showed promising results and for potential use in the visualization and chemical composition determination of latent fingerprints by nanoparticle assistance.

  15. Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

    2015-02-01

    Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

  16. Synthesis of pyridine-carboxylate derivatives of hydroxysteroids for liquid chromatography-electrospray ionization-mass spectrometry.

    Science.gov (United States)

    Yamashita, Kouwa; Kobayashi, Sayuri; Tsukamoto, Satoshi; Numazawa, Mitsuteru

    2007-01-01

    Synthesis and liquid chromatography-electrospray ionization-mass spectrometric (LC-ESI-MS) behaviors of the picolinoyl, 6-methylpicolinoyl, nicotinoyl, 2-methoxynicotinoyl and isonicotinoyl derivatives of the hydroxysteroids estrone, estradiol, 3beta-hydroxyandrost-5-en-17-one (dehydroepiandrosterone) and testosterone in positive mode were investigated. Each steroid was converted to the corresponding pyridine-carboxylate derivative by the acyl chloride method or the mixed anhydride method using the corresponding free acids and 2-methyl-6-nitrobenzoic anhydride; in each case, the latter method principally gave a better yield. The pyridine-carboxylate derivative of each steroid exhibited a clear single peak in liquid chromatography with a reversed phase column and CH(3)CN-0.1% CH(3)COOH as a mobile phase. The positive-ESI-mass spectra of the picolinoyl, 6-methylpicolinoyl and 2-methoxynicotinoyl derivatives showed a predominance of [M+H](+), whereas [M+H+CH(3)CN](+) was observed with high intensity in the nicotinoyl and isonicotinoyl derivatives. Even in the case of estradiol, with its two hydroxyl groups, a single charged ion of [M+H](+) or [M+H+CH(3)CN](+) was observed in the positive-ESI-mass spectrum of each derivative. The results revealed that picolinoyl derivatization is a simple and versatile method suitable for the sensitive and specific determination of hydroxysteroids by LC-ESI-MS (selected reaction monitoring).

  17. Feasibility of desorption atmospheric pressure photoionization and desorption electrospray ionization mass spectrometry to monitor urinary steroid metabolites during pregnancy.

    Science.gov (United States)

    Vaikkinen, Anu; Rejšek, Jan; Vrkoslav, Vladimír; Kauppila, Tiina J; Cvačka, Josef; Kostiainen, Risto

    2015-06-23

    Steroids have important roles in the progress of pregnancy, and their study in maternal urine is a non-invasive method to monitor the steroid metabolome and its possible abnormalities. However, the current screening techniques of choice, namely immunoassays and gas and liquid chromatography-mass spectrometry, do not offer means for the rapid and non-targeted multi-analyte studies of large sample sets. In this study, we explore the feasibility of two ambient mass spectrometry methods in steroid fingerprinting. Urine samples from pregnant women were screened by desorption electrospray ionization (DESI) and desorption atmospheric pressure photoionization (DAPPI) Orbitrap high resolution mass spectrometry (HRMS). The urine samples were processed by solid phase extraction for the DESI measurements and by enzymatic hydrolysis and liquid-liquid-extraction for DAPPI. Consequently, steroid glucuronides and sulfates were detected by negative ion mode DESI-HRMS, and free steroids by positive ion mode DAPPI-HRMS. In DESI, signals of eleven steroid metabolite ions were found to increase as the pregnancy proceeded, and in DAPPI ten steroid ions showed at least an order of magnitude increase during pregnancy. In DESI, the increase was seen for ions corresponding to C18 and C21 steroid glucuronides, while DAPPI detected increased excretion of C19 and C21 steroids. Thus both techniques show promise for the steroid marker screening in pregnancy. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. The protein profile of Theobroma cacao L. seeds as obtained by matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Bertazzo, Antonella; Agnolin, Fabio; Comai, Stefano; Zancato, Mirella; Costa, Carlo V L; Seraglia, Roberta; Traldi, Pietro

    2011-07-30

    The water-soluble protein profile of the seeds of green, red, and yellow Theobroma cacao L. fruits has been determined by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS). The seeds were powdered under liquid nitrogen and defatted. The residues were dialyzed and lyophilized. The obtained samples were suspended in the matrix solution of sinapinic acid. The obtained MALDI mass spectra showed the presence of a wide number of proteins with molecular weight ranging from 8000 to 13,000 Da and a cluster of peaks centered at 21,000 Da that were attributed to albumin. The abundance of this peak was found to depend on the different portion of the seed (husk, apical and cortical parts); however, the MALDI mass spectra obtained from the different varieties of cocoa were practically superimposable. Changes in the protein profiles were also observed after the cocoa seeds were treated by fermentation and roasting, which are processes usually employed for the commercial production of cocoa. Copyright © 2011 John Wiley & Sons, Ltd.

  19. VUV photon-induced ionization/dissociation of antipyrine and propyphenazone: mass spectrometric and theoretical insights.

    Science.gov (United States)

    Deng, Liulin; Zhang, Lidong; Guo, Huijun; Jia, Liangyuan; Pan, Yang; Yin, Hao; Qi, Fei

    2010-07-01

    Two analgesic and anti-inflammatory drugs, antipyrine and propyphenazone, were investigated with infrared laser desorption/tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (IR LD/VUV PIMS) and theoretical calculations. Mass spectra of the two drugs were measured at various photon energies. Fragment ions were gradually produced as photon energy increases. The structural assignment of the dominant fragment ions was supported by the results from a commercial electron impact time-of-flight mass spectrometer (EI-TOF MS). Primary fragmentation pathways were established from experimental observations combining with theoretical calculations. Methyl radical elimination is a common fragmentation pathway for two analytes. However, for propyphenazone cation, isopropyl group elimination to form antipyrine cation is another competitive pathway. 2010 John Wiley & Sons, Ltd.

  20. Thermal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrometry for investigating secondary organic aerosols in chamber experiments.

    Science.gov (United States)

    Fang, Wenzheng; Gong, Lei; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

    2011-12-01

    This paper describes thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for the real-time analysis of secondary organic aerosols (SOAs) in smog chamber experiments. SOAs are sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. Once the particles have entered the source region, they impact on a heater and are vaporized. The nascent vapor is then softly ionized by tunable VUV synchrotron radiation. TD-VUV-TOF-PIAMS was used in conjunction with the smog chamber to study SOA formation from the photooxidation of toluene with hydroxyl radicals. The ionization energies (IEs) of these SOA products are sometimes very different with each other. As the ideal photon source is tunable, its energy can be adjusted for each molecular to be ionized. The mass spectra obtained at different photon energies are then to be useful for molecular identification. Real-time analysis of the mass spectra of SOAs is compared with previous off-line measurements. These results illustrate the potential of TD-VUV-TOF-PIAMS for direct molecular characterization of SOAs in smog chamber experiments.

  1. The Radio Light Curve of the Gamma-Ray Nova in V407 CYG: Thermal Emission from the Ionized Symbiotic Envelope, Devoured from Within by the Nova Blast

    Science.gov (United States)

    Chomiuk, Laura; Krauss, Miriam I.; Rupen, Michael P.; Nelson, Thomas; Roy, Nirupam; Sokoloski, Jennifer L.; Mukai, Koji; Munari, Ulisse; Mioduszewski, Amy; Weston, Jeninfer; hide

    2012-01-01

    We present multi-frequency radio observations of the 2010 nova event in the symbiotic binary V407 Cygni, obtained with the Karl G. Jansky Very Large Array (VLA) and spanning 1.45 GHz and 17.770 days following discovery. This nova.the first ever detected in gamma rays.shows a radio light curve dominated by the wind of the Mira giant companion, rather than the nova ejecta themselves. The radio luminosity grewas the wind became increasingly ionized by the nova outburst, and faded as the wind was violently heated from within by the nova shock. This study marks the first time that this physical mechanism has been shown to dominate the radio light curve of an astrophysical transient. We do not observe a thermal signature from the nova ejecta or synchrotron emission from the shock, due to the fact that these components were hidden behind the absorbing screen of the Mira wind. We estimate a mass-loss rate for the Mira wind of .Mw approximately equals 10(exp -6) Solar mass yr(exp -1). We also present the only radio detection of V407 Cyg before the 2010 nova, gleaned from unpublished 1993 archival VLA data, which shows that the radio luminosity of the Mira wind varies by a factor of 20 even in quiescence. Although V407 Cyg likely hosts a massive accreting white dwarf, making it a candidate progenitor system for a Type Ia supernova, the dense and radially continuous circumbinary material surrounding V407 Cyg is inconsistent with observational constraints on the environments of most Type Ia supernovae.

  2. Phenotypic identification of Porphyromonas gingivalis validated with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Rams, Thomas E; Sautter, Jacqueline D; Getreu, Adam; van Winkelhoff, Arie J

    2016-05-01

    Porphyromonas gingivalis is a major bacterial pathogen in human periodontitis. This study used matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry to assess the accuracy of a rapid phenotypic identification scheme for detection of cultivable P. gingivalis in human subgingival plaque biofilms. A total of 314 fresh cultivable subgingival isolates from 38 adults with chronic periodontitis were presumptively identified on anaerobically-incubated enriched Brucella blood agar primary isolation plates as P. gingivalis based on dark-pigmented colony morphology, lack of a brick-red autofluorescence reaction under long-wave ultraviolet light, and a positive CAAM fluorescence test for trypsin-like enzyme activity. Each presumptive P. gingivalis isolate, and a panel of other human subgingival bacterial species, were subjected to MALDI-TOF mass spectrometry analysis using a benchtop mass spectrometer equipped with software containing mass spectra for P. gingivalis in its reference library of bacterial protein profiles. A MALDI-TOF mass spectrometry log score of ≥1.7 was required for species identification of the subgingival isolates. All 314 (100%) presumptive P. gingivalis subgingival isolates were confirmed as P. gingivalis with MALDI-TOF mass spectrometry analysis (Cohen's kappa coefficient = 1.0). MALDI-TOF mass spectrometry log scores between 1.7 and 1.9, and ≥2.0, were found for 92 (29.3%) and 222 (70.7%), respectively, of the presumptive P. gingivalis clinical isolates. No other tested bacterial species was identified as P. gingivalis by MALDI-TOF mass spectrometry. Rapid phenotypic identification of cultivable P. gingivalis in human subgingival biofilm specimens was found to be 100% accurate with MALDI-TOF mass spectrometry. These findings provide validation for the continued use of P. gingivalis research data based on this species identification methodology. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Mass accuracy improvement of reversed-phase liquid chromatography/electrospray ionization mass spectrometry based urinary metabolomic analysis by post-run calibration using sodium formate cluster ions.

    Science.gov (United States)

    Juo, Chiun-Gung; Chen, Chien-Lun; Lin, Shiang-Ting; Fu, Shu-Hsuan; Chen, Yi-Ting; Chang, Yu-Sun; Yu, Jau-Song

    2014-08-30

    Typically, a batch metabolomics analysis using liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOF MS) takes 2 to 3 days. However, the mass accuracy - which has an important influence on metabolite identification - can drift by as much as about 17 ppm in such a time period. In an untargeted urinary metabolomics analysis by reversed-phase liquid chromatography (RPLC)/ESI-MS, the signals of sodium formate cluster ions were detected at the column-washing step. The cluster ions were used to calibrate the mass spectrometer for more accurate detection. The spectra were calibrated post-run by the sodium formate cluster ions, which were used as the internal standard, in order to improve the mass accuracy. In the analysis of urine samples, we calibrated the spectra acquired by the micrOTOF with the sodium cluster ions. In positive mode ESI, the average errors of these cluster ions were improved to ±0.48 ppm and in negative mode ESI, to ±0.94 ppm after calibration. The mass accuracy remained within ±0.01 ppm over the duration of 6.25 days. An error window of 4 ppm appears to be suitable for metabolite identification when using post-calibration. The results showed that sodium formate cluster ions could be utilized for the calibration of LC/ESI-TOF MS and the average instrumental errors could be maintained at low levels for long-term analyses. This method could be applied not only to urine sample, but also to low sodium samples, such as saliva, by dissolving the sample in 1 μM sodium formate solution. This method provides a good solution for accurate mass detection of metabolomic analysis. Copyright © 2014 John Wiley & Sons, Ltd.

  4. Dimer ion formation and intermolecular fragmentation of 1,2-diacylglycerols revealed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for more comprehensive lipid analysis.

    Science.gov (United States)

    Müller, Constanze; Kanawati, Basem; Rock, Theresa M; Forcisi, Sara; Moritz, Franco; Schmitt-Kopplin, Philippe

    2014-08-15

    The ionization of neutral diacylglycerols (DAGs) by electrospray ionization mass spectrometry (ESI-MS) is challenging compared with other lipid classes which possess ionic head group conjugations. Although ESI-MS is the method of choice in lipidomic analysis, it is questionable whether all lipid classes can be efficiently ionized by this method. Actually, various lipids were not efficiently detected (due to poor ionization) in many studies which claimed to comprehensively describe lipid profiles. Since neutral lipids are precursors for the biosynthesis of most other lipid classes, the necessity for improved or alternative ionization and identification schemes becomes obvious. We identified the 1,2-diacylglycerol (DAG) dimer ion formation in the gas phase by ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in negative electrospray ionization ((-)ESI) mode. The geometry of the dimer ion was investigated by accurate density functional theory (DFT) calculations at the B3LYP/6-311+G(d)//B3LYP/LANL2DZ level of theory. Fragmentation of the dimer ions of many investigated DAGs has been achieved via collision-induced dissociation (CID) experiments with several elevated collision energies (0-12 eV). We revealed the possibility to ionize neutral DAGs as dimer ions in the negative ESI mode. Quantum mechanical calculations revealed a polar head-to-head intermolecular interaction between one charged DAG and one DAG neutral. This represents an energy minimum structure for the DAG dimer ions. We could furthermore detect CID fragmentation product ions that can only result from intermolecular reactions in this head-to-head conformation (SN2 nucleophilic substitution reactions inside the dimer DAG ion). Here, we present for the first time the opportunity to ionize and identify DAGs as dimer ions. This new finding provides a new alternative for investigations of important diacylglycerol lipids and provides the opportunity to obtain

  5. Analysis of degradation products of PAH and PCP using electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Pavlovich, J.G.; Stringfellow, W.; Kazunga, Chikoma; Aitken, M.D.; Charles, M.J. [Univ. of North Carolina, Chapel Hill, NC (United States)

    1994-12-31

    Bioremediation is an important strategy for the clean-up of hazardous waste sites. In the past, assessing the efficacy of bioremediation techniques has involved monitoring the disappearance of the pollutant with minimal regard to the products formed via microbial degradation of the initial contaminant. Aromatic hydrocarbons in the environment are subject to oxidation by a variety of mechanisms including photooxidation, microbial degradation and metabolism by higher organisms. These processes result in an array of oxygenated products including hydroxylated aromatics, ketones, quinones, and acids. In many animals, metabolically activated PAH bind covalently to cellular species including sulfate, glucuronic acid, glutathione, as well as proteins and DNA. In some cases, the oxygenated species have been shown to be more highly toxic than the parent hydrocarbon. Measures directed at either controlling the migration of toxic microbial metabolites, or precluding their formation in the first place, can be developed intelligently if the chemical characteristics of the toxic can be determined. It is, therefore, desirable to characterize fully the degradation products present in environmental samples not only as a means of elucidating the degradation pathways, but in order to assess the full hazard represented by the contamination and the effectiveness of the clean-up protocols employed. Conventional GC/MS techniques often require extensive sample clean-up and fractionation, while the more polar metabolites are intractable to GC altogether. Since electrospray ionization is well suited to analysis of such polar nonvolatile compounds, as well as compatible with HPLC clean-up and separations, the authors are applying this technique to the analysis of polar degradation products of aromatic hydrocarbons including polycyclic aromatic hydrocarbons and chlorinated phenols.

  6. Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Cha, Eunju; Kim, Sohee; Kim, Hee Won; Lee, Kang Mi; Kim, Ho Jun; Kwon, Oh-Seung; Lee, Jaeick

    2016-04-01

    The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Evaluation of phenylthiocarbamoyl-derivatized peptides by electrospray ionization mass spectrometry: selective isolation and analysis of modified multiply charged peptides for liquid chromatography-tandem mass spectrometry experiments.

    Science.gov (United States)

    Sanchez, Aniel; Perez-Riverol, Yasset; González, Luis Javier; Noda, Jesus; Betancourt, Lazaro; Ramos, Yassel; Gil, Jeovanis; Vera, Roberto; Padrón, Gabriel; Besada, Vladimir

    2010-10-15

    Edman degradation in the gas phase has been observed by collision activated dissociation of N-terminal phenylthiocarbamoyl (PTC) protonated peptide to yield abundant complementary b₁ and y(n-1) ion pairs. Here, we demonstrated the relation between the observed losses of aniline and/or the entire PTC derivatizing group with the availability of mobile protons using electrospray ionization mass spectrometry. In order to select the peptides with more efficient fragmentation, while simplifying the mixture of peptides, we extend the phenylisotiocyanate (PITC) derivatization of amino groups to the selective isolation of multiply charged peptides (those having the number of arginines and histidines residues higher than one) using a procedure previously developed in our group. Thus, it was possible to identify in the filtered protein database the sequence of the isolated multiply charged peptides derived from a single protein and a complex mixture of proteins extracted from Escherichia coli using only the molecular mass and the N-terminal amino acid information. For this purpose, we developed a novel bioinformatic tool for automatic identification of peptides from liquid chromatography-tandem mass spectrometry (LC-MS/MS) experiments, which potentially can be used in high-throughput proteomics.

  8. Forensic Analysis of Stains on Fabric Using Direct Analysis in Real-time Ionization with High-Resolution Accurate Mass-Mass Spectrometry.

    Science.gov (United States)

    Kern, Sara E; Crowe, John B; Litzau, Jonathan J; Heitkemper, Douglas T

    2017-06-12

    A rapid technique using direct analysis in real-time (DART) ambient ionization coupled to a high-resolution accurate mass-mass spectrometer (HRAM-MS) was employed to analyze stains on an individual's pants suspected to have been involved in a violent crime. The victim was consuming chocolate ice cream at the time of the attack, and investigators recovered the suspect's pants exhibiting splatter stains. Liquid chromatography with mass spectral detection (LC-MS) and stereoscopic light microscopy (SLM) were also utilized in this analysis. It was determined that the stains on the pants contained theobromine and caffeine, known components of chocolate. A shard from the ceramic bowl that contained the victim's ice cream and a control chocolate ice cream sample were also found to contain caffeine and theobromine. The use of DART-HRAM-MS was useful in this case due to its rapid analysis capability and because of the limited amount of sample present as a stain. Published 2017. This article is a U.S. Government work and is in the public domain in the USA.

  9. A Study of Heterogeneous Catalysis by Nanoparticle-Embedded Paper-Spray Ionization Mass Spectrometry.

    Science.gov (United States)

    Banerjee, Shibdas; Basheer, Chanbasha; Zare, Richard N

    2016-10-04

    We have developed nanoparticle-embedded paper-spray mass spectrometry for studying three types of heterogeneously catalyzed reactions: 1) Palladium-nanoparticle-catalyzed Suzuki cross-coupling reactions, 2) palladium- or silver-nanoparticle-catalyzed 4-nitrophenol reduction, and 3) gold-nanoparticle-catalyzed glucose oxidation. These reactions were almost instantaneous on the nanocatalyst-embedded paper, which subsequently transferred the transient intermediates and products to a mass spectrometer for their detection. This in situ method of capturing transient intermediates and products from heterogeneous catalysis is highly promising for investigating the mechanism of catalysis and rapidly screening catalytic activity under ambient conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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...... analysis. Illustrated on the direct infusion analysis (ESI-TOF-MS) of complex mixtures the method exploits the full quality of the high-resolution present in the mass spectra. Although the method is illustrated as a new library search method for high resolution MS, we demonstrate that the output...... of the preprocessing is applicable to cluster-, discriminant analysis, and related multivariate methods applied directly to mass spectra from direct infusion analysis of crude extracts. This is done to find the relationship between several terverticillate Penicillium species and identify the ions responsible...

  11. Depth-Resolved Nanospray Desorption Electrospray Ionization Mass Spectrometry in Biofilms

    Science.gov (United States)

    2015-11-16

    photograph of the tip of nano-DESI sensor. Right: A photograph of the nano- DESI sensor with connectors Stepper motor Mass Spectrometry Stepper ...Electrode holder Connected to A stepper motor 4 References Babauta, J.T., Beyenal, H., 2014. Local Current Variation by Depth in Geobacter... motor controller Bulk solution Biofilm solvent 30 µm Nano-DESI sensor solvent MS ~ 30 µm Solvent in Tip of the capillary Operating in the lab To MS

  12. Using electrospray ionization FTICR mass spectrometry to study competitive binding of inhibitors to carbonic anhydrase

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, X.; Chen, R.; Bruce, J.E.; Schwartz, B.L.; Anderson, G.A.; Hofstadler, S.A.; Gale, D.C.; Smith, R.D. [Pacific Northwest Lab., Richland, WA (United States); Gao, J.; Sigal, G.B.; Mammen, M.; Whitesides, G.M. [Harvard Univ., Cambridge, MA (United States)

    1995-08-30

    We report a method based on mass spectrometry for the characterization of noncovalent complexes of proteins with mixtures of ligands; this method is relevant to the study of drug leads and may be useful in screening libraries for tight-binding compounds. This study describes the competitive binding of inhibitors derived from para-substituted benzenesulfonamides to bovine carbonic anhydrase II (BCAII, EC 4.2.1.1) using this technique. Relative binding constants and structural information for a mixture of inhibitors can be obtained in a single experiment using ESI-FTICR-MS. The work demonstrates that ESI-MS has significant potential for measuring relative binding affinities and characterizing the structures of ligands associated noncovalently to proteins. We have detected noncovalent complexes in the gas phase for ligands having values of K{sub b} as low as 1.7 x 10{sup 6} M{sup -1} in solution. The technique also allowed identification of tightbinding ligands from small libraries. The structures of inhibitors having similar masses can be identified by the high-resolution and multistep dissociation mass spectrometry of which FTICR is uniquely capable. This range of capabilities for ESI-FTICR-MS should be widely useful in medicinal chemistry. 22 refs., 2 figs.

  13. Quantitative Thin-Layer Chromatography/Mass Spectrometry Analysis of Caffeine Using a Surface Sampling Probe Electrospray Ionization Tandem Mass Spectrometry System

    Energy Technology Data Exchange (ETDEWEB)

    Ford, Michael J [ORNL; Deibel, Michael A. [Earlham College; Tomkins, Bruce A [ORNL; Van Berkel, Gary J [ORNL

    2005-01-01

    Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 {mu}m/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 {mu}L) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by 8% or more) than the literature values.

  14. Coupling of gas chromatography and electrospray ionization high resolution mass spectrometry for the analysis of anabolic steroids as trimethylsilyl derivatives in human urine.

    Science.gov (United States)

    Cha, Eunju; Jeong, Eun Sook; Cha, Sangwon; Lee, Jaeick

    2017-04-29

    In this study, gas chromatography (GC) was interfaced with high resolution mass spectrometry (HRMS) with electrospray ionization source (ESI) and the relevant parameters were investigated to enhance the ionization efficiency. In GC-ESI, the distances (x-, y- and z) and angle between the ESI needle, GC capillary column and MS orifice were set to 7 (x-distance), 4 (y-distance), and 1 mm (z-distance). The ESI spray solvent, acid modifier and nebulizer gas flow were methanol, 0.1% formic acid and 5 arbitrary units, respectively. Based on these results, analytical conditions for GC-ESI/HRMS were established. In particular, the results of spray solvent flow indicated a concentration-dependent mechanism (peak dilution effect), and other parameters also greatly influenced the ionization performance. The developed GC-ESI/HRMS was then applied to the analysis of anabolic steroids as trimethylsilyl (TMS) derivatives in human urine to demonstrate its application. The ionization profiles of TMS-derivatized steroids were investigated and compared with those of underivatized steroids obtained from gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) and liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS). The steroids exhibited ionization profiles based on their structural characteristics, regardless of the analyte phase or derivatization. Groups I and II with conjugated or unconjugated keto functional groups at C3 generated the [M+H] + and [M+H-TMS] + ions, respectively. On the other hand, Groups III and IV gave rise to the characteristic fragment ions [M+H-TMS-H 2 O] + and [M+H-2TMS-H 2 O] + , corresponding to loss of a neutral TMS·H 2 O moiety from the protonated molecular ion by in-source dissociation. To the best of our knowledge, this is the first study to successfully ionize and analyze steroids as TMS derivatives using ESI coupled with GC. The present system has enabled the ionization of TMS derivatives under ESI conditions

  15. Monitoring Toxic Ionic Liquids in Zebrafish ( Danio rerio) with Desorption Electrospray Ionization Mass Spectrometry Imaging (DESI-MSI)

    Science.gov (United States)

    Perez, Consuelo J.; Tata, Alessandra; de Campos, Michel L.; Peng, Chun; Ifa, Demian R.

    2017-06-01

    Ambient mass spectrometry imaging has become an increasingly powerful technique for the direct analysis of biological tissues in the open environment with minimal sample preparation and fast analysis times. In this study, we introduce desorption electrospray ionization mass spectrometry imaging (DESI-MSI) as a novel, rapid, and sensitive approach to localize the accumulation of a mildly toxic ionic liquid (IL), AMMOENG 130 in zebrafish ( Danio rerio). The work demonstrates that DESI-MSI has the potential to rapidly monitor the accumulation of IL pollutants in aquatic organisms. AMMOENG 130 is a quaternary ammonium-based IL reported to be broadly used as a surfactant in commercialized detergents. It is known to exhibit acute toxicity to zebrafish causing extensive damage to gill secondary lamellae and increasing membrane permeability. Zebrafish were exposed to the IL in a static 96-h exposure study in concentrations near the LC50 of 1.25, 2.5, and 5.0 mg/L. DESI-MS analysis of zebrafish gills demonstrated the appearance of a dealkylated AMMOENG 130 metabolite in the lowest concentration of exposure identified by a high resolution hybrid LTQ-Orbitrap mass spectrometer as the trimethylstearylammonium ion, [C21H46N]+. With DESI-MSI, the accumulation of AMMOENG 130 and its dealkylated metabolite in zebrafish tissue was found in the nervous and respiratory systems. AMMOENG 130 and the metabolite were capable of penetrating the blood brain barrier of the fish with significant accumulation in the brain. Hence, we report for the first time the simultaneous characterization, distribution, and metabolism of a toxic IL in whole body zebrafish analyzed by DESI-MSI. This ambient mass spectrometry imaging technique shows great promise for the direct analysis of biological tissues to qualitatively monitor foreign, toxic, and persistent compounds in aquatic organisms from the environment. [Figure not available: see fulltext.

  16. Differentiation of Streptococcus pneumoniae conjunctivitis outbreak isolates by matrix-assisted laser desorption ionization-time of flight mass spectrometry.

    Science.gov (United States)

    Williamson, Yulanda M; Moura, Hercules; Woolfitt, Adrian R; Pirkle, James L; Barr, John R; Carvalho, Maria Da Gloria; Ades, Edwin P; Carlone, George M; Sampson, Jacquelyn S

    2008-10-01

    Streptococcus pneumoniae (pneumococcus [Pnc]) is a causative agent of many infectious diseases, including pneumonia, septicemia, otitis media, and conjunctivitis. There have been documented conjunctivitis outbreaks in which nontypeable (NT), nonencapsulated Pnc has been identified as the etiological agent. The use of mass spectrometry to comparatively and differentially analyze protein and peptide profiles of whole-cell microorganisms remains somewhat uncharted. In this report, we discuss a comparative proteomic analysis between NT S. pneumoniae conjunctivitis outbreak strains (cPnc) and other known typeable or NT pneumococcal and streptococcal isolates (including Pnc TIGR4 and R6, Streptococcus oralis, Streptococcus mitis, Streptococcus pseudopneumoniae, and Streptococcus pyogenes) and nonstreptococcal isolates (including Escherichia coli, Enterococcus faecalis, and Staphylococcus aureus) as controls. cPnc cells and controls were grown to mid-log phase, harvested, and subsequently treated with a 10% trifluoroacetic acid-sinapinic acid matrix mixture. Protein and peptide fragments of the whole-cell bacterial isolate-matrix combinations ranging in size from 2 to 14 kDa were evaluated by matrix-assisted laser desorption ionization-time of flight mass spectrometry. Additionally Random Forest analytical tools and dendrogramic representations (Genesis) suggested similarities and clustered the isolates into distinct clonal groups, respectively. Also, a peak list of protein and peptide masses was obtained and compared to a known Pnc protein mass library, in which a peptide common and unique to cPnc isolates was tentatively identified. Information gained from this study will lead to the identification and validation of proteins that are commonly and exclusively expressed in cPnc strains which could potentially be used as a biomarker in the rapid diagnosis of pneumococcal conjunctivitis.

  17. Matrix Assisted Laser Desorption Ionization Mass Fingerprinting for Identification of Acacia Gum in Microsamples from Works of Art.

    Science.gov (United States)

    Granzotto, Clara; Sutherland, Ken

    2017-03-07

    This paper reports an improved method for the identification of Acacia gum in cultural heritage samples using matrix assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) after enzymatic digestion of the polysaccharide component. The analytical strategy was optimized using a reference Acacia gum (gum arabic, sp. A. senegal) and provided an unambiguous MS profile of the gum, characterized by specific and recognized oligosaccharides, from as little as 0.1 μg of material. The enhanced experimental approach with reduced detection limit was successfully applied to the analysis of naturally aged (∼80 year) gum arabic samples, pure and mixed with lead white pigment, and allowed the detection of gum arabic in samples from a late painting (1949/1954) by Georges Braque in the collection of the Art Institute of Chicago. This first application of the technique to characterize microsamples from a painting, in conjunction with analyses by gas chromatography/mass spectrometry (GC/MS), provided important insights into Braque's unusual mixed paint media that are also helpful to inform appropriate conservation treatments for his works. The robustness of the analytical strategy due to the reproducibility of the gum MS profile, even in the presence of other organic and inorganic components, together with the minimal sample size required, demonstrate the value of this new MALDI-TOF MS method as an analytical tool for the identification of gum arabic in microsamples from museum artifacts.

  18. Differentiation of virulence of Helicobacter pylori by matrix-assisted laser desorption/ionization mass spectrometry and multivariate analyses.

    Science.gov (United States)

    Cho, Yi-Tzu; Kuo, Chao-Hung; Wang, Sophie S W; Chen, Yu-Syuan; Weng, Bi-Chuang; Lee, Yi-Chern; Cheng, Chu-Nian; Shiea, Jentaie; Wu, Deng-Chyang

    2013-09-23

    The ability to determine the virulence of a Helicobacter pylori strain would be helpful for predicting the development of gastrointestinal disease and suggesting medical treatment. A protocol based on matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI-TOF MS) was established for the efficient detection of peptides and proteins in extracts of H. pylori cells. Two multivariate statistical methods-principal component analysis (PCA) and hierarchical clustering analysis-were used to analyze the resulting MALDI mass spectra of reference strains and clinical isolated/inoculated strains. Based on differences in their peptide and protein profiles, H. pylori strains having similar virulence genotypes were grouped together on the PCA score plot. Hierarchical cluster analysis revealed high conformity between the protein profiles and the respective virulence genotypes. The inoculated H. pylori strain, which was clustered in the same group with the high-virulence reference strains, also resulted in severe histopathological lesions in gerbils. MALDI-TOF MS combined with multivariate analyses shows the ability to rapidly differentiate H. pylori strains in terms of their virulence. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Statistical analysis of fragmentation patterns of electron ionization mass spectra of enolized-trimethylsilylated anabolic androgenic steroids

    Science.gov (United States)

    Fragkaki, A. G.; Angelis, Y. S.; Tsantili-Kakoulidou, A.; Koupparis, M.; Georgakopoulos, C.

    2009-08-01

    Anabolic androgenic steroids (AAS) are included in the List of prohibited substances of the World Anti-Doping Agency (WADA) as substances abused to enhance athletic performance. Gas chromatography coupled to mass spectrometry (GC-MS) plays an important role in doping control analyses identifying AAS as their enolized-trimethylsilyl (TMS)-derivatives using the electron ionization (EI) mode. This paper explores the suitability of complementary GC-MS mass spectra and statistical analysis (principal component analysis, PCA and partial least squares-discriminant analysis, PLS-DA) to differentiate AAS as a function of their structural and conformational features expressed by their fragment ions. The results obtained showed that the application of PCA yielded a classification among the AAS molecules which became more apparent after applying PLS-DA to the dataset. The application of PLS-DA yielded a clear separation among the AAS molecules which were, thus, classified as: 1-ene-3-keto, 3-hydroxyl with saturated A-ring, 1-ene-3-hydroxyl, 4-ene-3-keto, 1,4-diene-3-keto and 3-keto with saturated A-ring anabolic steroids. The study of this paper also presents structurally diagnostic fragment ions and dissociation routes providing evidence for the presence of unknown AAS or chemically modified molecules known as designer steroids.

  20. Identifying Carbohydrate Ligands of a Norovirus P Particle using a Catch and Release Electrospray Ionization Mass Spectrometry Assay

    Science.gov (United States)

    Han, Ling; Kitova, Elena N.; Tan, Ming; Jiang, Xi; Klassen, John S.

    2014-01-01

    Noroviruses (NoVs), the major cause of epidemic acute gastroenteritis, recognize human histo-blood group antigens (HBGAs), which are present as free oligosaccharides in bodily fluid or glycolipids and glycoproteins on the surfaces of cells. The subviral P particle formed by the protruding (P) domain of the NoV capsid protein serves as a useful model for the study NoV-HBGA interactions. Here, we demonstrate the application of a catch-and-release electrospray ionization mass spectrometry (CaR-ESI-MS) assay for screening carbohydrate libraries against the P particle to rapidly identify NoV ligands and potential inhibitors. Carbohydrate libraries of 50 and 146 compounds, which included 18 and 24 analogs of HBGA receptors, respectively, were screened against the P particle of VA387, a member of the predominant GII.4 NoVs. Deprotonated ions corresponding to the P particle bound to carbohydrates were isolated and subjected to collision-induced dissociation to release the ligands in their deprotonated forms. The released ligands were identified by ion mobility separation followed by mass analysis. All 13 and 16 HBGA ligands with intrinsic affinities >500 M-1 were identified in the 50 and the 146 compound libraries, respectively. Furthermore, screening revealed interactions with a series of oligosaccharides with structures found in the cell wall of mycobacteria and human milk. The affinities of these newly discovered ligands are comparable to those of the HBGA receptors, as estimated from the relative abundance of released ligand ions.

  1. Improved analysis of membrane protein by PVDF-aided, matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Chang, Chih-Yang; Liao, Hsin-Kai; Juo, Chiun-Gung; Chen, Shu-Hua; Chen, Yu-Ju

    2006-01-18

    Characterization of membrane proteins remains an analytical challenge because of difficulties associated with tedious isolation and purification. This study presents the utility of the polyvinylidene difluoride (PVDF) membrane for direct sub-proteome profiling and membrane protein characterization by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The hydrophobic adsorption of protein, particularly membrane proteins, on the PVDF surface enables efficient on-PVDF washing to remove high concentrations of detergents and salts, such as up to 5% sodium dodecyl sulfate (SDS). The enhanced spectrum quality for MALDI detection is particularly notable for high molecular weight proteins. By using on-PVDF washing prior to MALDI detection, we obtained protein profiles of the detergent-containing and detergent-insoluble membrane fractions from Methylococcus capsulatus (Bath). Similar improvements of signal-to-noise ratios were shown on the MALDI spectra for proteins electroblotted from SDS-polyacrylamide gel electrophoresis (SDS-PAGE) onto the PVDF membrane. We have applied this strategy to obtain intact molecular weights of the particulate methane monooxygenase (pMMO) composed of three intrinsic membrane-bound proteins, PmoA, PmoB, and PmoC. Together with peptide sequencing by tandem mass spectrometry, post-translational modifications including N-terminal acetylation of PmoA and PmoC and alternative C-terminal truncation of PmoB were identified. The above results show that PVDF-aided MALDI-MS can be an effective approach for profiling and characterization of membrane proteins.

  2. Identification and localization of trauma-related biomarkers using matrix assisted laser desorption/ionization imaging mass spectrometry

    Science.gov (United States)

    Jones, Kirstin; Reilly, Matthew A.; Glickman, Randolph D.

    2017-02-01

    Current treatments for ocular and optic nerve trauma are largely ineffective and may have adverse side effects; therefore, new approaches are needed to understand trauma mechanisms. Identification of trauma-related biomarkers may yield insights into the molecular aspects of tissue trauma that can contribute to the development of better diagnostics and treatments. The conventional approach for protein biomarker measurement largely relies on immunoaffinity methods that typically can only be applied to analytes for which antibodies or other targeting means are available. Matrix assisted laser-assisted desorption/ionization imaging mass spectrometry (MALDI-IMS) is a specialized application of mass spectrometry that not only is well suited to the discovery of novel or unanticipated biomarkers, but also provides information about the spatial localization of biomarkers in tissue. We have been using MALDI-IMS to find traumarelated protein biomarkers in retina and optic nerve tissue from animal models subjected to ocular injury produced by either blast overpressure or mechanical torsion. Work to date by our group, using MALDI-IMS, found that the pattern of protein expression is modified in the injured ocular tissue as soon as 24 hr post-injury, compared to controls. Specific proteins may be up- or down-regulated by trauma, suggesting different tissue responses to a given injury. Ongoing work is directed at identifying the proteins affected and mapping their expression in the ocular tissue, anticipating that systematic analysis can be used to identify targets for prospective therapies for ocular trauma.

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

    Directory of Open Access Journals (Sweden)

    K. E. Altieri

    2009-04-01

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

  4. The study of large biopolymer complexes in solution and the gas phase using electrospray ionization-FTICR mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R.D.; Lei, Q.P.; Wu, Qinyuan; Hofstadler, A. [Pacific Northwest National Lab., Richland, WA (United States)] [and others

    1997-12-31

    Electrospray ionization (ESI) can transfer large biopolymers and many noncovalently bound complexes into the gas phase and to preserve specific noncovalent biomolecular associations for subsequent mass spectrometric analysis. Although a number of details of the ESI process remain a subject of debate, it is now incontestable that many weak associations can survive transfer to the gas phase and are stable for periods of at least seconds. In this presentation, the application of ESI-Fourier transform ion cyclotron resonance (FTICR) mass spectrometry methods for the study of large biopolymers and their noncovalent complexes will be described. It will also be shown that competitive binding studies can be used to quickly establish relative binding affinities in solution, allowing combinatorial libraries to be rapidly screened. After measurements of the intact complex, dissociation studies can be conducted to probe the structure of the individual constituents of complexes. Studies comparing the relative stabilities of protein-ligand complexes in solution and desolvated in the gas phase will also be presented, and discussed from both fundamental and analytical perspectives.

  5. Lipid characterization of embryo zones by silica plate laser desorption ionization mass spectrometry imaging (SP-LDI-MSI).

    Science.gov (United States)

    Ferreira, Mônica S; de Oliveira, Diogo N; Gonçalves, Roseli F; Catharino, Rodrigo R

    2014-01-07

    Lipid pathways play important biological roles in mammalian embryology, directing early developmental pathways to differentiation. Phospholipids and triglycerides, among others, are the main composing lipids of zona pellucida in several embryo species. Lipid analysis in embryos by mass spectrometry usually requires sample preparation and/or matrix application. This novel approach using silica plate laser desorption/ionization mass spectrometry imaging (SP-LDI-MSI) allows direct single-cell imaging and embryo region discrimination with no matrix coating. Its application is herein described for two- and eight-cell embryos. Lipid biomarkers for blastomere and intact zona pellucida are reported and corroborated by both fragmentation reactions (MS/MS) and images. Results obtained in this work are understood to be of great use for further developments on in vitro bovine fertilization. Since much of the processes can be monitored by characteristic biomarkers, it is now possible to precisely identify cell division errors during early embryo stages, as well as evaluate pre-implantation conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Quantitative analysis of cytokinins in plants by high performance liquid chromatography: electronspray ionization ion trap mass spectrometry.

    Science.gov (United States)

    Chen, Weiqi; Gai, Ying; Liu, Shichang; Wang, Renxiao; Jiang, Xiangning

    2010-10-01

    The present paper introduces a highly sensitive and selective method for simultaneous quantification of 12 cytokinins (free form and their conjugates). The method includes a protocol of extraction with methanol/water/formic acid (15/4/1, v/v/v) to the micro-scale samples, pre-purification with solid phase extraction (SPE) cartridges of the extracts, separation with a high performance liquid chromatography (HPLC) and detection by an electrospray ionization ion trap mass spectrometry (ESI-Ion trap-MS) system in a consecutive ion monitoring (CRM) mode at the three stage fragmentation of mass spectrometry (MS(3) ). The lowest detection level of the cytokinins of the method reaches 0.1-2.0 pg with a very wide range of linear regression from 1-512 pg, at the coefficient factors of 0.98-0.99. The feasibility of this method has been proven in the application of the method to the analysis of the trace-amount contents of cytokinins in the micro-scale samples of various types of plant materials, such as aerial parts of rice and poplar leaves etc. 12 endogenous cytokinins had been identified and quantified in the plant tissues, with an acceptable relatively higher recovery rate from 40% to 70%. © 2010 Institute of Botany, Chinese Academy of Sciences.

  7. Authentication of animal fats using direct analysis in real time (DART) ionization-mass spectrometry and chemometric tools.

    Science.gov (United States)

    Vaclavik, Lukas; Hrbek, Vojtech; Cajka, Tomas; Rohlik, Bo-Anne; Pipek, Petr; Hajslova, Jana

    2011-06-08

    A combination of direct analysis in real time (DART) ionization coupled to time-of-flight mass spectrometry (TOFMS) and chemometrics was used for animal fat (lard and beef tallow) authentication. This novel instrumentation was employed for rapid profiling of triacylglycerols (TAGs) and polar compounds present in fat samples and their mixtures. Additionally, fat isolated from pork, beef, and pork/beef admixtures was analyzed. Mass spectral records were processed by principal component analysis (PCA) and stepwise linear discriminant analysis (LDA). DART-TOFMS profiles of TAGs were found to be more suitable for the purpose of discrimination among the examined fat types as compared to profiles of polar compounds. The LDA model developed using TAG data enabled not only reliable classification of samples representing neat fats but also detection of admixed lard and tallow at adulteration levels of 5 and 10% (w/w), respectively. The presented approach was also successfully applied to minced meat prepared from pork and beef with comparable fat content. Using the DART-TOFMS TAG profiles of fat isolated from meat mixtures, detection of 10% pork added to beef and vice versa was possible.

  8. Molecular differentiation of five Cinnamomum camphora chemotypes using desorption atmospheric pressure chemical ionization mass spectrometry of raw leaves

    Science.gov (United States)

    Guo, Xiali; Cui, Meng; Deng, Min; Liu, Xingxing; Huang, Xueyong; Zhang, Xinglei; Luo, Liping

    2017-04-01

    Five chemotypes, the isoborneol-type, camphora-type, cineole-type, linalool-type and borneol-type of Cinnamomum camphora (L.) Presl have been identified at the molecular level based on the multivariate analysis of mass spectral fingerprints recorded from a total of 750 raw leaf samples (i.e., 150 leaves equally collected for each chemotype) using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Both volatile and semi-volatile metabolites of the fresh leaves of C. camphora were simultaneously detected by DAPCI-MS without any sample pretreatment, reducing the analysis time from half a day using conventional methods (e.g., GC-MS) down to 30 s. The pattern recognition results obtained using principal component analysis (PCA) was cross-checked by cluster analysis (CA), showing that the difference visualized by the DAPCI-MS spectral fingerprints was validated with 100% accuracy. The study demonstrates that DAPCI-MS meets the challenging requirements for accurate differentiation of all the five chemotypes of C. camphora leaves, motivating more advanced application of DAPCI-MS in plant science and forestry studies.

  9. Rapid fingerprinting and classification of extra virgin olive oil by microjet sampling and extractive electrospray ionization mass spectrometry.

    Science.gov (United States)

    Law, Wai Siang; Chen, Huan Wen; Balabin, Roman; Berchtold, Christian; Meier, Lukas; Zenobi, Renato

    2010-04-01

    Microjet sampling in combination with extractive electrospray ionization (EESI) mass spectrometry (MS) was applied to the rapid characterization and classification of extra virgin olive oil (EVOO) without any sample pretreatment. When modifying the composition of the primary ESI spray solvent, mass spectra of an identical EVOO sample showed differences. This demonstrates the capability of this technique to extract molecules with varying polarities, hence generating rich molecular information of the EVOO. Moreover, with the aid of microjet sampling, compounds of different volatilities (e.g.E-2-hexenal, trans-trans-2,4-heptadienal, tyrosol and caffeic acid) could be sampled simultaneously. EVOO data was also compared with that of other edible oils. Principal Component Analysis (PCA) was performed to discriminate EVOO and EVOO adulterated with edible oils. Microjet sampling EESI-MS was found to be a simple, rapid (less than 2 min analysis time per sample) and powerful method to obtain MS fingerprints of EVOO without requiring any complicated sample pretreatment steps.

  10. Silver cluster interferences in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry of nonpolar polymers.

    Science.gov (United States)

    Macha, S F; Limbach, P A; Hanton, S D; Owens, K G

    2001-06-01

    Potential difficulties associated with background silver salt clusters during matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) of nonpolar polymers are reported. Silver salt cluster ions were observed from m/z 1500 to 7000 when acidic, polar matrices, such as 2,5-dihydroxybenzoic acid (DHB), all-trans-retinoic acid (RTA) or 2-(4-hydroxyphenylazo)benzoic acid (HABA), were used for the analysis of nonpolar polymers. These background signals could be greatly reduced or eliminated by the use of nonpolar matrices such as anthracene or pyrene. Representative examples of these background interferences are demonstrated during the analysis of low molecular weight nonpolar polymers including polybutadiene and polystyrene. Nonpolar polymers analyzed with acidic, polar matrices (e.g., RTA) and silver cationization reagents can yield lower quality mass spectral results when interferences due to silver clusters are present. Replacing the polar matrices with nonpolar matrices or the silver salts with copper salts substantially improved the quality of the analytical results. In addition, it was found that silver contamination cannot be completely removed from standard stainless steel sample plates, although the presence of silver contamination was greatly reduced after thorough cleaning of the sample plate with aluminum oxide grit. Carry-over silver may cationize polymer samples and complicate the interpretation of data obtained using nonpolar matrices in the absence of added cationization reagents.

  11. Gas-phase reactivity of silver and copper coordinated monosaccharide cations studied by electrospray ionization and tandem mass spectrometry.

    Science.gov (United States)

    Boutreau, Laurence; Léon, Emmanuelle; Salpin, Jean-Yves; Amekraz, Badia; Moulin, Christophe; Tortajada, Jeanine

    2003-01-01

    The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings.

  12. An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS for fast PAN and PPN measurements

    Directory of Open Access Journals (Sweden)

    H. Schlager

    2011-02-01

    Full Text Available An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate and PPN (peroxypropionyl nitrate. The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent on-line calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis. PPN, the second most abundant PAN homologue, was measured simultaneously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

  13. [Identification of triacylglycerols in coix oil by high performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry].

    Science.gov (United States)

    Xiang, Zhi-Min; Zhu, Ming; Chen, Bi-Lian; Chen, Yong

    2005-09-01

    To identify triacylglycerols in coix oil. High performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry was used for identification. The experiment was operated under the conditions: spray voltage at 3 000 V, capillary temperature at 250 degrees C, APCI vaporizer temperature at 400 degrees C, and corona current of 4 microA. Sheath gas pressure (high purity liquid nitrogen) was 35 kPa. Mass spectra were obtained over the m/e range of 300 to 900 amu, scan duration of 1s and Q1 peak width at 0.7. The stationary phase was Zorbax Extend C18 column (4.6 mm x 250 mm, 5 microm). The mobile phase: dichloromethane-acetonitrile (35:65), flow rate: 1 mL x min(-1); column temperature: 25 degrees C. 12 triacylglycerols were identified by HPLC-MS method. The result can be used to identify the components in a fingerprint chromatogram of coix oil and its related injection product.

  14. Development of sensitive derivatization method for aldosterone in liquid chromatography-electrospray ionization tandem mass spectrometry of corticosteroids.

    Science.gov (United States)

    Yamashita, Kouwa; Okuyama, Mitsunobu; Nakagawa, Risa; Honma, Seijiro; Satoh, Fumitoshi; Morimoto, Ryo; Ito, Sadayoshi; Takahashi, Madoka; Numazawa, Mitsuteru

    2008-07-25

    A highly sensitive quantification method of aldosterone by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was investigated in a positive mode using recently developed picolinyl derivatization. Aldosterone was smoothly and quantitatively converted to the ethyl ether-picolinyl derivative by treatment with HCl-ethanol followed by the esterification with picolinic acid in the presence of 2-methyl-6-nitrobenzoic anhydride and 4-dimethylaminopyridine. The positive ion-ESI mass spectrum of the ethyl ether-picolinyl derivative was characterized by an appearance of protonated molecule ([M+H](+)) as a base peak. The ethyl ether-picolinyl derivatization gave a successful result in a separation of aldosterone from corticosterone, dehydrocorticosterone and cortexolone, and also provided an approximately 10-fold higher ESI response in the positive-LC-ESI-MS/MS (selected reaction monitoring; SRM) when compared to that of underivatized molecule (negative mode). The limit of quantification of aldosterone by SRM using ethyl ether-picolinyl derivatization (m/z 494-->m/z 448) was 1 pg/0.2 ml serum with accuracy and precision of 92.6% and 5.6%, respectively.

  15. Highly sensitive determination of estrone and estradiol in human serum by liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Yamashita, Kouwa; Okuyama, Mitsunobu; Watanabe, Yoko; Honma, Seijiro; Kobayashi, Sayuri; Numazawa, Mitsuteru

    2007-10-01

    A highly sensitive and specific quantification method of estrone and estradiol in human serum was described based upon the use of picolinoyl derivatization and liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) in a positive mode. Estrogens were treated with picolinoyl chloride hydrochloride or picolinic acid and 2-methyl-6-nitrobenzoic anhydride followed by a solid-phase extraction with ODS cartridge. Picolinoyl derivatization proceeded quantitatively even in a microscale, and the picolinoyl esters provided simple positive ESI-mass spectra showing [M+H](+) as base peaks for these estrogens. The picolinoyl derivatives of these estrogens showed 100-fold higher detection response compared to underivatized intact molecules by LC-ESI-MS (selected reaction monitoring). Using this derivatization, estrogens spiked in the charcoal treated human serum samples were analyzed with limit of quantification (LOQ), intra-day accuracy and precision of 1.0pg/ml, 96.0% and 9.9% for estrone, and 0.5pg/ml, 84.4% and 12.8% for estradiol, respectively. Estrone and estradiol added to the crude serum samples were recovered with comparable LOQ and accuracy obtained for the charcoal treated serum samples as well.

  16. Simultaneous determination of tetrahydrocortisol, allotetrahydrocortisol and tetrahydrocortisone in human urine by liquid chromatography-electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Yamashita, Kouwa; Nakagawa, Risa; Okuyama, Mitsunobu; Honma, Seijiro; Takahashi, Madoka; Numazawa, Mitsuteru

    2008-08-01

    Simultaneous quantification method of three major metabolites of cortisone and cortisol, tetrahydrocortisol, allotetrahydrocortisol and tetrahydrocortisone by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was investigated in a positive mode using a recently developed picolinyl derivatization. Conversion of each steroid into the corresponding picolinyl derivatives (1b, 2b or 3b) was performed by mixed anhydride method using picolinic acids and 2-methyl-6-nitrobenzoic anhydride. Derivatization proceeded smoothly to afford the corresponding 3, 21-dipicolinyl derivatives. Positive ion-ESI mass spectra of the picolinyl derivatives were dominated by an appearance of [M+H](+) as base peaks in all cases. The picolinyl derivatives provided 15 to 80-fold higher ESI response in the LC-ESI-MS/MS (selected reaction monitoring: SRM) when compared to those of underivatized molecules in a positive LC-ESI mode. The use of the picolinyl ester, solid-phase extraction, and deuterium labeled internal standards enabled the concentrations of these metabolites in human urine to be determined simultaneously by LC-ESI-MS/MS (SRM) with a small sample volume of less than 1microl urine.

  17. Mass spectral analysis of N-oxides of Chemical Weapons Convention related aminoethanols under electrospray ionization conditions.

    Science.gov (United States)

    Sridhar, L; Karthikraj, R; Murty, M R V S; Raju, N Prasada; Vairamani, M; Prabhakar, S

    2011-02-28

    N,N'-Dialkylaminoethanols are the hydrolyzed products or precursors of chemical warfare agents such as V-agents and nitrogen mustards, and they are prone to undergo oxidation in environmental matrices or during decontamination processes. Consequently, screening of the oxidized products of aminoethanols in aqueous samples is an important task in the verification of chemical weapons convention-related chemicals. Here we report the successful characterization of the N-oxides of N,N'-dialkylaminoethanols, alkyl diethanolamines, and triethanolamine using positive ion electrospray ionization mass spectrometry. The collision-induced dissociation (CID) spectra of the [M+H](+) and [M+Na](+) ions show diagnostic product ions that enable the unambiguous identification of the studied N-oxides, including those of isomeric compounds. The proposed fragmentation pathways are supported by high-resolution mass spectrometry data and product/precursor ion spectra. The CID spectra of [M+H](+) ions included [MH-CH(4)O(2)](+) as the key product ion, in addition to a distinctive alkene loss that allowed us to recognize the alkyl group attached to the nitrogen. The [M+Na](+) ions show characteristic product ions due to the loss of groups (R) attached to nitrogen either as a radical (R) or as a molecule [R+H or (R-H)] after hydrogen migration. Copyright © 2011 John Wiley & Sons, Ltd.

  18. Metabolic Effects of Clenbuterol and Salbutamol on Pork Meat Studied Using Internal Extractive Electrospray Ionization Mass Spectrometry.

    Science.gov (United States)

    Lu, Haiyan; Zhang, Hua; Zhu, Tenggao; Xiao, Yipo; Xie, Shaoxian; Gu, Haiwei; Cui, Meng; Luo, Liping

    2017-07-11

    Direct mass spectrometry analysis of metabolic effects of clenbuterol and salbutamol on pork quality at the molecular level is incredibly beneficial for food regulations, public health and the development of new anti-obesity drugs. With internal extractive electrospray ionization mass spectrometry (iEESI-MS), nutrients including creatine, amino acids, L-carnitine, vitamin B6, carnosine and phosphatidylcholines in pork tissue were identified, without sample pretreatment, using collision-induced dissociation (CID) experiments and by comparison with authentic compounds. Furthermore, normal pork samples were clearly differentiated from pork samples with clenbuterol and salbutamol via principal component analysis (PCA). Correlation analysis performed on the spectral data revealed that the above-mentioned nutrients strongly correlated with pork quality, and the absolute intensity of phosphatidylcholines in normal pork was much higher than pork contaminated by clenbuterol and salbutamol. Our findings suggested that clenbuterol and salbutamol may render effects on the activity of carnitine acyltransferase I, hence the process that L-carnitine transports long-chain fatty acids into mitochondria and the formation of phosphatidylcholines might be affected. However, the underlying metabolic mechanisms of clenbuterol and salbutamol on carnitine acyltransferase I requires more comprehensive studies in future work.

  19. Analysis of Microbial Mixtures by Matrix-assisted Laser Desorption/Ionization time-of-flight Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wahl, Karen L.; Wunschel, Sharon C.; Jarman, Kristin H.; Valentine, Nancy B.; Petersen, Catherine E.; Kingsley, Mark T.; Zartolas, Kimberly A.; Saenz, Adam J.

    2002-12-15

    Many different laboratories are currently developing mass-spectrometric techniques to analyze and identify microorganisms. However, minimal work has been done with mixtures of bacteria. To demonstrate that microbial mixtures could be analyzed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), mixed bacterial cultures were analyzed in a double-blind fashion. Nine different bacterial species currently in our MALDI-MS fingerprint library were used to generate 50 different simulated mixed bacterial cultures similar to that done for an initial blind study previously reported.(1) The samples were analyzed by MALDI-MS with automated data extraction and analysis algorithms developed in our laboratory. The components present in the sample were identified correctly to the species level in all but one of the samples. However, correctly eliminating closely related organisms was challenging for the current algorithms, especially in differentiating Serratia marcescens, Escherichia coli, and Yersinia enterocolitica, which have some similarities in their MALDI-MS fingerprints. Efforts to improve the specificity of the algorithms are in progress.

  20. Confirmation of clorsulon residues in cattle kidney by capillary gas chromatography-negative-ion chemical-ionization mass spectrometry.

    Science.gov (United States)

    Wehner, T A; Wood, J S; Walker, R; Downing, G V; Vandenheuvel, W J

    1987-07-24

    A confirmatory assay for residues of the anthelmintic agent clorsulon [4-amino-6-(trichloroethenyl)-1,3-benzenedisulfonamide] in cattle kidney tissue has been developed. The assay involves isolation of a drug-containing fraction by solvent extraction, methylation of the analyte, and fused-silica capillary column gas chromatography-negative-ion chemical-ionization mass spectrometry of the pentamethyl derivative of clorsulon. The intensities of four negative ions [m/z 406 and 408 (trichloro species) and m/z 413 and 415 (dichloro species)] are monitored. Confirmation of the presence of drug in an analyte requires that all four ions appear at the appropriate retention time with their intensity ratios within 10-15% of those arising from analysis of the reference standard, methylated clorsulon; the lower limit of detection is 3 ppb. Quantification of the drug is based on the intensity of the m/z 406 ion. Identification and quantification of residues by the gas chromatographic-mass spectrometric assay gave results in good agreement with those obtained with an electron-capture gas chromatographic assay.

  1. Determination of paclitaxel distribution in solid tumors by nano-particle assisted laser desorption ionization mass spectrometry imaging.

    Science.gov (United States)

    Morosi, Lavinia; Spinelli, Pietro; Zucchetti, Massimo; Pretto, Francesca; Carrà, Andrea; D'Incalci, Maurizio; Giavazzi, Raffaella; Davoli, Enrico

    2013-01-01

    A sensitive, simple and reproducible protocol for nanoparticle-assisted laser desorption/ionization mass spectrometry imaging technique is described. The use of commercially available TiO2 nanoparticles abolishes heterogeneous crystallization, matrix background interferences and enhances signal detection, especially in the low mass range. Molecular image normalization was based on internal standard deposition on tissues, allowing direct comparison of drug penetration and distribution between different organs and tissues. The method was applied to analyze the distribution of the anticancer drug paclitaxel, inside normal and neoplastic mouse tissue sections. Spatial resolution was good, with a linear response between different in vivo treatments and molecular imaging intensity using therapeutic drug doses. This technique distinguishes the different intensity of paclitaxel distribution in control organs of mice, such as liver and kidney, in relation to the dose. Animals treated with 30 mg/kg of paclitaxel had half of the concentration of those treated with 60 mg/kg. We investigated the spatial distribution of paclitaxel in human melanoma mouse xenografts, following different dosage schedules and found a more homogeneous drug distribution in tumors of mice given repeated doses (5×8 mg/kg) plus a 60 mg/kg dose than in those assigned only a single 60 mg/kg dose. The protocol can be readily applied to investigate anticancer drug distribution in neoplastic lesions and to develop strategies to optimize and enhance drug penetration through different tumor tissues.

  2. Determination of paclitaxel distribution in solid tumors by nano-particle assisted laser desorption ionization mass spectrometry imaging.

    Directory of Open Access Journals (Sweden)

    Lavinia Morosi

    Full Text Available A sensitive, simple and reproducible protocol for nanoparticle-assisted laser desorption/ionization mass spectrometry imaging technique is described. The use of commercially available TiO2 nanoparticles abolishes heterogeneous crystallization, matrix background interferences and enhances signal detection, especially in the low mass range. Molecular image normalization was based on internal standard deposition on tissues, allowing direct comparison of drug penetration and distribution between different organs and tissues. The method was applied to analyze the distribution of the anticancer drug paclitaxel, inside normal and neoplastic mouse tissue sections. Spatial resolution was good, with a linear response between different in vivo treatments and molecular imaging intensity using therapeutic drug doses. This technique distinguishes the different intensity of paclitaxel distribution in control organs of mice, such as liver and kidney, in relation to the dose. Animals treated with 30 mg/kg of paclitaxel had half of the concentration of those treated with 60 mg/kg. We investigated the spatial distribution of paclitaxel in human melanoma mouse xenografts, following different dosage schedules and found a more homogeneous drug distribution in tumors of mice given repeated doses (5×8 mg/kg plus a 60 mg/kg dose than in those assigned only a single 60 mg/kg dose. The protocol can be readily applied to investigate anticancer drug distribution in neoplastic lesions and to develop strategies to optimize and enhance drug penetration through different tumor tissues.

  3. Distinct features of matrix-assisted 6 microm infrared laser desorption/ionization mass spectrometry in biomolecular analysis.

    Science.gov (United States)

    Tajiri, Michiko; Takeuchi, Takae; Wada, Yoshinao

    2009-08-15

    Midinfrared-matrix-assisted laser desorption/ionization mass spectrometry (mid-IR-MALDI MS) with a laser emission in the 6 microm wavelength range, which utilizes energy absorption at the C=O double-bond stretch region, was applied to biomolecular analysis. The softness of IR-MALDI MS was evident in the negative ion mode yielding clean mass spectra of [M - H](-) ions for acidic biomolecules with sulfate, phosphate, or carboxylate groups, resulting in better sensitivity than ultraviolet (UV)-MALDI MS. There was no substantial loss of sialic acid due to the prompt fragmentation occurring in IR-MALDI of sialylated glycoconjugates such as gangliosides. Furthermore, the advantage of the low photon energy of IR is that, for the first time, intact protonated molecules of S-nitrosylated peptides can be detected by MALDI MS. In the analysis of redox-sensitive molecules including methylene blue and riboflavin, reductive hydrogenation was minimal, suggesting few hydrogen radicals to have formed in the plume, in contrast to UV-MALDI. In conjunction with a potent new matrix, oxamide, requiring smaller laser fluence, distinct features of the 6 microm IR wavelength range are anticipated to remove one of the limitations of MALDI MS for biomolecular analysis.

  4. Enhanced sensitivity for high spatial resolution lipid analysis by negative ion mode matrix assisted laser desorption ionization imaging mass spectrometry.

    Science.gov (United States)

    Angel, Peggi M; Spraggins, Jeffrey M; Baldwin, H Scott; Caprioli, Richard

    2012-02-07

    We have achieved enhanced lipid imaging to a ~10 μm spatial resolution using negative ion mode matrix assisted laser desorption ionization (MALDI) imaging mass spectrometry, sublimation of 2,5-dihydroxybenzoic acid as the MALDI matrix, and a sample preparation protocol that uses aqueous washes. We report on the effect of treating tissue sections by washing with volatile buffers at different pHs prior to negative ion mode lipid imaging. The results show that washing with ammonium formate, pH 6.4, or ammonium acetate, pH 6.7, significantly increases signal intensity and number of analytes recorded from adult mouse brain tissue sections. Major lipid species measured were glycerophosphoinositols, glycerophosphates, glycerolphosphoglycerols, glycerophosphoethanolamines, glycerophospho-serines, sulfatides, and gangliosides. Ion images from adult mouse brain sections that compare washed and unwashed sections are presented and show up to 5-fold increases in ion intensity for washed tissue. The sample preparation protocol has been found to be applicable across numerous organ types and significantly expands the number of lipid species detectable by imaging mass spectrometry at high spatial resolution. © 2012 American Chemical Society

  5. Quantitative profiling method for phytohormones and betaines in algae by liquid chromatography electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Wang, Xiujuan; Zhao, Peng; Liu, Xuemei; Chen, Juanjuan; Xu, Jilin; Chen, Haimin; Yan, Xiaojun

    2014-02-01

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the quantitative determination of phytohormones and betaines in algae. The results showed that phytohormones and betaines were separated with high efficiency on Hypersil Gold C18 and Cnwsil SCX columns. Mass spectrometric detection was performed using positive or negative electrospray ionization in selective reaction monitoring mode (SRM). Linearity of the method was good with correlation coefficients (r(2) > 0.9951 in the range of 0.005-5 mg/L. The limits of detection were from 0.004 to 0.86 µg/L and the limits of quantification were in the range from 0.01 to 2.8 µg/L for the investigated phytohormones and betaines. The obtained recoveries varied between 61.33 and 90.39%, and the relative standard deviations were Pyropia haitanensis, which were collected in Xiangshan, Zhejiang Province, China, were determined. Thus, LC-MS/MS was demonstrated to be a powerful tool for the comprehensive analysis of phytohormones and betaines in algae, owing to its large dynamic range and excellent sensitivity. Copyright © 2013 John Wiley & Sons, Ltd.

  6. Filamentous fungal characterizations by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Santos, C; Paterson, R R M; Venâncio, A; Lima, N

    2010-02-01

    Matrix-assisted laser desorption/ionization time-of-flight intact cell mass spectrometry (MALDI-TOF ICMS) is coming of age for the identification and characterization of fungi. The procedure has been used extensively with bacteria. UV-absorbing matrices function as energy mediators that transfer the absorbed photoenergy from an irradiation source to the surrounding sample molecules, resulting in minimum fragmentation. A surprisingly high number of fungal groups have been studied: (i) the terverticillate penicillia, (ii) aflatoxigenic, black and other aspergilli, (iii) Fusarium, (iv) Trichoderma, (iv) wood rotting fungi (e.g. Serpula lacrymans) and (v) dermatophytes. The technique has been suggested for optimizing quality control of fungal Chinese medicines (e.g. Cordyceps). MALDI-TOF ICMS offers advantages over PCR. The method is now used in taxonomic assessments (e.g. Trichoderma) as distinct from only strain characterization. Low and high molecular mass natural products (e.g. peptaibols) can be analysed. The procedure is rapid and requires minimal pretreatment. However, issues of reproducibility need to be addressed further in terms of strains of species tested and between run variability. More studies into the capabilities of MALDI-TOF ICMS to identify fungi are required.

  7. Improved specificity of serum phosphatidylcholine detection based on side-chain losses during negative electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Ritchie, Shawn A; Jayasinge, Dushmanthi; Wang, Li; Goodenowe, Dayan B

    2016-11-01

    Many current tandem mass spectrometry (MS) methods for measuring phosphatidylcholines (PtdChos) rely only on precursor ion scanning of the common 184 m/z phosphocholine fragment with positive electrospray ionization (+ESI), and thus measure pools of PtdChos rather than specific isoforms. In this paper, we developed and compared an isotope dilution, tandem MS method capable of quantifying PtdChos based on specific fatty acid side-chains to the traditional 184 m/z method. The method is based on the detection of PtdCho ammonium formate (AmF) adduct as parent ions and fatty acid fragment daughter ions under negative electrospray ionization (-ESI). Accuracy, imprecision, and recovery were below 15 %, with acceptable linearity (R 2 > 0.99) up to 5 μg/mL. We used the method to analyze the distributions of PtdChos with common side-chain combinations among 60 subjects and showed that it was possible for two individuals to have the same PtdCho pool concentration based on detection of the 184 m/z fragment, but up to a fourfold difference in the levels of specific isoforms comprising the pool based on our method. We then compared the results of both methods across 572 patients with mild cognitive impairment (MCI), Alzheimer's disease (AD), or no impairment (NI), which showed that statistically significant associations between specific PtdCho isoforms and AD were masked with the 184 m/z method. Our findings demonstrate the importance of isoform specificity for quantifying PtdChos, and suggest caution when interpreting analytical data based on pools of biomarkers.

  8. Determination of glycerol in oils and fats using liquid chromatography chloride attachment electrospray ionization mass spectrometry.

    Science.gov (United States)

    Jin, Chunfen; Viidanoja, Jyrki

    2017-01-15

    Existing liquid chromatography - mass spectrometry method for the analysis of short chain carboxylic acids was expanded and validated to cover also the measurement of glycerol from oils and fats. The method employs chloride anion attachment and two ions, [glycerol+35Cl]- and [glycerol+37Cl]-, as alternative quantifiers for improved selectivity of glycerol measurement. The averaged within run precision, between run precision and accuracy ranged between 0.3-7%, 0.4-6% and 94-99%, respectively, depending on the analyte ion and sample matrix. Selected renewable diesel feedstocks were analyzed with the method. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Analysis of Phospholipid Mixtures from Biological Tissues by Matrix-Assisted Laser Desorption and Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS): A Laboratory Experiment

    Science.gov (United States)

    Eibisch, Mandy; Fuchs, Beate; Schiller, Jurgen; Sub, Rosmarie; Teuber, Kristin

    2011-01-01

    Matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS) is increasingly used to investigate the phospholipid (PL) compositions of tissues and body fluids, often without previous separation of the total mixture into the individual PL classes. Therefore, the questions of whether all PL classes are detectable…

  10. Differentiation of Clinically Relevant mucorales Rhizopus microsporus and R. arrhizus by Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS)

    NARCIS (Netherlands)

    Dolatabadi, S.; Kolecka, A.; Versteeg, Matthijs; de Hoog, Sybren G; Boekhout, Teun

    This study addresses the usefulness of Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry (MALDI-TOF MS) for reliable identification of the two most frequently occuring clinical species of Rhizopus, namely R. arrhizus with its two varieties arrhizus and delemar and R.

  11. DIFFERENTIATION OF AEROMONAS ISOLATES OBTAINED FROM DRINKING WATER DISTRIBUTION SYSTEM USING MATRIX-ASSISTED LASER DESCRIPTION/IONIZATION-MASS SPECTROMETRY (MALDI-MS)

    Science.gov (United States)

    The genus Aeromonas is one of several medically significant genera that have gained prominence due to their evolving taxonomy and controversial role in human diseases. In this study, matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) was used to analyze the...

  12. Differentiation of Raoultella ornithinolytica/planticola and Klebsiella oxytoca clinical isolates by matrix-assisted laser desorption/ionization-time of flight mass spectrometry.

    NARCIS (Netherlands)

    Jong, Eefje de; Jong, A.S. de; Smidts-van den Berg, N.; Rentenaar, R.J.

    2013-01-01

    Ninety-nine clinical isolates previously identified as Klebsiella oxytoca were evaluated using matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS). Eight isolates were identified as Raoultella spp., being 5 Raoultella spp. and 3 K. oxytoca, by 16S rRNA

  13. Structural analysis of (methyl-esterified) oligogalacturonides using post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Alebeek, van G.J.W.M.; Zabotina, O.; Beldman, G.; Schols, H.A.; Voragen, A.G.J.

    2000-01-01

    The use of post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for the structural analysis of ((partly) methyl-esterified) oligogalacturonides (oligoGalA) is described. The fragmentation behavior of purified (un)saturated oligoGalA (degree of polymerization

  14. Macroscopic and microscopic spatially-resolved analysis of food contaminants and constituents using laser-ablation electrospray ionization mass spectrometry imaging

    NARCIS (Netherlands)

    Nielen, M.W.F.; Beek, van T.A.

    2014-01-01

    Laser-ablation electrospray ionization (LAESI) mass spectrometry imaging (MSI) does not require very flat surfaces, high-precision sample preparation, or the addition of matrix. Because of these features, LAESI-MSI may be the method of choice for spatially-resolved food analysis. In this work, LAESI

  15. Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

    NARCIS (Netherlands)

    Portoles, T.; Mol, J.G.J.; Sancho, J.V.; Lopez, F.J.; Hernandez, F.

    2014-01-01

    A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target

  16. Characterization of polychlorinated n-alkanes using comprehensive two-dimensional gas chromatography-electron-capture negative ionization time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Korytar, P.; Parera, J.; Leonards, P.E.G.; Santos, F.J.; Boer, de J.; Brinkman, U.A.Th.

    2005-01-01

    Comprehensive two-dimensional gas chromatography with electron-capture negative ionization time-of-flight mass spectrometry (GC × GC¿ECNI-TOF-MS) is used to study the composition and characteristics of short-, medium- and long-chain polychlorinated n-alkane (PCA) mixtures. Distinct ordered

  17. REAL TIME, ON-LINE CHARACTERIZATION OF DIESEL GENERATOR AIR TOXIC EMISSIONS BY RESONANCE ENHANCED MULTI-PHOTON IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

    Science.gov (United States)

    The laser based resonance, enhanced multi-photon ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds ...

  18. Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Mortensen, Sarah Kelly; Trier, Xenia Thorsager; Foverskov, Annie

    2005-01-01

    A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo...

  19. Identification of glyceollin metabolites derived from conjugation with glutathione and glucuronic acid in rats by on-line liquid chromatography-electrospray ionization tandem mass spectrometry

    Science.gov (United States)

    Glyceollin-related metabolites produced in rats following oral glyceollin administration were screened and identified by precursor and product ion scanning using liquid chromatography, coupled on-line with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), to identify all glyceollin me...

  20. Matrix-Assisted Ionization-Ion Mobility Spectrometry-Mass Spectrometry: Selective Analysis of a Europium-PEG Complex in a Crude Mixture.

    Science.gov (United States)

    Fischer, Joshua L; Lutomski, Corinne A; El-Baba, Tarick J; Siriwardena-Mahanama, Buddhima N; Weidner, Steffen M; Falkenhagen, Jana; Allen, Matthew J; Trimpin, Sarah

    2015-12-01

    The analytical utility of a new and simple to use ionization method, matrix-assisted ionization (MAI), coupled with ion mobility spectrometry (IMS) and mass spectrometry (MS) is used to characterize a 2-armed europium(III)-containing poly(ethylene glycol) (Eu-PEG) complex directly from a crude sample. MAI was used with the matrix 1,2-dicyanobenzene, which affords low chemical background relative to matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). MAI provides high ion abundance of desired products in comparison to ESI and MALDI. Inductively coupled plasma-MS measurements were used to estimate a maximum of 10% of the crude sample by mass was the 2-arm Eu-PEG complex, supporting evidence of selective ionization of Eu-PEG complexes using the new MAI matrix, 1,2-dicyanobenzene. Multiply charged ions formed in MAI enhance the IMS gas-phase separation, especially relative to the singly charged ions observed with MALDI. Individual components are cleanly separated and readily identified, allowing characterization of the 2-arm Eu-PEG conjugate from a mixture of the 1-arm Eu-PEG complex and unreacted starting materials. Size-exclusion chromatography, liquid chromatography at critical conditions, MALDI-MS, ESI-MS, and ESI-IMS-MS had difficulties with this analysis, or failed. Graphical Abstract ᅟ.

  1. Warm dark matter and the ionization history of the Universe

    Science.gov (United States)

    Lopez-Honorez, Laura; Mena, Olga; Palomares-Ruiz, Sergio; Villanueva-Domingo, Pablo

    2017-11-01

    In warm dark matter scenarios structure formation is suppressed on small scales with respect to the cold dark matter case, reducing the number of low-mass halos and the fraction of ionized gas at high redshifts and thus, delaying reionization. This has an impact on the ionization history of the Universe and measurements of the optical depth to reionization, of the evolution of the global fraction of ionized gas and of the thermal history of the intergalactic medium, can be used to set constraints on the mass of the dark matter particle. However, the suppression of the fraction of ionized medium in these scenarios can be partly compensated by varying other parameters, as the ionization efficiency or the minimum mass for which halos can host star-forming galaxies. Here we use different data sets regarding the ionization and thermal histories of the Universe and, taking into account the degeneracies from several astrophysical parameters, we obtain a lower bound on the mass of thermal warm dark matter candidates of mX>1.3 keV , or ms>5.5 keV for the case of sterile neutrinos nonresonantly produced in the early Universe, both at 90% confidence level.

  2. Characterizing changes in snow crab (Chionoecetes opilio) cryptocyanin protein during molting using matrix-assisted laser desorption/ionization mass spectrometry and tandem mass spectrometry.

    Science.gov (United States)

    Demian, Wael L L; Jahouh, Farid M; Stansbury, Don; Randell, Edward; Brown, Robert J; Banoub, Joseph H

    2014-02-28

    We report the matrix-assisted laser desorption/ionization mass spectrometric (MALDI-MS) characterization of the cryptocyanin proteins of the juvenile Chionoecetes opilio crabs during their molting and non-molting phases. In order to assess the structural cryptocyanin protein differences between the molting and non-molting phases, the obtained peptides were sequenced by MALDI low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS). The cryptocyanin protein was isolated by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and analyzed by MALDI-TOF/TOF-MS. The purified cryptocyanin protein was sequenced, using the 'bottom-up' approach. After tryptic digestion, the peptide mixture was analyzed by MALDI-QqTOF-MS/MS and the data obtained were used for the peptide mass fingerprinting (PMF) identification by means of the Mascot database. It was demonstrated using MALDI-TOF/TOF-MS that the actual molecular weights of the non-molting and molting cryptocyanin proteins were different; these were, respectively, 67.6 kDa and 68.1 kDa. Using low-energy CID-MS/MS we have sequenced the trytic peptides to monitor the differences and similarities between the cryptocyanin molecular structures during the molting and non-molting stages. We have demonstrated for the first time that the actual molecular masses of the cryptocyanin protein during the molting and non-molting phases were different. The MALDI-CID-MS/MS analyses allowed the sequencing of the cryptocyanins after tryptic digestion, during the molting and non-molting stages, and showed some similarities and staggering differences between the identified cryptocyanin peptides. Copyright © 2013 John Wiley & Sons, Ltd.

  3. BioAerosol Mass Spectrometry: Reagentless Detection of Individual Airborne Spores and Other Bioagent Particles Based on Laser Desorption/Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Steele, Paul Thomas [Univ. of California, Davis, CA (United States)

    2004-09-01

    Better devices are needed for the detection of aerosolized biological warfare agents. Advances in the ongoing development of one such device, the BioAerosol Mass Spectrometry (BAMS) system, are described here in detail. The system samples individual, micrometer-sized particles directly from the air and analyzes them in real-time without sample preparation or use of reagents. At the core of the BAMS system is a dual-polarity, single-particle mass spectrometer with a laser based desorption and ionization (DI) system. The mass spectra produced by early proof-of-concept instruments were highly variable and contained limited information to differentiate certain types of similar biological particles. The investigation of this variability and subsequent changes to the DI laser system are described. The modifications have reduced the observed variability and thereby increased the usable information content in the spectra. These improvements would have little value without software to analyze and identify the mass spectra. Important improvements have been made to the algorithms that initially processed and analyzed the data. Single particles can be identified with an impressive level of accuracy, but to obtain significant reductions in the overall false alarm rate of the BAMS instrument, alarm decisions must be made dynamically on the basis of multiple analyzed particles. A statistical model has been developed to make these decisions and the resulting performance of a hypothetical BAMS system is quantitatively predicted. The predictions indicate that a BAMS system, with reasonably attainable characteristics, can operate with a very low false alarm rate (orders of magnitude lower than some currently fielded biodetectors) while still being sensitive to small concentrations of biological particles in a large range of environments. Proof-of-concept instruments, incorporating some of the modifications described here, have already performed well in independent testing.

  4. Use of Mass Spectrometry with Electrospray Ionization and Exploratory Analysis for Classification of Extra Virgin Olive Oil Adulterated with Vegetable Oils

    OpenAIRE

    Hery Mitsutake; Universidade Federal de Uberlândia; Lucas C. Gontijo; Universidade Federal de Uberlândia; Felipe B. Santana; Universidade Federal de Uberlândia; Eloiza Guimarães; Universidade Federal de Uberlândia; Lilian Lúcia da Rocha; Universidade Federal de Juiz de Fora; Waldomiro Borges Neto; Universidade Federal de Uberlândia

    2015-01-01

    Due to the economic value and health benefits of the extra virgin olive oil (EVOO), this product is mainly the subject of adulteration by addition of cheaper vegetable oils. Thus, this study evaluated the detection of extra virgin olive samples oil adulterated with oils of canola, sunflower, corn and soybeans through exploratory multivariate analysis. The oil fingerprints were obtained by mass spectrometry with electrospray ionization in positive ion mode (ESI(+)-MS). The mass spectrometry da...

  5. Reactions of anionic porphyrin with group 11 elements: a spectrophotometric and electrospray ionization mass spectrometry study.

    Science.gov (United States)

    Giovannetti, Rita; Bartocci, Vito; Pucciarelli, Filippo; Ricciutelli, Massimo

    2004-07-08

    The reaction of 3,8,13,18-tetramethyl-21H,23H-porphine-2,7,12,17-tetrapropionic acid or coproporphyrin-I (CPI) with the elements of 11 group have been studied. CPI is an anionic porphyrin that slowly reacts with copper ion to form Cu(II)CPI and with silver ions to form Ag(II)CPI, Ag(III)CPI complexes and colloidal silver. Gold ions do not form complexes with CPI, but, in the main, colloidal gold and some CPI-N-oxide. The kinetics of the reactions with copper and silver were spectrophotometerically studied and the rate constants were calculated. The identification and characterization of this water-soluble anionic porphyrin and its metal complexes have been performed by electrospray mass spectrometry (ESI-MS) that proved to be an excellent method for these determinations. The multiple charged parent ions for metal free ligand and their metal complexes were identified.

  6. Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

    Science.gov (United States)

    Kern, Sara E.; Lin, Lora A.; Fricke, Frederick L.

    2014-08-01

    U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]+) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]+ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]+ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The

  7. MIL-101(Cr) as matrix for sensitive detection of quercetin by matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Han, Guobin; Zeng, Qiaoling; Jiang, Zhongwei; Xing, Tiantian; Huang, Chengzhi; Li, Yuanfang

    2017-03-01

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has been proven as a useful and advanced technique in the identification of polymers and proteins. However, MALDI-TOF-MS still has the unavoidable drawback of self-signal interference with traditional organic matrices, which could suppress and overlap with the analyte signals in the low-mass region. In this work, MIL-101(Cr), a kind of metal-organic frameworks which possess high molecular weight, π-conjugated 3-D structure, coordinately unsaturated chromium sites (CUS) and strong absorption in the UV range, was employed to replace traditional organic matrices, and it was found that MIL-101(Cr) can dramatically eliminate the background peaks, showing high signal-to-noise level in the analysis of small molecules. As proof-of-concept, quercetin, daidzein, genistein and naringenin, members of flavonol family which widely exists in food and natural products, were successfully determined by utilizing MIL-101(Cr) as the surface-assisted matrix, and the detection of quercetin was sensitive with good salt tolerance and reproducibility. Under optimal conditions, the mass peak intensity exhibited good linear relationships in the range from 0.25µg/mL-7.00µg/mL for quercetin (R2=0.996) with detection limit 2.11ng/mL (3σ/k), making the identification of quercetin in sophora japonica successfully. With this strategy we have demonstrated the potentiality of MIL-101(Cr) nanomaterials as MALDI-MS matrix for the detection of small molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Ion/molecule reactions in the orifice-skimmer region of an atmospheric pressure Penning ionization mass spectrometer.

    Science.gov (United States)

    Furuya, Hiroko; Fujimaki, Susumu; Kambara, Shizuka; Suzuki, Shigeo; Hashimoto, Yutaka; Okazaki, Shigemitsu; Wada, Akira; Beech, Iwona B; Sunner, Jan; Hiraoka, Kenzo

    2005-01-01

    Atmospheric pressure Penning ionization mass spectra of methanol were measured as functions of Ar or He gas pressure in the first vacuum chamber, the position of the skimmer, and the voltage applied between the orifice and the skimmer. When the orifice and the skimmer were coaxial with a distance of 4 mm, the distribution of CH3OH2+(CH3OH)n clusters was only weakly dependent on both Ar pressure (in the range of 19-220 Pa) and orifice-skimmer voltage (in the range of 1-45 V). The ion/molecule reaction CH3OH2+ + CH3OH --> CH3+(CH3OH) + H2O was observed in the free jet expansion, especially at high orifice-skimmer voltage values. When the orifice and the skimmer were off-centered and the distance between them was increased to 18 mm, the formation of large CH3OH2+(CH3OH)n clusters, as well as their dissociation, were seen. The endothermic proton transfer reaction, CH3+(CH3OH) + CH3OH --> CH3OH2+ + CH3OCH3, occurred at high orifice-skimmer voltage. The collision-induced dissociation of cluster ions by He gas in the first vacuum chamber was much more efficient than by Ar. These results demonstrated that the mass spectra are highly dependent on skimmer position and on orifice-skimmer voltage and that ions observed by mass spectrometry do not necessarily reflect the abundance of ions produced in the atmospheric pressure ion source. Copyright (c) 2005 John Wiley & Sons, Ltd.

  9. Time-resolved molecular characterization of limonene/ozone aerosol using high-resolution electrospray ionization mass spectrometry.

    Science.gov (United States)

    Bateman, Adam P; Nizkorodov, Sergey A; Laskin, Julia; Laskin, Alexander

    2009-09-28

    Molecular composition of limonene/O3 secondary organic aerosol (SOA) was investigated using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) as a function of reaction time. SOA was generated by ozonation of D-limonene in a reaction chamber and sampled at different time intervals using a cascade impactor. The SOA samples were extracted into acetonitrile and analyzed using a HR-ESI-MS instrument with a resolving power of 100,000 (m/Deltam). The resulting mass spectra provided detailed information about the extent of oxidation inferred from the O:C ratios, double bond equivalency (DBE) factors, and aromaticity index (AI) values in hundreds of identified individual SOA species. The chemical composition of SOA was approximately the same for all size-fractionated samples studied in this experiment (0.05 to 0.5 microm range). The SOA constituents quickly reached an average O:C ratio of 0.43, which grew to 0.46 after one hour of additional oxidation of particles by the excess ozone. The dominant mechanism of oligomerization, inferred from high resolution ESI-MS data, was reaction between Criegee intermediates and stable first-generation products of limonene ozonolysis. Although the SOA composition was dominated by various oxidized aliphatic compounds, a small fraction of products appeared to contain aromatic rings. SOA generation was also studied in the presence of UV radiation and at elevated relative humidity (RH). The presence of UV radiation had a negligible effect on the SOA composition. The presence of water vapor resulted in a slight redistribution of peak intensities in the mass spectrum likely arising from hydration of certain SOA constituents. The data are consistent with fast production of the first-generation SOA constituents, including oligomers, followed by very slow aging processes that have a relatively small effect on the average molecular composition on the timescale of our experiments.

  10. Retention behavior of lipids in reversed-phase ultrahigh-performance liquid chromatography-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Ovčačíková, Magdaléna; Lísa, Miroslav; Cífková, Eva; Holčapek, Michal

    2016-06-10

    Reversed-phase ultrahigh-performance liquid chromatography (RP-UHPLC) method using two 15cm sub-2μm particles octadecylsilica gel columns is developed with the goal to separate and unambiguously identify a large number of lipid species in biological samples. The identification is performed by the coupling with high-resolution tandem mass spectrometry (MS/MS) using quadrupole - time-of-flight (QTOF) instrument. Electrospray ionization (ESI) full scan and tandem mass spectra are measured in both polarity modes with the mass accuracy better than 5ppm, which provides a high confidence of lipid identification. Over 400 lipid species covering 14 polar and nonpolar lipid classes from 5 lipid categories are identified in total lipid extracts of human plasma, human urine and porcine brain. The general dependences of relative retention times on relative carbon number or relative double bond number are constructed and fit with the second degree polynomial regression. The regular retention patterns in homologous lipid series provide additional identification point for UHPLC/MS lipidomic analysis, which increases the confidence of lipid identification. The reprocessing of previously published data by our and other groups measured in the RP mode and ultrahigh-performance supercritical fluid chromatography on the silica column shows more generic applicability of the polynomial regression for the description of retention behavior and the prediction of retention times. The novelty of this work is the characterization of general trends in the retention behavior of lipids within logical series with constant fatty acyl length or double bond number, which may be used as an additional criterion to increase the confidence of lipid identification. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Three-Dimensional Imaging of Lipids and Metabolites in Tissues by Nanospray Desorption Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lanekoff, Ingela T.; Burnum-Johnson, Kristin E.; Thomas, Mathew; Cha, Jeeyeon; Dey, Sudhansu K.; yang, Pengxiang; Prieto, Mari; Laskin, Julia

    2015-03-01

    Abstract Three-dimensional (3D) imaging of tissue sections is a new frontier in mass spectrometry imaging (MSI). Here we report on fast 3D imaging of lipids and metabolites associated with mouse uterine decidual cells and embryo at the implantation site on day 6 of pregnancy. 2D imaging of 16-20 serial tissue sections deposited on the same glass slide was performed using nanospray desorption electrospray ionization (nano-DESI) – an ambient ionization technique that enables sensitive localized analysis of analytes on surfaces without special sample pre-treatment. In this proof-of-principle study, nano-DESI was coupled to a high-resolution Q-Exactive instrument operated at high repetition rate of >5 Hz with moderate mass resolution of 35,000 (m/Δm at m/z 200), which enabled acquisition of the entire 3D image with a spatial resolution of ~150 μm in less than 4.5 hours. The results demonstrate localization of acetylcholine in the primary decidual zone (PDZ) of the implantation site throughout the depth of the tissue examined, indicating an important role of this signaling molecule in decidualization. Choline and phosphocholine – metabolites associated with cell growth – are enhanced in the PDZ and abundant in other cellular regions of the implantation site. Very different 3D distributions were obtained for fatty acids (FA), oleic acid and linoleic acid (FA 18:1 and FA 18:2), differing only by one double bond. Localization of FA 18:2 in the PDZ indicates its important role in decidualization while FA 18:1 is distributed more evenly throughout the tissue. In contrast, several lysophosphatidylcholines (LPC) observed in this study show donut-like distributions with localization around the PDZ. Complementary distributions with minimal overlap were observed for LPC 18:0 and FA 18:2 while the 3D image of the potential precursor phosphatidylcholine (PC 36:2) showed a significant overlap with both LPC 18:0 and FA 18:2.

  12. Airborne intercomparison of HOx measurements using laser-induced fluorescence and chemical ionization mass spectrometry during ARCTAS

    Directory of Open Access Journals (Sweden)

    J. H. Crawford

    2012-08-01

    Full Text Available The hydroxyl (OH and hydroperoxyl (HO2 radicals, collectively called HOx, play central roles in tropospheric chemistry. Accurate measurements of OH and HO2 are critical to examine our understanding of atmospheric chemistry. Intercomparisons of different techniques for detecting OH and HO2 are vital to evaluate their measurement capabilities. Three instruments that measured OH and/or HO2 radicals were deployed on the NASA DC-8 aircraft throughout Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS in the spring and summer of 2008. One instrument was the Penn State Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS for OH and HO2 measurements based on Laser-Induced Fluorescence (LIF spectroscopy. A second instrument was the NCAR Selected-Ion Chemical Ionization Mass Spectrometer (SI-CIMS for OH measurement. A third instrument was the NCAR Peroxy Radical Chemical Ionization Mass Spectrometer (PeRCIMS for HO2 measurement. Formal intercomparison of LIF and CIMS was conducted for the first time on a same aircraft platform. The three instruments were calibrated by quantitative photolysis of water vapor by ultraviolet (UV light at 184.9 nm with three different calibration systems. The absolute accuracies were ±32% (2σ for the LIF instrument, ±65% (2σ for the SI-CIMS instrument, and ±50% (2σ for the PeRCIMS instrument. In general, good agreement was obtained between the CIMS and LIF measurements of both OH and HO2 measurements. Linear regression of the entire data set yields [OH]CIMS = 0.89 × [OH]LIF + 2.8 × 104 cm−3 with a correlation coefficient r2 = 0.72 for OH, and [HO2]CIMS = 0.86 × [HO2]LIF + 3.9 parts per trillion by volume (pptv, equivalent to pmol mol−1 with a correlation coefficient r2 = 0.72 for HO2. In general, the difference between CIMS and LIF instruments for OH and HO2 measurements can be explained by their combined measurement uncertainties. Comparison with box model results shows some

  13. Plasmonic Thermal Decomposition/Digestion of Proteins: A Rapid On-Surface Protein Digestion Technique for Mass Spectrometry Imaging.

    Science.gov (United States)

    Zhou, Rong; Basile, Franco

    2017-09-05

    A method based on plasmon surface resonance absorption and heating was developed to perform a rapid on-surface protein thermal decomposition and digestion suitable for imaging mass spectrometry (MS) and/or profiling. This photothermal process or plasmonic thermal decomposition/digestion (plasmonic-TDD) method incorporates a continuous wave (CW) laser excitation and gold nanoparticles (Au-NPs) to induce known thermal decomposition reactions that cleave peptides and proteins specifically at the C-terminus of aspartic acid and at the N-terminus of cysteine. These thermal decomposition reactions are induced by heating a solid protein sample to temperatures between 200 and 270 °C for a short period of time (10-50 s per 200 μm segment) and are reagentless and solventless, and thus are devoid of sample product delocalization. In the plasmonic-TDD setup the sample is coated with Au-NPs and irradiated with 532 nm laser radiation to induce thermoplasmonic heating and bring about site-specific thermal decomposition on solid peptide/protein samples. In this manner the Au-NPs act as nanoheaters that result in a highly localized thermal decomposition and digestion of the protein sample that is independent of the absorption properties of the protein, making the method universally applicable to all types of proteinaceous samples (e.g., tissues or protein arrays). Several experimental variables were optimized to maximize product yield, and they include heating time, laser intensity, size of Au-NPs, and surface coverage of Au-NPs. Using optimized parameters, proof-of-principle experiments confirmed the ability of the plasmonic-TDD method to induce both C-cleavage and D-cleavage on several peptide standards and the protein lysozyme by detecting their thermal decomposition products with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The high spatial specificity of the plasmonic-TDD method was demonstrated by using a mask to digest designated sections of

  14. Determination of porphyrins in oral bacteria by liquid chromatography electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Fyrestam, Jonas; Bjurshammar, Nadja; Paulsson, Elin; Johannsen, Annsofi; Östman, Conny

    2015-09-01

    Biofilms in the oral cavity can be visualized by fluorescence and a common assumption is that the endogenously produced porphyrins in certain bacteria give rise to this fluorescence. Porphyrin content in oral bacteria has been sparingly investigated, and non-selective detection techniques such as utilizing the Soret fluorescence band of porphyrins are often used. In the present study, a quantitative and selective method for the determination of porphyrins in oral bacteria has been developed and validated using high performance liquid chromatography-tandem mass spectrometry. Lysis of bacteria using Tris-EDTA buffer together with ultrasonication showed high microbial killing efficiency ≥99.98%, and sample clean-up using C18-solid phase extraction resulted in low matrix effects ≤14% for all analytes. Using this method, the porphyrin content was determined in the two oral pathogens Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis, as well as for baker's yeast, Saccharomyces cerevisiae. Uroporphyrin, 7-carboxylporphyrin, 6-carboxylporphyrin, coproporphyrin, and protoporphyrin IX were identified in the investigated microorganisms, and it was shown that the porphyrin profile differs between the two bacteria, as well as for S. cerevisiae. To our knowledge, this is the first time the porphyrin profile has been determined for the bacterium A. actinomycetemcomitans.

  15. Simultaneous determination of monosaccharides and oligosaccharides in dates using liquid chromatography-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Ghfar, Ayman A; Wabaidur, Saikh M; Ahmed, A Yacine Badjah Hadj; Alothman, Zeid A; Khan, Mohammad R; Al-Shaalan, Nora H

    2015-06-01

    Ultra performance liquid chromatography coupled to mass spectrometry was used for the simultaneous separation and determination of reducing monosaccharides (fructose and glucose), a non-reducing disaccharide (sucrose) and oligosaccharides (kestose and nystose) in HILIC mode. The chromatographic separation of all saccharides was performed on a BEH amide column using an acetonitrile-water gradient elution. The detection was carried out using selected ion recording (SIR) acquisition mode. The validation of the proposed method showed that the limit of detection and limit of quantification values for the five analyzed compounds were in the range of 0.25-0.69μg/mL and 0.82-3.58μg/mL, respectively; while the response was linear in the range of 1-50μg/mL. The developed method showed potential usefulness for a rapid and sensitive analysis of underivatized saccharides and was used for determination of sugars in three date samples (Sefri, Mabroom, Ghassab) which were soxhlet extracted by ethanol. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls

    Directory of Open Access Journals (Sweden)

    Robertson Larry W

    2009-03-01

    Full Text Available Abstract Background Polychlorinated biphenyls are persistent organic pollutants that can be metabolized via hydroxylated PCBs to PCB sulfate metabolites. The sensitive and selective analysis of PCB sulfate monoesters by gas chromatography-mass spectrometry (GC-MS requires their derivatization, for example, as PCB 2,2,2-trichloroethyl (TCE sulfate monoesters. To aid in the identification of unknown PCB sulfate metabolites isolated from biological samples, the electron impact MS fragmentation pathways of selected PCB TCE sulfate diesters were analyzed and compared to the fragmentation pathways of the corresponding methoxylated PCBs. Results The most abundant and characteristic fragment ions of PCB TCE sulfate diesters were formed by releasing CHCCl3, SO3, HCl2 and/or CCl3 from the TCE sulfate moiety and Cl2, HCl, ethyne and chloroethyne from an intermediate phenylcyclopentadienyl cation. The fragmentation pattern depended on the degree of chlorination and the position of the TCE sulfate moiety (i.e., ortho vs. meta/para to the second phenyl ring, but were independent of the chlorine substitution pattern. These fragmentation pathways are similar to the fragmentation pathways of structurally related methoxylated PCBs. Conclusion Knowledge of the fragmentation patterns of PCB TCE sulfate diesters will greatly aid in determining the position of sulfate moiety (ortho vs. meta/para of unknown PCB sulfate metabolites isolated from environmental or laboratory samples.

  17. Probing combustion chemistry in a miniature shock tube with synchrotron VUV photo ionization mass spectrometry.

    Science.gov (United States)

    Lynch, Patrick T; Troy, Tyler P; Ahmed, Musahid; Tranter, Robert S

    2015-02-17

    Tunable synchrotron-sourced photoionization time-of-flight mass spectrometry (PI-TOF-MS) is an important technique in combustion chemistry, complementing lab-scale electron impact and laser photoionization studies for a wide variety of reactors, typically at low pressure. For high-temperature and high-pressure chemical kinetics studies, the shock tube is the reactor of choice. Extending the benefits of shock tube/TOF-MS research to include synchrotron sourced PI-TOF-MS required a radical reconception of the shock tube. An automated, miniature, high-repetition-rate shock tube was developed and can be used to study high-pressure reactive systems (T > 600 K, P shock waves. In this paper, we present results of a PI-TOF-MS study at the Advanced Light Source at Lawrence Berkeley National Laboratory. Dimethyl ether pyrolysis (2% CH3OCH3/Ar) was observed behind the reflected shock (1400 shock tube studies. The signal levels attained and data throughput rates with this technique are comparable to those with other synchrotron-based PI-TOF-MS reactors, and it is anticipated that this high pressure technique will greatly complement those lower pressure techniques.

  18. MoS2/Ag nanohybrid: A novel matrix with synergistic effect for small molecule drugs analysis by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    Science.gov (United States)

    Zhao, Yaju; Deng, Guoqing; Liu, Xiaohui; Sun, Liang; Li, Hui; Cheng, Quan; Xi, Kai; Xu, Danke

    2016-09-21

    This paper reports a facile synthesis of molybdenum disulfide nanosheets/silver nanoparticles (MoS2/Ag) hybrid and its use as an effective matrix in negative ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The nanohybrid exerts a strong synergistic effect, leading to high performance detection of small molecule analytes including amino acids, peptides, fatty acids and drugs. The enhancement of laser desorption/ionization (LDI) efficiency is largely attributed to the high surface roughness and large surface area for analyte adsorption, better dispersibility, increased thermal conductivity and enhanced UV energy absorption as compared to pure MoS2. Moreover, both Ag nanoparticles and the edge of the MoS2 layers function as deprotonation sites for proton capture, facilitating the charging process in negative ion mode and promoting formation of negative ions. As a result, the MoS2/Ag nanohybrid proves to be a highly attractive matrix in MALDI-TOF MS, with desired features such as high desorption/ionization efficiency, low fragmentation interference, high salt tolerance, and no sweet-spots for mass signal. These characteristic properties allowed for simultaneous analysis of eight different drugs and quantification of acetylsalicylic acid in the spiked human serum. This work demonstrates for the first time the fabrication and application of a novel MoS2/Ag hybrid, and provides a new platform for use in the rapid and high throughput analysis of small molecules by mass spectrometry. Copyright © 2016. Published by Elsevier B.V.

  19. 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

  20. Cyclic organic peroxides identification and trace analysis by Raman microscopy and open-air chemical ionization mass spectrometry

    Science.gov (United States)

    Pena-Quevedo, Alvaro Javier

    The persistent use of cyclic organic peroxides in explosive devices has increased the interest in study these compounds. Development of methodologies for the detection of triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) has become an urgent priority. However, differences in physical properties between cyclic organic peroxides make difficult the development of a general method for peroxide analysis and detection. Following this urgency, the first general technique for the analysis of any peroxide, regarding its structural differences is reported. Characterization and detection of TATP and HMTD was performed using an Open-Air Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer. The first spectrometric analysis for tetramethylene diperoxide dicarbamide (TMDD) and other nitrogen based peroxides using Raman Microscopy and Mass Spectrometry is reported. Analysis of cyclic peroxides by GC-MS was also conducted to compare results with OACI-HRTOF data. In the OACI mass spectrum, HMTD showed a clear signal at m/z 209 MH + and a small adduct peak at m/z 226 [M+NH4]+ that allowed its detection in commercial standard solutions and lab made standards. TMDD presented a molecular peak of m/z 237 MH+ and an adduct peak of m/z 254 [M+NH4]+. TATP showed a single peak at m/z 240 [M+NH4]+, while the peak of m/z 223 or 222 was completely absent. This evidence suggests that triperoxides are stabilized by the ammonium ion. TATP samples with deuterium enrichment were analyzed to compare results that could differentiate from HMTD. Raman microscopy was used as a complementary characterization method and was an essential tool for cyclic peroxides identification, particularly for those which could not be extensively purified. All samples were characterized by Raman spectroscopy to confirm the Mass Spectrometry results. Peroxide O-O vibrations were observed around 750-970 cm-1. D18-TATP studies had identified ketone triperoxide nu(O-O) vibration around

  1. Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: probing chemical composition of D2O ice beneath a H2O ice layer.

    Science.gov (United States)

    Yang, Rui; Gudipati, Murthy S

    2014-03-14

    In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D2O ices by novel infrared (IR) laser ablation of a layered non-absorbing D2O ice (spectator) containing the analytes and an ablation-active IR-absorbing H2O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry, previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H2O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D2O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D2O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was