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Sample records for pressure ionization mass

  1. Atmospheric-pressure Penning ionization mass spectrometry.

    PubMed

    Hiraoka, Kenzo; Fujimaki, Susumu; Kambara, Shizuka; Furuya, Hiroko; Okazaki, Shigemitsu

    2004-01-01

    A preliminary study on the atmospheric-pressure Penning ionization (APP(e)I) of gaseous organic compounds with Ar* has been made. The metastable argon atoms (Ar*: 11.55 eV for (3)P(2) and 11.72 eV for (3)P(0)) were generated by the negative-mode corona discharge of atmospheric-pressure argon gas. By applying a high positive voltage (+500 to +1000 V) to the stainless steel capillary for the sample introduction (0.1 mm i.d., 0.3 mm o.d.), strong ion signals could be obtained. The ions formed were sampled through an orifice into the vacuum and mass-analyzed by an orthogonal time-of-flight mass spectrometer. The major ions formed by APP(e)I are found to be molecular-related ions for alkanes, aromatics, and oxygen-containing compounds. Because only the molecules with ionization energies less than the internal energy of Ar* are ionized, the present method will be a selective and highly sensitive interface for gas chromatography/mass spectrometry.

  2. High pressure (>1 atm) electrospray ionization mass spectrometry.

    PubMed

    Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

    2011-03-01

    High pressure electrospray ionization mass spectrometry has been performed by pressurizing a custom made ion source chamber with compressed air to a pressure higher than the atmospheric pressure. The ion source was coupled to a commercial time-of-flight mass spectrometer using a nozzle-skimmer arrangement. The onset voltage for the electrospray of aqueous solution was found to be independent on the operating pressure. The onset voltage for the corona discharge, however, increased with the rise of pressure following the Paschen's law. Thus, besides having more working gas for the desolvation process, gaseous breakdown could also be avoided by pressurizing the ESI ion source with air to an appropriate level. Stable electrospray ionization has been achieved for the sample solution with high surface tension such as pure water in both positive and negative ion modes. Fragmentation of labile compounds during the ionization process could also be reduced by optimizing the operating pressure of the ion source.

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

    PubMed

    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.

  4. Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    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.

  5. Low-Pressure, Field-Ionizing Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Hartley, Frank; Smith, Steven

    2009-01-01

    A small mass spectrometer utilizing a miniature field ionization source is now undergoing development. It is designed for use in a variety of applications in which there are requirements for a lightweight, low-power-consumption instrument that can analyze the masses of a wide variety of molecules and ions. The device can operate without need for a high-vacuum, carrier-gas feed radioactive ionizing source, or thermal ionizer. This mass spectrometer can operate either in the natural vacuum of outer space or on Earth at any ambient pressure below 50 torr (below about 6.7 kPa) - a partial vacuum that can easily be reached by use of a small sampling pump. This mass spectrometer also has a large dynamic range - from singly charged small gas ions to deoxyribonucleic acid (DNA) fragments larger than 104 atomic mass units - with sensitivity adequate for detecting some molecules and ions at relative abundances of less than one part per billion. This instrument (see figure) includes a field ionizer integrated with a rotating-field mass spectrometer (RFMS). The field ionizer effects ionization of a type characterized as "soft" in the art because it does not fragment molecules or initiate avalanche arcing. What makes the "soft" ionization mode possible is that the distance between the ionizing electrodes is less than mean free path for ions at the maximum anticipated operating pressure, so that the ionizer always operates on the non-breakdown side of the applicable Paschen curve (a standard plot of breakdown potential on the ordinate and pressure electrode separation on the abscissa). The field ionizer in this instrument is fabricated by micromachining a submicron-thick membrane out of an electrically nonconductive substrate, coating the membrane on both sides to form electrodes, then micromachining small holes through the electrodes and membrane. Because of the submicron electrode separation, even a potential of only 1 V applied between the electrodes gives rise to an electric

  6. Development of an Atmospheric Pressure Ionization Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    1998-01-01

    A commercial atmospheric pressure ionization mass spectrometer (APIMS) was purchased from EXTREL Mass Spectrometry, Inc. (Pittsburgh, PA). Our research objectives were to adapt this instrument and develop techniques for real-time determinations of the concentrations of trace species in the atmosphere. The prototype instrument is capable of making high frequency measurements with no sample preconcentrations. Isotopically labeled standards are used as an internal standard to obtain high precision and to compensate for changes in instrument sensitivity and analyte losses in the sampling manifold as described by Bandy and coworkers. The prototype instrument is capable of being deployed on NASA C130, Electra, P3, and DC8 aircraft. After purchasing and taking delivery by June 1994, we assembled the mass spectrometer, data acquisition, and manifold flow control instrumentation in electronic racks and performed tests.

  7. Microchip atmospheric pressure chemical ionization source for mass spectrometry.

    PubMed

    Ostman, Pekka; Marttila, Seppo J; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2004-11-15

    A novel microchip heated nebulizer for atmospheric pressure chemical ionization mass spectrometry is presented. Anisotropic wet etching is used to fabricate the flow channels, inlet, and nozzle on a silicon wafer. An integrated heater of aluminum is sputtered on a glass wafer. The two wafers are jointed by anodic bonding, creating a two-dimensional version of an APCI source with a sample channel in the middle and gas channels symmetrically on both sides. The ionization is initiated with an external corona-discharge needle positioned 2 mm in front of the microchip heated nebulizer. The microchip APCI source provides flow rates down to 50 nL/min, stable long-term analysis with chip lifetime of weeks, good quantitative repeatability (RSD < 10%) and linearity (r(2) > 0.995) with linear dynamic rage of at least 4 orders of magnitude, and cost-efficient manufacturing. The limit of detection (LOD) for acridine measured with microchip APCI at flow rate of 6.2 muL/min was 5 nM, corresponding to a mass flow of 0.52 fmol/s. The LOD with commercial macro-APCI at a flow rate of 1 mL/min for acridine was the same, 5 nM, corresponding to a significantly worse mass flow sensitivity (83 fmol/s) than measured with microchip APCI. The advantages of microchip APCI makes it a very attractive new microfluidic detector.

  8. The updated bottom up solution applied to atmospheric pressure photoionization and electrospray ionization mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    The Updated Bottom Up Solution (UBUS) was recently applied to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) of triacylglycerols (TAGs). This report demonstrates that the UBUS applies equally well to atmospheric pressure photoionization (APPI) MS and to electrospray ionizatio...

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

    PubMed

    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. Graphical Abstract ᅟ.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Plasma Ion Sources for Atmospheric Pressure Ionization Mass Spectrometry.

    NASA Astrophysics Data System (ADS)

    Zhao, Jian-Guo

    1994-01-01

    Atmospheric pressure ionization (API) sources using direct-current (DC) and radio-frequency (RF) plasma have been developed in this thesis work. These ion sources can provide stable discharge currents of ~ 1 mA, 2-3 orders of magnitude larger than that of the corona discharge, a widely used API source. The plasmas can be generated and maintained in 1 atm of various buffer gases by applying -500 to -1000 V (DC plasma) or 1-15 W with a frequency of 165 kHz (RF plasma) on the needle electrode. These ion sources have been used with liquid injection to detect various organic compounds of pharmaceutical, biotechnological and environmental interest. Key features of these ion sources include soft ionization with the protonated molecule as the largest peak, and superb sensitivity with detection limits in the low picogram or femtomole range and a linear dynamic range over ~4 orders of magnitude. The RF plasma has advantages over the DC plasma in its ability to operate in various buffer gases and to produce a more stable plasma. Factors influencing the performance of the ion sources have been studied, including RF power level, liquid flow rate, chamber temperature, solvent composition, and voltage affecting the collision induced dissociation (CID). Ionization of hydrocarbons by the RF plasma API source was also studied. Soft ionization is generally produced. To obtain high sensitivity, the ion source must be very dry and the needle-to-orifice distance must be small. Nitric oxide was used to enhance the sensitivity. The RF plasma source was then used for the analysis of hydrocarbons in auto emissions. Comparisons between the corona discharge and the RF plasma have been made in terms of discharge current, ion residence time, and the ion source model. The RF plasma source provides larger linear dynamic range and higher sensitivity than the corona discharge, due to its much larger discharge current. The RF plasma was also observed to provide longer ion residence times and was not

  12. Atmospheric pressure soft ionization for gas chromatography with dielectric barrier discharge ionization-mass spectrometry (GC-DBDI-MS).

    PubMed

    Mirabelli, Mario F; Wolf, Jan-Christoph; Zenobi, Renato

    2017-05-30

    In this study, a gas chromatography (GC) system was interfaced to a high-resolution Orbitrap mass spectrometer by means of an active capillary plasma ionization source, based on dielectric barrier discharge ionization (DBDI). This allowed highly efficient soft ionization of gas-phase, chromatographically resolved compounds at ambient pressure. Several pesticides and illicit drugs were analyzed, and the limits of detections (LODs) were as low as 30 pg mL(-1) for the GC-DBDI-MS coupling (corresponding to 60 fg on-column sensitivity) and 30 fg mL(-1) for SPME-GC-DBDI-MS.

  13. Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids.

    PubMed

    Swider, Paweł; Lewtak, Jan P; Gryko, Daniel T; Danikiewicz, Witold

    2013-10-01

    The porphyrinoids chemistry is greatly dependent on the data obtained in mass spectrometry. For this reason, it is essential to determine the range of applicability of mass spectrometry ionization methods. In this study, the sensitivity of three different atmospheric pressure ionization techniques, electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization, was tested for several porphyrinods and their metallocomplexes. Electrospray ionization method was shown to be the best ionization technique because of its high sensitivity for derivatives of cyanocobalamin, free-base corroles and porphyrins. In the case of metallocorroles and metalloporphyrins, atmospheric pressure photoionization with dopant proved to be the most sensitive ionization method. It was also shown that for relatively acidic compounds, particularly for corroles, the negative ion mode provides better sensitivity than the positive ion mode. The results supply a lot of relevant information on the methodology of porphyrinoids analysis carried out by mass spectrometry. The information can be useful in designing future MS or liquid chromatography-MS experiments.

  14. Atmospheric Pressure Ionization Permanent Magnet Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    PubMed Central

    Vilkov, Andrey N.; Gamage, Chaminda M.; Misharin, Alexander S.; Doroshenko, Vladimir M.; Tolmachev, Dmitry A.; Tarasova, Irina A.; Kharybin, Oleg N.; Novoselov, Konstantin P.; Gorshkov, Michael V.

    2007-01-01

    A new Fourier Transform Ion Cyclotron Resonance mass spectrometer based on a permanent magnet with an atmospheric pressure ionization source was designed and constructed. A mass resolving power (full-width-at-half-maximum) of up to 80,000 in the electron ionization mode and 25,000 in the electrospray mode was obtained. Also, a mass measurement accuracy at low-ppm level has been demonstrated for peptide mixtures in a mass range of up to 1,200 m/z in the isotopically resolved mass spectra. PMID:17587594

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

    PubMed

    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.

  16. Super-atmospheric pressure ionization mass spectrometry and its application to ultrafast online protein digestion analysis.

    PubMed

    Chen, Lee Chuin; Ninomiya, Satoshi; Hiraoka, Kenzo

    2016-06-01

    Ion source pressure plays a significant role in the process of ionization and the subsequent ion transmission inside a mass spectrometer. Pressurizing the ion source to a gas pressure greater than atmospheric pressure is a relatively new approach that aims to further improve the performance of atmospheric pressure ionization sources. For example, under a super-atmospheric pressure environment, a stable electrospray can be sustained for liquid with high surface tension such as pure water, because of the suppression of electric discharge. Even for nano-electrospray ionization (nano-ESI), which is known to work with aqueous solution, its stability and sensitivity can also be enhanced, particularly in the negative mode when the ion source is pressurized. A brief review on the development of super-atmospheric pressure ion sources, including high-pressure electrospray, field desorption and superheated ESI, and the strategies to interface these ion sources to a mass spectrometer will be given. Using a recent ESI prototype with an operating temperature at 220 °C under 27 atm, we also demonstrate that it is possible to achieve an online Asp-specific protein digestion analysis in which the whole processes of digestion, ionization and MS acquisition could be completed on the order of a few seconds. This method is fast, and the reaction can even be monitored on a near-real-time basis. Copyright © 2016 John Wiley & Sons, Ltd.

  17. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    DOE PAGES

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: 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. METHODS: 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 mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creatingmore » a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: 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. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.« less

  18. An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J.; Kertesz, Vilmos

    2015-01-01

    RATIONALE: 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. METHODS: 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 mass spectrometer ionization source 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. RESULTS: 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. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.

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

    PubMed

    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.

  20. Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

    2015-08-01

    A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

  1. Atmospheric Pressure Surface Sampling/Ionization Techniques for Direct Coupling of Planar Separations with Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Van Berkel, Gary J

    2010-01-01

    Planar separations, which include thin layer chromatography and gel electrophoresis, are in widespread use as important and powerful tools for conducting separations of complex mixtures. To increase the utility of planar separations, new methods are needed that allow in-situ characterization of the individual components of the separated mixtures. A large number of atmospheric pressure surface sampling and ionization techniques for use with mass spectrometry have emerged in the past several years, and several have been investigated as a means for mass spectrometric read-out of planar separations. In this article, we review the atmospheric pressure surface sampling and ionization techniques that have been used for the read-out of planar separation media. For each technique, we briefly explain the operational basics and discuss the analyte type for which it is appropriate and some specific applications from the literature.

  2. Gas Chromatography/Atmospheric Pressure Chemical Ionization Tandem Mass Spectrometry for Fingerprinting the Macondo Oil Spill.

    PubMed

    Lobodin, Vladislav V; Maksimova, Ekaterina V; Rodgers, Ryan P

    2016-07-05

    We report the first application of a new mass spectrometry technique (gas chromatography combined to atmospheric pressure chemical ionization tandem mass spectrometry, GC/APCI-MS/MS) for fingerprinting a crude oil and environmental samples from the largest accidental marine oil spill in history (the Macondo oil spill, the Gulf of Mexico, 2010). The fingerprinting of the oil spill is based on a trace analysis of petroleum biomarkers (steranes, diasteranes, and pentacyclic triterpanes) naturally occurring in crude oil. GC/APCI enables soft ionization of petroleum compounds that form abundant molecular ions without (or little) fragmentation. The ability to operate the instrument simultaneously in several tandem mass spectrometry (MS/MS) modes (e.g., full scan, product ion scan, reaction monitoring) significantly improves structural information content and sensitivity of analysis. For fingerprinting the oil spill, we constructed diagrams and conducted correlation studies that measure the similarity between environmental samples and enable us to differentiate the Macondo oil spill from other sources.

  3. Precursor ion scan profiles of acylcarnitines by atmospheric pressure thermal desorption chemical ionization tandem mass spectrometry.

    PubMed

    Paglia, Giuseppe; D'Apolito, Oceania; Corso, Gaetano

    2008-12-01

    The fatty acyl esters of L-carnitine (acylcarnitines) are useful biomarkers for the diagnosis of some inborn errors of metabolism analyzed by liquid chromatography/tandem mass spectrometry. In this study the acylcarnitines were analyzed by atmospheric pressure thermal desorption chemical ionization using a commercial tandem mass spectrometer (APTDCI-MS/MS). The method is based on the precursor ion scan mode determination of underivatized acylcarnitines desorbed from samples by a hot desolvation gas flow and ionized by a corona pin discharge. During desorption/ionization step the temperature induces the degradation of acylcarnitines; nevertheless, the common fragment to all acylcarnitines [MH-59](+) is useful for analyzing their profile. APTDCI parameters, including angle of collection and incidence, gas flows and temperatures, were optimized for acylcarnitines. The experiments were performed drying 2 microL of an equimolar mixture of acylcarnitine standards on a glass slide. The specificity was evaluated by comparing product ion spectra and the precursor ion spectra of 85 m/z of acylcarnitines obtained by the APTDCI method and by electrospray ionization flow injection analysis (ESI-FIA). The method was also employed to analyze acylcarnitines extracted from a pathological dried blood spot and a control. The method enables analysis of biological samples and recognition of some acylcarnitines that are diagnostic markers of inherited metabolic diseases. The intrinsic high-throughput analysis of the ambient desorption ionization methods offers a new opportunity either for its potential application in clinical chemistry and for the expanded screening of some inborn errors of metabolism.

  4. A subambient pressure ionization with nanoelectrospray (SPIN) source and interface for improved sensitivity in mass spectrometry

    PubMed Central

    Page, Jason S.; Tang, Keqi; Kelly, Ryan T.; Smith, Richard D.

    2008-01-01

    An electrospray ionization mass spectrometry (ESI-MS) source and interface has been designed that enables efficient ion production and transmission in a 30 Torr pressure environment using solvents compatible with typical reversed-phase liquid chromatography (RPLC) separations. In this design, the electrospray emitter is located inside the mass spectrometer in the same region as an electrodynamic ion funnel. This avoids the use of a conductance limit ion inlet, as required by a conventional atmospheric pressure ESI source, and allows more efficient ion transmission to the mass analyzer. The new source, titled Subambient Pressure Ionization with Nanoelectrospray (SPIN), improves instrument sensitivity, increases the understanding of the electrospray process, and enables new electrospray interface designs. Performance of the SPIN source was evaluated by electrospraying standard solutions at 300 nL/min, and comparing results with those obtained from a standard atmospheric pressure ESI source that used a heated capillary inlet. The importance of desolvation was also investigated by electrospraying at different flow rates, which showed that the ion funnel provided an effective desolvation region to aid the creation of gas phase analyte ions. This initial study demonstrated a ∼ 5-fold improvement in sensitivity when the SPIN source was used compared to a standard atmospheric pressure ESI source. PMID:18237189

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

    PubMed

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

    2017-08-04

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

  6. Desorption electro-flow focusing ionization of explosives and narcotics for ambient pressure mass spectrometry.

    PubMed

    Forbes, Thomas P; Brewer, Tim M; Gillen, Greg

    2013-10-07

    Desorption electro-flow focusing ionization (DEFFI), a desorption-based ambient ion source, was developed, characterized, and evaluated as a possible source for field deployable ambient pressure mass spectrometry (APMS). DEFFI, based on an electro-flow focusing system, provides a unique configuration for the generation of highly charged energetic droplets for sample analysis and ionization. A concentrically flowing carrier gas focuses the liquid emanating from a capillary through a small orifice, generating a steady fluid jet. An electric field is applied across this jet formation region, producing high velocity charged droplets that impinge on an analyte laden surface. This configuration separates the jet charging region from the external environment, eliminating detrimental effects from droplet space charge or target surface charging. The sample desorption and ionization processes operate similar to desorption electrospray ionization (DESI). DEFFI demonstrated strong signal intensities and improved signal-to-noise ratios in both positive and negative mode mass spectrometry for narcotics, i.e., cocaine, and explosives, i.e., cyclotrimethylenetrinitramine (RDX), respectively. A characterization of DEFFI ionization mechanisms identified operation regimes of both electrospray and corona discharge based analyte ionization, as well as limitations in overall signal. In addition, the DEFFI response was directly compared to DESI-MS under similar operating conditions. This comparison established a wider and more stable optimal operating range, while requiring an order of magnitude lower applied gas pressure and applied potential for DEFFI than DESI. These reductions are due to the physical mode of jet formation and geometric configuration differences between DEFFI and DESI, pointing to a potential benefit of DEFFI-MS for field implementation.

  7. Basic rules for the interpretation of atmospheric pressure ionization mass spectra of small molecules.

    PubMed

    Holcapek, Michal; Jirásko, Robert; Lísa, Miroslav

    2010-06-18

    This review summarizes the basic rules for the interpretation of atmospheric pressure ionization (API) mass spectra of small molecules written with the style primarily intended for beginners and low-experienced researchers with the mass spectra interpretation. The first and basic step in any interpretation of mass spectra is always the determination of molecular weight, which is relatively easy in case of soft ionization techniques due to the limited extend of fragmentation and the prevailing presence of (de)protonated molecules in the full scan mass spectra. These [M+H](+) and [M-H](-) ions are often accompanied by low abundant molecular adducts, which can be used as the supplementary information for the unambiguous determination of molecular weights. In certain cases, adduct ions may dominate the spectra. The subsequent interpretation of full scan and tandem mass spectra is more complicated due to a high number of possible functional groups, structural subunits and their combinations resulting in numerous competitive fragmentation pathways. Typical neutral losses and the effect of individual functional groups on the fragmentation are discussed in detail and illustrated with selected examples. Modern mass analyzers have powerful features for the structural elucidation, for example high resolving power, high mass accuracy, multistage tandem mass spectrometry, dedicated softwares for the interpretation of mass spectra and prediction of their fragmentation. Background information on differences among individual ionization techniques suitable for the HPLC-MS coupling and basic types of mass analyzers with consequences for the data interpretation is briefly discussed as well. Selected examples illustrate that the right optimization of chromatographic separation and the use of other than mass spectrometric detectors can bring valuable complementary information. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  8. Microplasma discharge vacuum ultraviolet photoionization source for atmospheric pressure ionization mass spectrometry.

    PubMed

    Symonds, Joshua M; Gann, Reuben N; Fernández, Facundo M; Orlando, Thomas M

    2014-09-01

    In this paper, we demonstrate the first use of an atmospheric pressure microplasma-based vacuum ultraviolet (VUV) photoionization source in atmospheric pressure mass spectrometry applications. The device is a robust, easy-to-operate microhollow cathode discharge (MHCD) that enables generation of VUV photons from Ne and Ne/H(2) gas mixtures. Photons were detected by excitation of a microchannel plate detector and by analysis of diagnostic sample ions using a mass spectrometer. Reactive ions, charged particles, and metastables produced in the discharge were blocked from entering the ionization region by means of a lithium fluoride window, and photoionization was performed in a nitrogen-purged environment. By reducing the output pressure of the MHCD, we observed heightened production of higher-energy photons, making the photoionization source more effective. The initial performance of the MHCD VUV source has been evaluated by ionizing model analytes such as acetone, azulene, benzene, dimethylaniline, and glycine, which were introduced in solid or liquid phase. These molecules represent species with both high and low proton affinities, and ionization energies ranging from 7.12 to 9.7 eV.

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

    NASA Astrophysics Data System (ADS)

    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 (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported 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

  10. Fast Differential Analysis of Propolis Using Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Huang, Xue-yong; Guo, Xia-li; Luo, Huo-lin; Fang, Xiao-wei; Zhu, Teng-gao; Zhang, Xing-lei; Chen, Huan-wen; Luo, Li-ping

    2015-01-01

    Mass spectral fingerprints of 24 raw propolis samples, including 23 from China and one from the United States, were directly obtained using surface desorption atmospheric pressure chemical ionization mass spectrometry (SDAPCI-MS) without sample pretreatment. Under the optimized experimental conditions, the most abundant signals were detected in the mass ranges of 70 to 500 m/z and 200 to 350 m/z, respectively. Principal component analyses (PCA) for the two mass ranges showed similarities in that the colors had a significant correlation with the first two PCs; in contrast there was no correlation with the climatic zones from which the samples originated. Analytes such as chrysin, pinocembrin, and quercetin were detected and identified using multiple stage mass spectrometry within 3 min. Therefore, SDAPCI-MS can be used for rapid and reliable high-throughput analysis of propolis. PMID:26339245

  11. "Magic" Ionization Mass Spectrometry.

    PubMed

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The “magic” that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  12. "Magic" Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The "magic" that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  13. Atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry--a method to differentiate isomers by mass spectrometry.

    PubMed

    Ahmed, Arif; Kim, Sunghwan

    2013-12-01

    In this report, a method for in-source hydrogen/deuterium (H/D) exchange at atmospheric pressure is reported. The method was named atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry (APPI HDX MS). H/D exchange was performed by mixing samples dissolved in toluene with CH3OD solvent and analyzing the mixture using atmospheric pressure photo ionization mass spectrometry (APPI-MS). The APPI HDX spectra obtained with contact times between the analyte solution and methanol-OD (CH3OD) of < 0.5 s or 1 h showed the same pattern of H/D exchange. Therefore, it was concluded that APPI HDX occurred in the source but not in the solution. The proposed method does not require a specific type of mass spectrometer and can be performed at atmospheric pressure. H/D exchange can be performed in any laboratory with a mass spectrometer and a commercial APPI source. Using this method, multiple H/D exchanges of aromatic hydrogen and/or H/D exchange of active hydrogen were observed. These results demonstrated that H/D exchange can be used to distinguish between isomers containing primary, secondary, and tertiary amines, as well as pyridine and pyrrole functional groups.

  14. Laser-Induced Acoustic Desorption/Atmospheric Pressure Chemical Ionization Mass Spectrometry

    PubMed Central

    Gao, Jinshan; Borton, David J.; Owen, Benjamin C.; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M.; Madden, Jeremy T.; Qian, Kuangnan; Kenttämaa, Hilkka I.

    2010-01-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a linear quadrupole ion trap mass spectrometer (LQIT). Model compounds representing a wide variety of different types, including basic nitrogen and oxygen compounds, aromatic and aliphatic compounds, as well as unsaturated and saturated hydrocarbons, were tested separately and as a mixture. These model compounds were successfully evaporated into the gas phase by using LIAD and then ionized by using APCI with different reagents. Four APCI reagent systems were tested: the traditionally used mixture of methanol and water, neat benzene, neat carbon disulfide, and nitrogen gas (no liquid reagent). The mixture of methanol and water produced primarily protonated molecules, as expected. However, only the most basic compounds yielded ions under these conditions. In sharp contrast, using APCI with either neat benzene or neat carbon disulfide as the reagent resulted in the ionization of all the analytes studied to predominantly yield stable molecular ions. Benzene yielded a larger fraction of protonated molecules than carbon disulfide, which is a disadvantage. A similar amount of fragmentation was observed for these reagents. When the experiment was performed without a liquid reagent(nitrogen gas was the reagent), more fragmentation was observed. Analysis of a known mixture as well as a petroleum cut was also carried out. In summary, the new experiment presented here allows the evaporation of thermally labile compounds, both polar and nonpolar, without dissociation or aggregation, and their ionization to form stable molecular ions. PMID:21472571

  15. Laser-induced acoustic desorption/atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Gao, Jinshan; Borton, David J; Owen, Benjamin C; Jin, Zhicheng; Hurt, Matt; Amundson, Lucas M; Madden, Jeremy T; Qian, Kuangnan; Kenttämaa, Hilkka I

    2011-03-01

    Laser-induced acoustic desorption (LIAD) was successfully coupled to a conventional atmospheric pressure chemical ionization (APCI) source in a commercial linear quadrupole ion trap mass spectrometer (LQIT). Model compounds representing a wide variety of different types, including basic nitrogen and oxygen compounds, aromatic and aliphatic compounds, as well as unsaturated and saturated hydrocarbons, were tested separately and as a mixture. These model compounds were successfully evaporated into the gas phase by using LIAD and then ionized by using APCI with different reagents. From the four APCI reagent systems tested, neat carbon disulfide provided the best results. The mixture of methanol and water produced primarily protonated molecules, as expected. However, only the most basic compounds yielded ions under these conditions. In sharp contrast, using APCI with either neat benzene or neat carbon disulfide as the reagent resulted in the ionization of all the analytes studied to predominantly yield stable molecular ions. Benzene yielded a larger fraction of protonated molecules than carbon disulfide, which is a disadvantage. A similar but minor amount of fragmentation was observed for these two reagents. When the experiment was performed without a liquid reagent (nitrogen gas was the reagent), more fragmentation was observed. Analysis of a known mixture as well as a petroleum cut was also carried out. In summary, the new experiment presented here allows the evaporation of thermally labile compounds, both polar and nonpolar, without dissociation or aggregation, and their ionization to predominantly form stable molecular ions.

  16. Gas chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Luosujärvi, Laura; Haapala, Markus; Grigoras, Kestas; Ketola, Raimo A; Kotiaho, Tapio; Franssila, Sami; Kostiainen, Risto

    2006-05-01

    An atmospheric pressure chemical ionization (APCI) microchip is presented for combining a gas chromatograph (GC) to a mass spectrometer (MS). The chip includes capillary insertion channel, stopper, vaporizer channel, nozzle and nebulizer gas inlet fabricated on the silicon wafer, and a platinum heater sputtered on a glass wafer. These two wafers are joined by anodic bonding creating a two-dimensional version of an APCI microchip. The sample from GC is directed via heated transfer line capillary to the vaporizer channel of the APCI chip. The etched nozzle forms narrow sample plume, which is ionized by an external corona discharge needle, and the ions are analyzed by a mass spectrometer. The GC-microchip APCI-MS combination provides an efficient method for qualitative and quantitative analysis. The spectra produced by microchip APCI show intensive protonated molecule and some fragmentation products as in classical chemical ionization for structure elucidation. In quantitative analysis the GC-microchip APCI-MS showed good linearity (r(2) = 0.9989) and repeatability (relative standard deviation 4.4%). The limits of detection with signal-to-noise ratio of three were between 0.5 and 2 micromol/L with MS mode using selected ion monitoring and 0.05 micromol/L with MS/MS using multiple reaction monitoring.

  17. Performance of dielectric barrier discharge ionization mass spectrometry for pesticide testing: a comparison with atmospheric pressure chemical ionization and electrospray ionization.

    PubMed

    Gilbert-López, Bienvenida; Geltenpoth, Helma; Meyer, Cordula; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan F; Franzke, Joachim

    2013-02-15

    The present study reports on the evaluation of dielectric barrier discharge microplasma ionization (DBDI) for liquid chromatography/high resolution mass spectrometry (LC/HRMS) analyses of pesticide residues in fruit and vegetables. Ionization, fragmentation, analytical performance and matrix effects displayed by LC/DBDI-MS were critically evaluated and compared with both atmospheric pressure chemical ionization (APCI) and electrospray (ESI), using a set of over 40 representative multiclass pesticides. Sample preparation was accomplished using standard QuEChERS procedure and the identification and quantitation of the pesticides tested accomplished by means of LC/MS with a hybrid linear quadrupole ion trap (LIT)-Fourier transform ion cyclotron resonance (FTICR) mass spectrometer operated in full-scan positive ion mode using DBDI, APCI and ESI sources. The developed LC/DBDI-MS method allowed the screening of 43 pesticides in three different vegetable matrices: apple, orange and tomato. Minor matrix effects (i.e. signal suppression or enhancement ≤20%) were observed in most of the studied compounds: 95%, 70% and 81% of the studied compounds showed minor matrix effects in extracts of apple, orange and tomato, respectively. The results of the analysis of spiked orange extracts showed that the sensitivity obtained with LC/DBDI-MS is appropriate for multi-residue analysis of pesticide residues in fruit and vegetable samples. The limits of quantitation (LOQs) obtained for most of the studied pesticides were in compliance with the European Regulation 396/2005 (and subsequent updates) on food commodities (default maximum residue level of 10 µg kg(-1)). Comparative studies with commercial sources demonstrate the suitability of DBDI as an ionization technique for residue analysis, because of the combination of the following two advantages: (1) the use of DBDI provides minimized matrix effects compared with APCI, and (2) improved the detection - in terms of sensitivity - of

  18. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

  19. Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Bergloff, J. F.; Rodriguez, J. E.; Munro, W.; Karpas, Z.

    1999-01-01

    Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

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

    SciTech Connect

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

    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.

  1. Vapor Pressure of Hexamethylene Triperoxide Diamine (HMTD) Estimated Using Secondary Electrospray Ionization Mass Spectrometry.

    PubMed

    Aernecke, Matthew J; Mendum, Ted; Geurtsen, Geoff; Ostrinskaya, Alla; Kunz, Roderick R

    2015-11-25

    A rapid method for vapor pressure measurement was developed and used to derive the vapor pressure curve of the thermally labile peroxide-based explosive hexamethylene triperoxide diamine (HMTD) over the temperature range from 28 to 80 °C. This method uses a controlled flow of vapor from a solid-phase HMTD source that is presented to an ambient-pressure-ionization mass spectrometer equipped with a secondary-electrospray-ionization (SESI) source. The subpart-per-trillion sensitivity of this system enables direct detection of HMTD vapor through an intact [M + H](+) ion in real time at temperatures near 20 °C. By calibrating this method using vapor sources of cocaine and heroin, which have known pressure-temperature (P-T) curves, the temperature dependence of HMTD vapor was determined, and a Clausius-Clapeyron plot of ln[P (Pa)] vs 1/[T (K)] yielded a straight line with the expression ln[P (Pa)] = {(-11091 ± 356) × 1/[T (K)]} + 25 ± 1 (error limits are the standard error of the regression analysis). From this equation, the sublimation enthalpy of HMTD was estimated to be 92 ± 3 kJ/mol, which compares well with the theoretical estimate of 95 kJ/mol, and the vapor pressure at 20 °C was estimated to be ∼60 parts per trillion by volume, which is within a factor of 2 of previous theoretical estimates. Thus, this method provides not only the first direct experimental determination of HMTD vapor pressure but also a rapid, near-real-time capability to quantitatively measure low-vapor-pressure compounds, which will be useful for aiding in the development of training aids for bomb-sniffing canines.

  2. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ.

  3. In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2016-07-01

    We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

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

    PubMed

    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.

  5. Microfluidic Chip Coupled with Thermal Desorption Atmospheric Pressure Ionization Mass Spectrometry

    PubMed Central

    Chang, Chia-Hsien; Chen, Tsung-Yi; Chen, Yu-Chie

    2014-01-01

    Microfluidic chips have been used as platforms for a diversity of research purposes such as for separation and micro-reaction. One of the suitable detectors for microfluidic chip is mass spectrometry. Because microfluidic chips are generally operated in an open air condition, mass spectrometry coupled with atmospheric pressure ion sources can suit the requirement with minimum compromise. In this study, we develop a new interface to couple a microfluidic chip with mass spectrometry. A capillary tip coated with a layer of graphite, capable of absorbing energy of near-infrared (NIR) light is used to interface microfluidic chip with mass spectrometry. An NIR laser diode (λ=808 nm) is used to irradiate the capillary tip for assisting the generation of spray from the eluent of the microfluidic chip. An electrospray is provided to fuse with the spray generated from the microfluidic chip for post-ionization. Transesterification is used as the example to demonstrate the feasibility of using this interface to couple microfluidic chip with mass spectrometry. PMID:26839753

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  8. HPLC/atmospheric pressure chemical ionization-mass spectroscopy of eight regulated sulfonamides.

    PubMed

    Combs, M T; Ashraf-Khorassani, M; Taylor, L T

    1999-03-01

    Reversed phase high performance liquid chromatography coupled with on-line atmospheric pressure chemical ionization mass spectrometry, HPLC,APCI-MS, has been applied to a mixture of eight sulfonamides. In full scan mode, extracted ion chromatograms produced minimum detectable quantities (MDQ) of 0.8 ng on column, for six of the eight regulated sulfonamides investigated. Selected ion monitoring yielded a 50 pg MDQ for sulfamerazine, sulfadiazine and sulfamethazine, while, the other compounds presented higher values. Analysis of supercritical fluid extracts of chicken liver containing sulfadimethoxine were found to be easily detected by HPLC/APCI-MS. In extracts of chicken liver spiked with 25 microg/kg(-1) (25 ppb) of sulfadimethoxine this compound could be detected in selected ion mode, while 100 pg/microl(-1) was detectable in either full scan or single ion modes. The analysis method for extracted sulfadimethoxine also demonstrated good linearity and reproducibility in both single ion and scan mode.

  9. Established and Emerging Atmospheric Pressure Surface Sampling/Ionization Techniques for Mass Spectrometry

    SciTech Connect

    Van Berkel, Gary J; Pasilis, Sofie P; Ovchinnikova, Olga S

    2008-01-01

    The number and type of atmospheric pressure techniques suitable for sampling analytes from surfaces, forming ions from those analytes, and subsequently transporting those ions into vacuum for interrogation by mass spectrometry has 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 review, we sort this vast array of techniques into a 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.

  10. Capillary liquid chromatography-microchip atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Ostman, Pekka; Jäntti, Sirkku; Grigoras, Kestas; Saarela, Ville; Ketola, Raimo A; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto

    2006-07-01

    A miniaturized nebulizer chip for capillary liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (capillary LC-microchip APCI-MS) is presented. The APCI chip consists of two wafers, a silicon wafer and a Pyrex glass wafer. The silicon wafer has a DRIE etched through-wafer nebulizer gas inlet, an edge capillary insertion channel, a stopper, a vaporizer channel and a nozzle. The platinum heater electrode and pads for electrical connection were patterned on to the Pyrex glass wafer. The two wafers were joined by anodic bonding, creating a microchip version of an APCI-source. The sample inlet capillary from an LC column is directly connected to the vaporizer channel of the APCI chip. The etched nozzle in the microchip forms a narrow sample plume, which is ionized by an external corona needle, and the formed ions are analyzed by a mass spectrometer. The nebulizer chip enables for the first time the use of low flow rate separation techniques with APCI-MS. The performance of capillary LC-microchip APCI-MS was tested with selected neurosteroids. The capillary LC-microchip APCI-MS provides quantitative repeatability and good linearity. The limits of detection (LOD) with a signal-to-noise ratio (S/N) of 3 in MS/MS mode for the selected neurosteroids were 20-1000 fmol (10-500 nmol l(-1)). LODs (S/N = 3) with commercial macro APCI with the same compounds using the same MS were about 10 times higher. Fast heat transfer allows the use of the optimized temperature for each compound during an LC run. The microchip APCI-source provides a convenient and easy method to combine capillary LC to any API-MS equipped with an APCI source. The advantages and potentials of the microchip APCI also make it a very attractive interface in microfluidic APCI-MS.

  11. Sample introduction and pressure measuring system for chemical ionization mass spectrometers

    SciTech Connect

    Illies, A.J.; Bowers, M.T.; Meisels, G.G.

    1981-08-01

    One of the difficulties with using chemical ionization mass spectrometry (CIMS) in magnetic sector instruments has been that of electrical dischargers through the gaseous sample between the ion source, which may be at potentials at 10kV and ground. A sample introduction method is presented to offset this. It was first used at the University of Nebraska, Lincoln on a modified Atlas CH-4 mass spectrometer operated at ion source potentials up to 3 kV and pressures up to 3 torr. The same technique has been extended at the University of California, Santa Barbara (UCSB), for use with a VG-Micromass ZAB-2F mass spectrometer operated at source potentials as high as 10 kV and pressures up to 1 torr. The basic features of the design are presented. The sample leak valve which is at ground potential feeds into a glass tube which has been packed with approximately 4 in. of glass wool. The end of this glass tube is in contact with the ion source potential. The authors believe that the glass wool may prevent discharging by reducing the positive ion velocities below that required for the emission of secondary electrons and/or providing a very large surface area which may act as the third body in the ion-electron recombination reaction I/sup +/ + e/sup -/ + M ..-->.. I + M. At UCSB this sample introduction system is used for all gaseous and volatile liquid samples in both EI and CI modes. The only disadvantage with the sample introduction system involves the removal of very polar samples from the glass wool. However, overnight pumping has removed all samples we have used to date.

  12. Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

    USDA-ARS?s Scientific Manuscript database

    A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...

  13. 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.

    PubMed

    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.

  14. Probe electrospray ionization (PESI) mass spectrometry with discontinuous atmospheric pressure interface (DAPI).

    PubMed

    Hiraoka, Kenzo; Usmanov, Dilshadbek T; Chen, Lee Chuin; Ninomiya, Satoshi; Mandal, Mridul K; Saha, Subhrakanti

    2015-01-01

    Probe electrospray ionization (PESI) using a 0.2 mm outside diameter titanium wire was performed and the generated ions were introduced into the mass spectrometer via a discontinuous atmospheric pressure interface using a pinch valve. Time-lapse PESI mass spectra were acquired by gradually increasing delay time for the pinch valve opening with respect to the start of each electrospray event when a high voltage was applied. The opening time of the pinch valve was 20 ms. Time-resolved PESI mass spectra showed marked differences for 10 mM NaCl, 10(-5) M gramicidin S and insulin in H(2)O/CH(3)OH/CH(3)COOH/CH(3)COONH(4) (65/35/1) with and without the addition of 10 mM CH(3)COONH(4). This was ascribed to the pH change of the liquid attached to the needle caused by electrochemical reactions taking place at the interface between the metal probe and the solution. NaCl cluster ions appeared only after the depletion of analytes. For the mixed solution of 10(-5) M cytochrome c, insulin, and gramicidin S in H(2)O/CH(3)OH/CH(3)COOH (65/35/1), a sequential appearance of analyte ions in the order of cytochrome c→insulin→gramicidin S was observed. The present technique was applied to three narcotic samples; methamphetamine, morphine and codeine. Limits of detection for these compounds were 10 ppb in H(2)O/CH(3)OH (1/1) for the single sampling with a pinch valve opening time of 200 ms.

  15. Direct coupling of supercritical fluid chromatography with tandem mass spectrometry for the analysis of amino acids and related compounds: Comparing electrospray ionization and atmospheric pressure chemical ionization.

    PubMed

    Wolrab, Denise; Frühauf, Peter; Gerner, Christopher

    2017-08-15

    For acceptance of supercritical fluid chromatography (SFC) as a routine analysis method, the hyphenation to mass spectrometry (MS), which is typically achieved either by a splitting device or by the employment of an additional make up flow, has to be improved. Direct coupling of SFC to MS (/MS) would simplify the handling of this method. Consequently, this work focused on the direct coupling of SFC to mass spectrometry and the influence of the employed ion source on signal intensities of polar and ionic compounds in biological samples. A method for separating metabolites of the tryptophan pathway as well as other amino acids is shown. Results demonstrate that SFC is capable of separating analytes of polar and ionic nature. Modifications of the SFC system by cryostat cooling lead to higher temperature stability in the booster pump and therefore to a better reproducibility of retention times and a low dispersion nozzle inside the active back pressure regulator (ABPR) significantly improves peak shape and sensitivity when using the MS. The comparison of the ionization efficiencies using electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) in positive and negative ion mode shows analyte depending sensitivities. However, results indicate that APCI is better suitable for the ionization of amino acids with polar side chains, whereas ESI proved superior for the ionization of amino acids featuring hydrophobic residues. Analyte signals were suppressed with ESI when using a complex matrix such as human serum, but rather enhanced when using APCI. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging.

    PubMed

    Li, Ming; Jia, Bin; Ding, Liying; Hong, Feng; Ouyang, Yongzhong; Chen, Rui; Zhou, Shumin; Chen, Huanwen; Fang, Xiang

    2013-09-01

    Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS), which was operated in either a gasless, solvent-free or methanol vapor-assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI-MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI-MS imaging differentiated a 10-min old from two 4 h old samples. Non-destructive forensic analysis of forged signatures either handwritten or computer-assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI-MS. The experimental results show that DAPCI-MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications.

  17. Determination of nitrogen monoxide in high purity nitrogen gas with an atmospheric pressure ionization mass spectrometer

    NASA Technical Reports Server (NTRS)

    Kato, K.

    1985-01-01

    An atmospheric pressure ionization mass spectrometric (API-MS) method was studied for the determination of residual NO in high purity N2 gas. The API-MS is very sensitive to NO, but the presence of O2 interferes with the NO measurement. Nitrogen gas in cylinders as sample gas was mixed with NO standard gas and/or O2 standard gas, and then introduced into the API-MS. The calibration curves of NO and O2 has linearity in the region of 0 - 2 ppm, but the slopes changed with every cylinder. The effect of O2 on NO+ peak was additive and proportional to O2 concentration in the range of 0 - 0.5 ppm. The increase in NO+ intensity due to O2 was (0.07 - 0.13)%/O2, 1 ppm. Determination of NO and O2 was carried out by the standard addition method to eliminate the influence of variation of slopes. The interference due to O2 was estimated from the product of the O2 concentration and the ratio of slope A to Slope B. Slope A is the change in the NO+ intensity with the O2 concentration. Slope B is the intensity with O2 concentration.

  18. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

  19. Characterization of Nonpolar Lipids and Selected Steroids by Using Laser-Induced Acoustic Desorption/Chemical Ionization, Atmospheric Pressure Chemical Ionization, and Electrospray Ionization Mass Spectrometry†

    PubMed Central

    Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

    2011-01-01

    Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ 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-H2O) with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O 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(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids. PMID:21528012

  20. Clinical Application of Ambient Ionization Mass Spectrometry

    PubMed Central

    Li, Li-Hua; Hsieh, Hua-Yi; Hsu, Cheng-Chih

    2017-01-01

    Ambient ionization allows mass spectrometry analysis directly on the sample surface under atmospheric pressure with almost zero sample pretreatment. Since the development of desorption electrospray ionization (DESI) in 2004, many other ambient ionization techniques were developed. Due to their simplicity and low operation cost, rapid and on-site clinical mass spectrometry analysis becomes real. In this review, we will highlight some of the most widely used ambient ionization mass spectrometry approaches and their applications in clinical study. PMID:28337399

  1. Specific interaction between negative atmospheric ions and organic compounds in atmospheric pressure corona discharge ionization mass spectrometry.

    PubMed

    Sekimoto, Kanako; Sakai, Mami; Takayama, Mitsuo

    2012-06-01

    The interaction between negative atmospheric ions and various types of organic compounds were investigated using atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. Atmospheric negative ions such as O(2)(-), HCO(3)(-), COO(-)(COOH), NO(2)(-), NO(3)(-), and NO(3)(-)(HNO(3)) having different proton affinities served as the reactant ions for analyte ionization in APCDI in negative-ion mode. The individual atmospheric ions specifically ionized aliphatic and aromatic compounds with various functional groups as atmospheric ion adducts and deprotonated analytes. The formation of the atmospheric ion adducts under certain discharge conditions is most likely attributable to the affinity between the analyte and atmospheric ion and the concentration of the atmospheric ion produced under these conditions. The deprotonated analytes, in contrast, were generated from the adducts of the atmospheric ions with higher proton affinity attributable to efficient proton abstraction from the analyte by the atmospheric ion.

  2. Ambient ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    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.

  3. Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

    PubMed

    Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

    2016-04-29

    An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method.

  4. Absolute method for the assay of oleuropein in olive oils by atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    De Nino, Antonio; Di Donna, Leonardo; Mazzotti, Fabio; Muzzalupo, Enzo; Perri, Enzo; Sindona, Giovanni; Tagarelli, Antonio

    2005-09-15

    Oleuropein (OLP, 1), the active ingredient present (i) in food integrators extracted from olive leaves, (ii) in table olives, and (iii) in extra virgin olive oils is a nutraceutical whose health benefits have been widely documented. A new analytical method for its assay, which is based on the utilization of atmospheric pressure chemical ionization tandem mass spectrometry and on the use of a synthetic labeled analogue, the 4-trideuteriocarboxyoleuropein (2), as an internal standard, is presented. The results obtained with extra virgin olive oils from different cultivars and different Italian regions are discussed.

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

    PubMed

    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.

  6. Commercial intermediate pressure MALDI ion mobility spectrometry mass spectrometer capable of producing highly charged laserspray ionization ions.

    PubMed

    Inutan, Ellen D; Wang, Beixi; Trimpin, Sarah

    2011-02-01

    The first examples of highly charged ions observed under intermediate pressure (IP) vacuum conditions are reported using laser ablation of matrix/analyte mixtures. The method and results are similar to those obtained at atmospheric pressure (AP) using laserspray ionization (LSI) and/or matrix assisted inlet ionization (MAII). Electrospray ionization (ESI), LSI, and MAII are methods operating at AP and have been shown, with or without the use of a voltage or a laser, to produce highly charged ions with very similar ion abundance and charge states. A commercial matrix-assisted laser desorption/ionization ion mobility spectrometry (IMS) mass spectrometry (MS) instrument (SYNAPT G2) was used for the IP developments. The necessary conditions for producing highly charged ions of peptides and small proteins at IP appear to be a pressure drop region and the use of suitable matrixes and laser fluence. Ionization to produce these highly charged ions under the low pressure conditions of IP does not require specific heating or a special inlet ion transfer region. However, under the current setup, ubiquitin is the highest molecular weight protein observed. These findings are in accord with the need to provide thermal energy in the pressure drop region, similar to LSI and MAII, to improve sensitivity and extend the types of compounds that produce highly charged ions. The practical utility of IP-LSI in combination with IMS-MS is demonstrated for the analysis of model mixtures composed of a lipid, peptides, and a protein. Further, endogenous multiply charged peptides are observed directly from delipified mouse brain tissue with drift time distributions that are nearly identical in appearance to those obtained from a synthesized neuropeptide standard analyzed by either LSI- or ESI-IMS-MS at AP. Efficient solvent-free gas-phase separation enabled by the IMS dimension separates the multiply charged peptides from lipids that remained on the delipified tissue. Lipid and peptide

  7. Gas Chromatography Coupled to Atmospheric Pressure Chemical Ionization FT-ICR Mass Spectrometry for Improvement of Data Reliability.

    PubMed

    Schwemer, Theo; Rüger, Christopher P; Sklorz, Martin; Zimmermann, Ralf

    2015-12-15

    Atmospheric pressure chemical ionization (APCI) offers the advantage of molecular ion information with low fragmentation. Hyphenating APCI to gas chromatography (GC) and ultrahigh resolution mass spectrometry (FT-ICR MS) enables an improved characterization of complex mixtures. Data amounts acquired by this system are very huge, and existing peak picking algorithms are usually extremely time-consuming, if both gas chromatographic and ultrahigh resolution mass spectrometric data are concerned. Therefore, automatic routines are developed that are capable of handling these data sets and further allow the identification and removal of known ionization artifacts (e.g., water- and oxygen-adducts, demethylation, dehydrogenation, and decarboxylation). Furthermore, the data quality is enhanced by the prediction of an estimated retention index, which is calculated simply from exact mass data combined with a double bond equivalent correction. This retention index is used to identify mismatched elemental compositions. The approach was successfully tested for analysis of semivolatile components in heavy fuel oil and diesel fuel as well as primary combustion particles emitted by a ship diesel research engine. As a result, 10-28% of the detected compounds, mainly low abundant species, classically assigned by using only the mass spectrometric information, were identified as not valid and removed. Although GC separation is limited by the slow acquisition rate of the FT-ICR MS (<1 Hz), a database driven retention time comparison, as commonly used for low resolution GC/MS, can be applied for revealing isomeric information.

  8. Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

    PubMed

    Sales, Carlos; Portolés, Tania; Sancho, Juan Vicente; Abad, Esteban; Ábalos, Manuela; Sauló, Jordi; Fiedler, Heidelore; Gómara, Belén; Beltrán, Joaquim

    2016-01-01

    A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/μL to 100 pg/μL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/μL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.

  9. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

    2014-06-13

    Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

  10. Planar differential mobility spectrometer as a pre-filter for atmospheric pressure ionization mass spectrometry

    PubMed Central

    Schneider, Bradley B.; Covey, Thomas R.; Coy, Stephen L.; Krylov, Evgeny V.

    2010-01-01

    Ion filters based on planar DMS can be integrated with the inlet configuration of most mass spectrometers, and are able to enhance the quality of mass analysis and quantitative accuracy by reducing chemical noise, and by pre-separating ions of similar mass. This paper is the first in a series of three papers describing the optimization of DMS / MS instrumentation. In this paper the important physical parameters of a planar DMS-MS interface including analyzer geometry, analyzer coupling to a mass spectrometer, and transport gas flow control are considered. The goal is to optimize ion transmission and transport efficiency, provide optimal and adjustable resolution, and produce stable operation under conditions of high sample contamination. We discuss the principles of DMS separations and highlight the theoretical underpinnings. The main differences between planar and cylindrical geometries are presented, including a discussion of the advantages and disadvantages of RF ion focusing. In addition, we present a description of optimization of the frequency and amplitude of the DMS fields for resolution and ion transmission, and a discussion of the influence and importance of ion residence time in DMS. We have constructed a mass spectrometer interface for planar geometries that takes advantage of atmospheric pressure gas dynamic principles, rather than ion focusing, to minimize ion losses from diffusion in the analyzer and to maximize total ion transport into the mass spectrometer. A variety of experimental results has been obtained that illustrate the performance of this type of interface, including tests of resistance to high contamination levels, and the separation of stereoisomers. In a subsequent publication the control of the chemical interactions that drive the separation process of a DMS / MS system will be considered. In a third publication we describe novel electronics designed to provide the high voltages asymmetric waveform fields (SV) required for these

  11. Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer

    SciTech Connect

    Albrecht, Sascha Stroh, Fred; Klopotowski, Sebastian Derpmann, Valerie Klee, Sonja Brockmann, Klaus J. Benter, Thorsten

    2014-01-15

    In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID.

  12. Application of Atmospheric Pressure Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for Rapid Identification of Neisseria Species

    PubMed Central

    Gudlavalleti, Seshu K.; Sundaram, Appavu K; Razumovski, Jane; Doroshenko, Vladimir

    2008-01-01

    Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI MS) was applied to develop a proteomics-based method to detect and identify Neisseria species. Heat-inactivated clinical isolate cell suspensions of Neisseria gonorrhoeae and strains belonging to five serogroups (A, B, C, W135, and Y) of Neisseria meningitidis were subjected to on-probe protein/peptide extraction and tryptic digestion followed by AP-MALDI tandem MS (MS/MS)-based proteomic analysis. Amino acid sequences derived from three protonated peptides with m/z values of 1743.8, 1894.8, and 1946.8 were identified by AP-MALDI MS/MS and MASCOT proteome database search analysis as belonging to neisserial acyl carrier protein, neisserial-conserved hypothetical protein, and neisserial putative DNA binding protein, respectively. These three peptide masses can thus be potential biomarkers for neisserial species identification by AP-MALDI MS. PMID:19137107

  13. Laserspray ionization on a commercial atmospheric pressure-MALDI mass spectrometer ion source: selecting singly or multiply charged ions.

    PubMed

    McEwen, Charles N; Larsen, Barbara S; Trimpin, Sarah

    2010-06-15

    Multiply charged ions, similar to those obtained with electrospray ionization, are produced at atmospheric pressure (AP) using standard MALDI conditions of laser fluence and reflective geometry. Further, the charge state can be switched to singly charged ions nearly instantaneously by changing the voltage applied to the MALDI target plate. Under normal AP-MALDI operating conditions in which a voltage is applied to the target plate, primarily singly charged ions are observed, but at or near zero volts, highly charged ions are observed for peptides and proteins. Thus, switching between singly and multiply charged ions requires only manipulation of a single voltage. As in ESI, multiple charging, produced using the AP-MALDI source, allows compounds with molecular weights beyond the mass-to-charge limit of the mass spectrometer to be observed and improves the fragmentation relative to singly charged ions.

  14. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis.

    PubMed

    Hoffmann, William D; Kertesz, Vilmos; Srijanto, Bernadeta R; Van Berkel, Gary J

    2017-03-07

    The use of atomic force microscopy controlled nanothermal analysis probes for reproducible spatially resolved thermally assisted sampling of micrometer-sized areas (ca. 11 × 17 μm wide × 2.4 μm deep) from relatively low number-average molecular weight (Mn < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nanothermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. The procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed, and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data-dependent tandem mass spectra was also demonstrated. The material type limits to the current sampling and analysis approach as well as possible improvements in nanothermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415 °C are also discussed.

  15. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis

    SciTech Connect

    Hoffmann, William D; Kertesz, Vilmos; Srijanto, Bernadeta R; Van Berkel, Gary J

    2017-01-01

    The use of atomic force microscopy controlled nano-thermal analysis probes for reproducible spatially resolved thermally-assisted sampling of micrometer-sized areas (ca. 11 m 17 m wide 2.4 m deep) from relatively low number average molecular weight (Mn < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nano-thermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. The procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data dependent tandem mass spectra was also demonstrated. The material type limits to the current sampling and analysis approach as well as possible improvements in nano-thermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415 oC are also discussed.

  16. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis

    DOE PAGES

    Hoffmann, William D.; Kertesz, Vilmos; Srijanto, Bernadeta R.; ...

    2017-02-20

    The use of atomic force microscopy controlled nano-thermal analysis probes for reproducible spatially resolved thermally-assisted sampling of micrometer-sized areas (ca. 11 m 17 m wide 2.4 m deep) from relatively low number average molecular weight (Mn < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nano-thermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. Furthermore, the procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed and the oligomermore » distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data dependent tandem mass spectra was also demonstrated. We also discuss the material type limits to the current sampling and analysis approach as well as possible improvements in nano-thermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415°C.« less

  17. Automatic sampling and analysis of organics and biomolecules by capillary action-supported contactless atmospheric pressure ionization mass spectrometry.

    PubMed

    Hsieh, Cheng-Huan; Meher, Anil Kumar; Chen, Yu-Chie

    2013-01-01

    Contactless atmospheric pressure ionization (C-API) method has been recently developed for mass spectrometric analysis. A tapered capillary is used as both the sampling tube and spray emitter in C-API. No electric contact is required on the capillary tip during C-API mass spectrometric analysis. The simple design of the ionization method enables the automation of the C-API sampling system. In this study, we propose an automatic C-API sampling system consisting of a capillary (∼1 cm), an aluminium sample holder, and a movable XY stage for the mass spectrometric analysis of organics and biomolecules. The aluminium sample holder is controlled by the movable XY stage. The outlet of the C-API capillary is placed in front of the orifice of a mass spectrometer, whereas the sample well on the sample holder is moved underneath the capillary inlet. The sample droplet on the well can be readily infused into the C-API capillary through capillary action. When the sample solution reaches the capillary outlet, the sample spray is readily formed in the proximity of the mass spectrometer applied with a high electric field. The gas phase ions generated from the spray can be readily monitored by the mass spectrometer. We demonstrate that six samples can be analyzed in sequence within 3.5 min using this automatic C-API MS setup. Furthermore, the well containing the rinsing solvent is alternately arranged between the sample wells. Therefore, the C-API capillary could be readily flushed between runs. No carryover problems are observed during the analyses. The sample volume required for the C-API MS analysis is minimal, with less than 1 nL of the sample solution being sufficient for analysis. The feasibility of using this setup for quantitative analysis is also demonstrated.

  18. Automatic Sampling and Analysis of Organics and Biomolecules by Capillary Action-Supported Contactless Atmospheric Pressure Ionization Mass Spectrometry

    PubMed Central

    Hsieh, Cheng-Huan; Meher, Anil Kumar; Chen, Yu-Chie

    2013-01-01

    Contactless atmospheric pressure ionization (C-API) method has been recently developed for mass spectrometric analysis. A tapered capillary is used as both the sampling tube and spray emitter in C-API. No electric contact is required on the capillary tip during C-API mass spectrometric analysis. The simple design of the ionization method enables the automation of the C-API sampling system. In this study, we propose an automatic C-API sampling system consisting of a capillary (∼1 cm), an aluminium sample holder, and a movable XY stage for the mass spectrometric analysis of organics and biomolecules. The aluminium sample holder is controlled by the movable XY stage. The outlet of the C-API capillary is placed in front of the orifice of a mass spectrometer, whereas the sample well on the sample holder is moved underneath the capillary inlet. The sample droplet on the well can be readily infused into the C-API capillary through capillary action. When the sample solution reaches the capillary outlet, the sample spray is readily formed in the proximity of the mass spectrometer applied with a high electric field. The gas phase ions generated from the spray can be readily monitored by the mass spectrometer. We demonstrate that six samples can be analyzed in sequence within 3.5 min using this automatic C-API MS setup. Furthermore, the well containing the rinsing solvent is alternately arranged between the sample wells. Therefore, the C-API capillary could be readily flushed between runs. No carryover problems are observed during the analyses. The sample volume required for the C-API MS analysis is minimal, with less than 1 nL of the sample solution being sufficient for analysis. The feasibility of using this setup for quantitative analysis is also demonstrated. PMID:23762484

  19. Analysis of lipids with desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) and desorption electrospray ionization-mass spectrometry (DESI-MS).

    PubMed

    Suni, Niina M; Aalto, Henni; Kauppila, Tiina J; Kotiaho, Tapio; Kostiainen, Risto

    2012-05-01

    In this article, the effect of spray solvent on the analysis of selected lipids including fatty acids, fat-soluble vitamins, triacylglycerols, steroids, phospholipids, and sphingolipids has been studied by two different ambient mass spectrometry (MS) methods, desorption electrospray ionization-MS (DESI-MS) and desorption atmospheric pressure photoionization-MS (DAPPI-MS). The ionization of the lipids with DESI and DAPPI was strongly dependent on the spray solvent. In most cases, the lipids were detected as protonated or deprotonated molecules; however, other ions were also formed, such as adduct ions (in DESI), [M-H](+) ions (in DESI and DAPPI), radical ions (in DAPPI), and abundant oxidation products (in DESI and DAPPI). DAPPI provided efficient desorption and ionization for neutral and less polar as well as for ionic lipids but caused extensive fragmentation for larger and more labile compounds because of a thermal desorption process. DESI was more suitable for the analysis of the large and labile lipids, but the ionization efficiency for less polar lipids was poor. Both methods were successfully applied to the direct analysis of lipids from pharmaceutical and food products. Although DESI and DAPPI provide efficient analysis of lipids, the multiple and largely unpredictable ionization reactions may set challenges for routine lipid analysis with these methods. Copyright © 2012 John Wiley & Sons, Ltd.

  20. Design and Performance of a Novel Interface for Combined Matrix-Assisted Laser Desorption Ionization at Elevated Pressure and Electrospray Ionization with Orbitrap Mass Spectrometry.

    PubMed

    Belov, Mikhail E; Ellis, Shane R; Dilillo, Marialaura; Paine, Martin R L; Danielson, William F; Anderson, Gordon A; de Graaf, Erik L; Eijkel, Gert B; Heeren, Ron M A; McDonnell, Liam A

    2017-07-18

    Matrix-Assisted Laser Desorption Ionization, MALDI, has been increasingly used in a variety of biomedical applications, including tissue imaging of clinical tissue samples, and in drug discovery and development. These studies strongly depend on the performance of the analytical instrumentation and would drastically benefit from improved sensitivity, reproducibility, and mass/spatial resolution. In this work, we report on a novel combined MALDI/ESI interface, which was coupled to different Orbitrap mass spectrometers (Elite and Q Exactive Plus) and extensively characterized with peptide and protein standards, and in tissue imaging experiments. In our approach, MALDI is performed in the elevated pressure regime (5-8 Torr) at a spatial resolution of 15-30 μm, while ESI-generated ions are injected orthogonally to the interface axis. We have found that introduction of the MALDI-generated ions into an electrodynamic dual-funnel interface results in increased sensitivity characterized by a limit of detection of ∼400 zmol, while providing a mass measurement accuracy of 1 ppm and a mass resolving power of 120 000 in analysis of protein digests. In tissue imaging experiments, the MALDI/ESI interface has been employed in experiments with rat brain sections and was shown to be capable of visualizing and spatially characterizing very low abundance analytes separated only by 20 mDa. Comparison of imaging data has revealed excellent agreement between the MALDI and histological images.

  1. Detection of non-prescription heroin markers in urine with liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Bogusz, M J; Maier, R D; Erkens, M; Kohls, U

    2001-09-01

    The planned introduction of a prescription heroin program in Germany created a need for differentiation between non-prescription and prescribed diamorphine use. The following substances were chosen as markers of non-prescription heroin: acetylcodeine (AC); its metabolites codeine (C) and codeine 6-glucuronide (C6G); papaverine (P); and noscapine (N). Typical heroin markers diamorphine (DAM) and its metabolites monoacetylmorphine (MAM) and morphine (M) were also determined. The drugs were extracted from urine samples with solid-phase extraction (C18) using standard 200-mg columns and 96-well microplates (100 mg). The extracts were examined with liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (positive ionization) in two isocratic systems. Selected ion monitoring procedures were applied for protonated molecular masses and characteristic fragments of drugs involved. The limits of detection were in the range of 0.5-1 ng/mL urine. The occurrence of selected heroin markers was investigated in 25 urine samples collected from heroin abusers (road traffic offenders and overdosed patients). C6G was found in all samples, C in 24 samples, N in 22 samples, MAM in 16 samples, P in 14 samples, DAM in 12 samples, and AC in 4 samples. The appearance of these compounds in urine reflects their pharmacokinetic properties and the composition of non-prescription heroin.

  2. Mass spectrometry in the characterization of ambers. I. Studies of amber samples of different origin and ages by laser desorption ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization mass spectrometry.

    PubMed

    Tonidandel, Loris; Ragazzi, Eugenio; Roghi, Guido; Traldi, Pietro

    2008-01-01

    Amber is a fossil resin constituted of organic polymers derived through complex maturation processes of the original plant resin. A classification of eight samples of amber of different geological age (Miocene to Triassic) and geographical origin is here proposed using direct mass spectrometric techniques, i.e. laser desorption ionization (LDI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI), in order to obtain a fingerprint related to the amber origin. Differences and similarities were detected among the spectra with the four methods, showing quite complex spectra, full of ionic species in the mass range investigated (up to m/z 2000). The evaluation required statistical analysis involving multivariate techniques. Cluster analysis or principal component analysis (PCA) generally did not show a clear clustering with respect to the age of samples, except for the APPI method, which allowed a satisfying clustering. Using the total ion current (TIC) obtained by the different analytical approaches on equal quantities of the different amber samples and plotted against the age, the only significant correlation appeared to be that involving APPI. To validate the method, four amber samples from Cretaceous of Spain were analyzed. Also in this case a significant correlation with age was found only with APPI data. PCA obtained with TIC values from all the MS methods showed a fair grouping of samples, according to their age. Three main clusters could be detected, belonging to younger, intermediate and older fossil resins, respectively. This MS analysis on crude amber, either solid or extract, followed by appropriate multivariate statistical evaluation, can provide useful information on amber age. The best results are those obtained by APPI, indicating that the quantity of amber soluble components that can be photoionized decreases with increasing age, in agreement with the formation of highly stable, insoluble polymers.

  3. Desorption electrospray ionization-mass spectrometric analysis of low vapor pressure chemical particulates collected from a surface.

    PubMed

    Ewing, K J; Gibson, D; Sanghera, J; Miklos, F

    2015-01-01

    The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization-mass spectrometry (DESI-MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI-MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively.

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

    PubMed

    Brust, Hanneke; van Asten, Arian; Koeberg, Mattijs; Dalmolen, Jan; van der Heijden, Antoine; Schoenmakers, Peter

    2014-04-18

    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 post-explosion and naturally degraded PETN could be achieved based on the relative amounts of the degradation products. This information can be used as evidence when investigating a possible relationship between a suspect and a post-explosion crime scene. The present work focuses on accurate quantitation of PETN and its degradation products, using PETriN, PEDiN and PEMN standards specifically synthesized for this purpose. With the use of these standards, the ionization behavior of these compounds was studied, and a quantitative method was developed. Quantitation of PETN and trace levels of its degradation products was shown to be possible with accuracy between 85.7% and 103.7% and a precision ranging from 1.3% to 11.5%. The custom-made standards resulted in a more robust and reliable method to discriminate between post-explosion and naturally-degraded PETN. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Trace determination of 13 haloacetamides in drinking water using liquid chromatography triple quadrupole mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Chu, Wenhai; Gao, Naiyun; Yin, Daqiang; Krasner, Stuart W; Templeton, Michael R

    2012-04-27

    The haloacetamides (HAcAms) are disinfection by-products (DBPs) in drinking water which are currently receiving increased scientific attention due to their elevated toxicity relative to regulated disinfection by-products. A simultaneous determination method of 13 HAcAms, combining solid-phase extraction (SPE) enrichment, liquid chromatographic (LC) separation, and triple quadrupole mass spectrometry (tqMS) detection with atmospheric pressure chemical ionization (APCI) using selective reaction monitoring in positive mode, was developed to measure HAcAms, including chlorinated, brominated, and iodinated analogs. Ammonium chloride and Oasis HLB were selected as the dechlorinating reagent and polymeric SPE sorbent of HAcAm samples. The used tqMS apparatus showed higher sensitivity for the studied HAcAms in the APCI mode than electrospray ionization. 13 HAcAms were separated by LC in 9.0 min, and the detection limits ranged from 7.6 to 19.7 ng/L. The SPE-LC/tqMS method was successfully applied to quantify 13 HAcAms in drinking water samples for the first time, and first indentified tribromoacetamide and chloroiodoacetamide as DBPs in drinking water.

  6. Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

    PubMed

    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

  7. Feasibility of desorption atmospheric pressure photoionization and desorption electrospray ionization mass spectrometry to monitor urinary steroid metabolites during pregnancy.

    PubMed

    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.

  8. Analysis of polycyclic aromatic hydrocarbons using desorption atmospheric pressure chemical ionization coupled to a portable mass spectrometer.

    PubMed

    Jjunju, Fred P M; Maher, Simon; Li, Anyin; Badu-Tawiah, Abraham K; Taylor, Stephen; Cooks, R Graham

    2015-02-01

    Desorption atmospheric pressure chemical ionization (DAPCI) is implemented on a portable mass spectrometer and applied to the direct detection of polycyclic aromatic hydrocarbons (PAHs) and alkyl substituted benzenes. The presence of these compounds in the environment poses a significant threat to the health of both humans and wildlife because of their carcinogenic, toxic, and mutagenic properties. As such, instant detection outside of the laboratory is of particular importance to allow in-situ measurement at the source. Using a rapid, high throughput, miniature, handheld mass spectrometer, several alkyl substituted benzenes and PAHs (i.e., 1,2,3,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, fluoranthene, anthracene, benzo[k]fluoranthene, dibenz[a,h]anthracene, acenaphthene, indeno[1,2,3-c,d]pyrene, 9-ethylfluorene, and 1-benzyl-3-methyl-naphthalene) were identified and characterized using tandem mass spectrometry (MS/MS) from ambient surfaces, in the open air. This method can provide almost instantaneous information while minimizing sample preparation, which is advantageous in terms of both cost and simplicity of analysis. This MS-based technique is applicable to a wide range of environmental organic molecules.

  9. Atmospheric pressure ionization of chlorinated ethanes in ion mobility spectrometry and mass spectrometry

    SciTech Connect

    Ewing, Robert G.; Atkinson, David A.; Benson, Michael T.

    2015-05-16

    This study investigates the APCI mechanisms associated with chlorinated ethanes in an attempt to define conditions under which unique pseudo-molecular adducts, in addition to chloride ion, can be produced for analytical measurements using IMS and MS. The ionization chemistry of chlorinated compounds typically leads to the detection of only the halide ions. Using molecular modeling, which provides insights into the ion formation and relative binding energies, predictions for the formation of pseudo-molecular adducts are postulated. Predicted structures of the chloride ion with multiple hydrogens on the ethane backbone was supported by the observation of specific pseudo-molecular adducts in IMS and MS spectra. With the proper instrumental conditions, such as short reaction times and low temp.

  10. Capillary electrochromatography-atmospheric pressure ionization mass spectrometry of pesticides using a surfactant-bound monolithic column

    PubMed Central

    Gu, Congying; Shamsi, Shahab A.

    2011-01-01

    A surfactant bound poly (11-acrylaminoundecanoic acid-ethylene dimethacrylate) (AAUA-EDMA) monolithic column was simply prepared by in-situ co-polymerization of AAUA and EDMA with 1-propanol, 1,4-butanediol and water as porogens in 100 µm id fused silica capillary in one step. This column was used in capillary electrochromatography (CEC)-atmospheric pressure photoionization (APPI)-mass spectrometry system for separation and detection of N-methylcarbamates (NMCs) pesticides. Numerous parameters are optimized for CEC-APPI-MS. After evaluation of the mobile phase composition, sheath liquid composition and the monolithic capillary outlet position, a fractional factorial design (FFD) was selected as a screening procedure to identify factors of ionization source parameters, such as sheath liquid flow rate, drying gas flow rate, drying gas temperature, nebulizing gas pressure, vaporizer temperature, and capillary voltage, which significantly influence APPI-MS sensitivity. A face-centered central composite design (CCD) was further utilized to optimize the most significant parameters and predict the best sensitivity. Under optimized conditions signal-to-noise ratios (S/N) around 78 were achieved for an injection of 100 ng/mL of each pesticide. Finally, this CEC-APPI-MS method was successfully applied to the analysis of nine NMCs in spiked apple juice sample after solid phase extraction with recoveries in the range of 65 to 109%. PMID:20349511

  11. Molecular differentiation of five Cinnamomum camphora chemotypes using desorption atmospheric pressure chemical ionization mass spectrometry of raw leaves.

    PubMed

    Guo, Xiali; Cui, Meng; Deng, Min; Liu, Xingxing; Huang, Xueyong; Zhang, Xinglei; Luo, Liping

    2017-04-20

    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.

  12. Molecular differentiation of five Cinnamomum camphora chemotypes using desorption atmospheric pressure chemical ionization mass spectrometry of raw leaves

    NASA Astrophysics Data System (ADS)

    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.

  13. Quantitation of ceramides in nude mouse skin by normal-phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Liou, Yi-Bo; Sheu, Ming-Thau; Liu, Der-Zen; Lin, Shan-Yang; Ho, Hsiu-O

    2010-06-01

    A sensitive and accurate normal-phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) method for determining the standard ceramide [NS] (Cer[NS]) was developed and validated so as to improve the traditional thin-layer chromatography (TLC) technique and LC-electrospray ionization (ESI)-MS method to profile and quantify ceramides in nude mouse skin. Normal-phase LC-APCI-MS was optimized to separate the nine classes of ceramides presented in the stratum corneum (SC) of nude mouse skin. A normal-phase silica column eluted with the gradient system from heptane:acetone/butanol (90:10, v/v) of 75:25 to 100% acetone/butanol (90:10, v/v) (with each solvent containing 0.1% [v/v] triethylamine and 0.1% [v/v] formic acid) at a flow rate of 0.8 ml/min was found to be optimal for analyzing standard Cer[NS]. The analysis of Cer[NS] was validated and employed as the standard for constructing a calibration curve to quantitate all classes of ceramides. This method was applied to profile the classes and contents of ceramides in the SC of nude mouse skin and proved to be workable. It was concluded that this improved method can be used to directly detect and quantify all classes of ceramides in the SC of nude mouse skin and that it is more convenient and labor-saving than the traditional TLC method.

  14. Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection.

    PubMed

    Helale, Murad I H; Tanaka, Kazuhiko; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Haddad, Paul R

    2002-05-17

    A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). A mobile phase consisting of 0.85 mM benzoic acid in 10% aqueous methanol (pH 3.89) was used to separate the above carboxylic acids in about 40 min. For LC-MS, the APCI interface was used in the negative ionization mode. Linear plots of peak area versus concentration were obtained over the range 1-30 mM (r2=0.9982) and 1-30 mM (r2=0.9958) for conductimetric and MS detection, respectively. The detection limits of the target carboxylic acids calculated at S/N=3 ranged from 0.078 to 2.3 microM for conductimetric and photometric detection and from 0.66 to 3.82 microM for ion-exclusion chromatography-APCI-MS. The reproducibility of retention times was 0.12-0.16% relative standard deviation for ion-exclusion chromatography and 1.21-2.5% for ion-exclusion chromatography-APCI-MS. The method was applied to the determination of carboxylic acids in red wine, white wine, apple vinegar, and Japanese rice wine.

  15. Direct probe atmospheric pressure photoionization/atmospheric pressure chemical ionization high-resolution mass spectrometry for fast screening of flame retardants and plasticizers in products and waste.

    PubMed

    Ballesteros-Gómez, A; Brandsma, S H; de Boer, J; Leonards, P E G

    2014-04-01

    In this study, we develop fast screening methods for flame retardants and plasticizers in products and waste based on direct probe (DP) atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) coupled to a high-resolution (HR) time-of-flight mass spectrometer. DP-APPI is reported for the first time in this study, and DP-APCI that has been scarcely exploited is optimized for comparison. DP-APPI was more selective than DP-APCI and also more sensitive for the most hydrophobic compounds. No sample treatment was necessary, and only a minimal amount of sample (few milligrams) was used for analysis that was performed within a few minutes. Both methods were applied to the analysis of plastic products, electronic waste, and car interiors. Polybrominated diphenylethers, new brominated flame retardants, and organophosphorus flame retardants were present in most of the samples. The combination of DP with HR mass spectra and data processing based on mass accuracy and isotopic patterns allowed the unambiguous identification of chemicals at low levels of about 0.025 % (w/w). Under untargeted screening, resorcinol bis(biphenylphosphate) and bisphenol A bis(bisphenylphosphate) were identified in many of the consumer products of which literature data are still very limited.

  16. High pressure xenon ionization detector

    DOEpatents

    Markey, J.K.

    1989-11-14

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

  17. High pressure xenon ionization detector

    DOEpatents

    Markey, John K.

    1989-01-01

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

  18. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods.

    PubMed

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-03-10

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

  19. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

    PubMed Central

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-01-01

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate. PMID:28281659

  20. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

    NASA Astrophysics Data System (ADS)

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-03-01

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

  1. A novel method for analyzing solanesyl esters in tobacco leaves using atmospheric pressure chemical ionization/mass spectrometer.

    PubMed

    Ishida, Naoyuki

    2010-09-10

    A direct and simple method for analyzing solanesyl esters found in tobacco leaves was developed. Sample preparation was performed by accelerated solvent extractor 200 (ASE200) using n-hexane followed by evaporating solution in vacuo and dissolving residue with acetone. The separation of analytes was conducted through high-performance liquid chromatography (HPLC) equipped with an SIL-C18/5C column and the non-aqueous reversed phase chromatography (NARP) technique using acetone and acetonitrile as the mobile phase with a linear gradient. Atmospheric pressure chemical ionization/mass spectrometer (APCI/MS) in positive mode was used to detect solanesyl esters in the following conditions: capillary voltage 4000 V, corona current 10 microA, drying gas flow 5 mL/min, fragmentor voltage 200 V, nebulizer pressure 60 psi, and vaporizer temperature 500 degrees C. Each solanesyl ester was identified by the comparison of analyte with synthesized solanesyl esters. Quantification was conducted by selected ion monitoring (SIM) mode in order to detect the specific product ion (613.6 m/z) fragmented from solanesyl ester. The calibration curve was made in the range of 0.1-40 microg/mL with a regression coefficient over 0.999 on almost all solanesyl esters. The limit of detection (LOD) and limit of quantification (LOQ) ranged from 0.01 to 0.05 microg/mL and from 0.03 to 0.15 microg/mL, respectively, on the SIM mode of MS for quantification. Recovery (%) ranged from about 80 to 120%. The direct quantification using the developed method succeeded in showing a different amount and composition of solanesyl esters among various tobacco leaves.

  2. Normal phase liquid chromatography coupled to quadrupole time of flight atmospheric pressure chemical ionization mass spectrometry for separation, detection and mass spectrometric profiling of neutral sphingolipids and cholesterol.

    PubMed

    Farwanah, Hany; Wirtz, Jennifer; Kolter, Thomas; Raith, Klaus; Neubert, Reinhard H H; Sandhoff, Konrad

    2009-10-01

    Many lipidomic approaches focus on investigating aspects of sphingolipid metabolism. Special emphasis is put on neutral sphingolipids and cholesterol and their interaction. Such an interest is attributed to the fact that those lipids are altered in a series of serious disorders including various sphingolipidoses. High performance thin-layer chromatography (HPTLC) has become a widely used technique for lipid analysis. However, mass spectrometric profiling is irreplaceable for gaining an overview about the various molecular species within a lipid class. In this work we have developed a sensitive method based on a gradient normal phase high performance liquid chromatography (HPLC) coupled to quadrupole time of flight (QTOF) atmospheric pressure chemical ionization mass spectrometry (APCI-MS) in positive mode, which for the first time enables separation, on-line detection, and mass spectrometric profiling of multiple neutral sphingolipids including ceramide, glucosylceramide, lactosylceramide, globotriaosylceramide, globotetraosylceramide, sphingomyelin as well as cholesterol within less than 15min. An important advantage of the presented HPLC/APCI-MS approach is that the separation pattern emulates the one obtained by an optimized HPTLC method with a multiple stage development. Thus, the lipid classes previously separated and quantified by HPTLC can be easily screened regarding their mass spectrometric profiles by HPLC/APCI-MS. In addition, the selected ionization conditions enable in-source fragmentation providing useful structural information. The methods (HPLC/APCI-MS and the optimized HPTLC) were applied for the analysis of the mentioned lipids in human fibroblasts. This approach is aimed basically at investigators who perform studies based on genetic modifications or treatment with pharmacological agents leading to changes in the biochemical pathways of neutral sphingolipids and cholesterol. In addition, it can be of interest for research on disorders related to

  3. Desorption Flame-Induced Atmospheric Pressure Chemical Ionization Mass Spectrometry for Rapid Real-World Sample Analysis

    PubMed Central

    Cheng, Sy-Chyi; Chen, Shih-His; Shiea, Jentaie

    2017-01-01

    Flame-induced atmospheric pressure chemical ionization (FAPCI) is a solvent and high voltage-free APCI technique. It uses a flame to produce charged species that reacts with analytes for ionization, and generates intact molecular ions from organic compounds with minimal fragmentation. In this study, desorption FAPCI/MS was developed to rapidly characterize thermally stable organic compounds in liquid, cream, and solid states. Liquid samples were introduced into the ion source through a heated nebulizer, and the analytes formed in the heated nebulizer reacted with charged species in the source. For cream and solid sample analysis, the samples were positioned near the flame of the FAPCI source for thermal desorption and ionization. This approach provided a useful method to directly characterize samples with minimal pretreatment. Standards and real-world samples, such as drug tablets, ointment, and toy were analyzed to demonstrate the capability of desorption FAPCI/MS for rapid organic compound analysis. PMID:28573084

  4. Analysis of gaseous toxic industrial compounds and chemical warfare agent simulants by atmospheric pressure ionization mass spectrometry.

    PubMed

    Cotte-Rodríguez, Ismael; Justes, Dina R; Nanita, Sergio C; Noll, Robert J; Mulligan, Christopher C; Sanders, Nathaniel L; Cooks, R Graham

    2006-04-01

    The suitability of atmospheric pressure chemical ionization mass spectrometry as sensing instrumentation for the real-time monitoring of low levels of toxic compounds is assessed, especially with respect to public safety applications. Gaseous samples of nine toxic industrial compounds, NH3, H2S, Cl2, CS2, SO2, C2H4O, HBr, C6H6 and AsH3, and two chemical warfare agent simulants, dimethyl methylphosphonate (DMMP) and methyl salicylate (MeS), were studied. API-MS proves highly suited to this application, with speedy analysis times (<30 seconds), high sensitivity, high selectivity towards analytes, good precision, dynamic range and accuracy. Tandem MS methods were implemented in selected cases for improved selectivity, sensitivity, and limits of detection. Limits of detection in the parts-per-billion and parts-per-trillion range were achieved for this set of analytes. In all cases detection limits were well below the compounds' permissible exposure limits (PELs), even in the presence of added complex mixtures of alkanes. Linear responses, up to several orders of magnitude, were obtained over the concentration ranges studied (sub-ppb to ppm), with relative standard deviations less than 3%, regardless of the presence of alkane interferents. Receiver operating characteristic (ROC) curves are presented to show the performance trade-off between sensitivity, probability of correct detection, and false positive rate. A dynamic sample preparation system for the production of gas phase analyte concentrations ranging from 100 pptr to 100 ppm and capable of admixing gaseous matrix compounds and control of relative humidity and temperature is also described.

  5. Evaluation of gas chromatography-atmospheric pressure chemical ionization-mass spectrometry as an alternative to gas chromatography-electron ionization-mass spectrometry: avocado fruit as example.

    PubMed

    Hurtado-Fernández, Elena; Pacchiarotta, Tiziana; Longueira-Suárez, Enrique; Mayboroda, Oleg A; Fernández-Gutiérrez, Alberto; Carrasco-Pancorbo, Alegría

    2013-10-25

    Although GC-APCI-MS was developed more than 40 years ago this coupling is still far from being a routine technique. One of the reasons explaining the limited use of GC-APCI so far is the lack of spectral database which facilitates the identification of the compounds under study. The first application of a very recently developed GC-APCI database to identify as many compounds as possible in a complex matrix such as avocado fruit is presented here. The results achieved by using this database has been checked against those obtained using traditional GC-EI-MS and a comparison of the MS signals observed in both ionization sources has been carried out. 100 compounds belonging to different chemical families were identified in the matrix under study. Considering the results of this study, the wide range of application (in terms of polarity and size of analytes) and the robustness of APCI as interface, the high quality of TOF spectra, and our library as a publicly available resource, GC-APCI-TOF MS is definitively a valuable addition to the "metabolomics toolbox". Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Identification and determination of glycosides in tobacco leaves by liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Pang, Tao; Yuan, Zhongyi; Dai, Yongsheng; Wang, Chang; Yang, Jun; Peng, Liming; Xu, Guowang

    2007-02-01

    HPLC-atmospheric pressure chemical ionization MS (HPLC-APCI-MS) was used to screen and identify glycosides in tobacco leaf. MS/MS and MS3 and photodiode array (PDA) detection were also used in the characterization. A total of 12 glycosides were found and four of them were identified based on their abundant [M + H]+ ions, UV spectra, and MS/MS analysis and they are scopolin, rutin, quercetin-3-glycoside, and kaempferol-3-rutinoside. Analytical characteristics of the method were investigated. The contents of these glycosides were obtained and compared based on the relative peak area to the internal standard in seven kinds of tobacco leaf.

  7. Accurate mass fragment library for rapid analysis of pesticides on produce using ambient pressure desorption ionization with high-resolution mass spectrometry.

    PubMed

    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

  8. Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    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

  9. Characterization and quantification of triacylglycerols in peanut oil by off-line comprehensive two-dimensional liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Hu, Jun; Wei, Fang; Dong, Xu-Yan; Lv, Xin; Jiang, Mu-Lan; Li, Guang-Ming; Chen, Hong

    2013-01-01

    The complexity of natural triacylglycerols (TAGs) in various edible oils is prodigious due to the hundreds of set is of TAG compositions, which makes the identification of TAGs quite difficult. In this investigation, the off-line 2D system coupling of nonaqueous RP and silver-ion HPLC with atmospheric pressure chemical ionization MS detection has been applied to the identification and quantification of TAGs in peanut oil. The method was successful in the separation of a high number of TAG solutes, and the TAG structures were evaluated by analyzing their atmospheric pressure chemical ionization mass spectra information. HPLC and MS conditions have been optimized and the fragmentation mechanisms of isomers have been validated. In addition, an internal standard approach has been developed for TAG quantification. Then this system was applied in peanut oil samples and there was a total of 48 TAGs including regioisomers that have been determined and quantified.

  10. Stability studies of propoxur herbicide in environmental water samples by liquid chromatography-atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Sun, Lei; Lee, Hian Kee

    2003-10-03

    Liquid chromatography-atmospheric pressure ionization ion-trap mass spectrometry has been investigated for the analysis of polar pesticides in water. The degradation behavior of propoxur, selected as a model pesticide belonging to the N-methylcarbamate group, in various aqueous matrices (Milli-Q water, drinking water, rain water, seawater and river water) was investigated. Two interfaces of atmospheric pressure ionization, atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), were compared during the study. Propoxur and its transformation product (N-methylformamide) were best ionized as positive ions with both APCI and ESI, while another transformation product (2-isopropoxyphenol) yielded stronger signals as negative ions only with APCI. In addition, the effects of various pH, matrix type and irradiation sources (sunlight, darkness, indoor lighting and artificial UV lamp) on the chemical degradation (hydrolysis) were also assessed. From the kinetic studies of degradation, it was found that the half-life of propoxur was reduced from 327 to 161 h in Milli-Q water with variation of irradiation conditions from dark to sunlight exposure. Degradation rates largely increased with increasing pH. The half-life of the target compound dissolved in Milli-Q water under darkness decreased from 407 to 3 h when the pH of Milli-Q water was increased from 5 to 8.5. These suggest that hydrolysis of propoxur is light-intensity and pH-dependent. In order to mimic contaminated natural environmental waters, propoxur was spiked into real water samples at 30 microg/l. The degradation of propoxur in such water samples under various conditions were studied in detail and compared. With the ion trap run in a time-scheduled single ion monitoring mode, typical limits of detection of the instrument were in the range of 1-10 microg/l.

  11. Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

    PubMed

    Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

    2016-02-12

    Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51).

  12. Surface swabbing technique for the rapid screening for pesticides using ambient pressure desorption ionization with high-resolution mass spectrometry.

    PubMed

    Edison, Sara E; Lin, Lora A; Gamble, Bryan M; Wong, Jon; Zhang, Kai

    2011-01-15

    A rapid screening method for pesticides has been developed to promote more efficient processing of produce entering the United States. Foam swabs were used to recover a multiclass mixture of 132 pesticides from the surfaces of grapes, apples, and oranges. The swabs were analyzed using direct analysis in real time (DART) ionization coupled with a high-resolution Exactive Orbitrap™ mass spectrometer. By using a DART helium temperature gradient from 100-350°C over 3 min, a minimal separation of analytes based on volatility differences was achieved. This, combined with the Exactive's mass resolution of 100,00, allowed the chromatographic step, along with the typical compositing and extraction steps associated with gas chromatography/mass spectrometry (GC/MS) or liquid chromatography/mass spectrometry (LC/MS) approaches, to be eliminated. Detection of 86% of the analytes present was consistently achieved at levels of 2 ng/g (per each apple or orange) and 10 ng/g (per grape). A resolution study was conducted with four pairs of isobaric compounds analyzed at a mass resolution of 100 000. Baseline separation was achieved with analyte ions differing in mass by 25 ppm and analyte ions with a mass difference of 10 ppm were partially resolved. In addition, field samples that had undergone traditional sample preparation using QuEChERS (quick, easy, cheap, rugged, and safe) were analyzed using both LC/MS and DART-MS and the results from the two techniques were found to be comparable in terms of identification of the pesticides present. The use of swabs greatly increased sample throughput by reducing sample preparation and analysis time.

  13. High performance liquid chromatography/atmospheric pressure ionization/tandem mass spectrometry (HPLC/API/MS/MS) in drug metabolism and toxicology.

    PubMed

    Kamel, Amin; Prakash, Chandra

    2006-12-01

    Studies of the metabolic fate of drugs and other xenobiotics in living systems may be divided into three broad areas: (1) elucidation of biotransformation pathways through identification of circulatory and excretory metabolites (qualitative studies); (2) determination of pharmacokinetics of the parent drug and/or its primary metabolites (quantitative studies); and (3) identification of chemically-reactive metabolites, which play a key role as mediators of drug-induced toxicities (mechanistic studies). Mass spectrometry has been regarded as one of the most important analytical tools in studies of drug metabolism, pharmacokinetics and biochemical toxicology. With the commercial introduction of new ionization methods such as those based on atmospheric pressure ionization (API) techniques and the combination of liquid chromatography-mass spectrometry (LC-MS), it has now become a truly indispensable technique in pharmaceutical research. Triple stage quadrupole and ion trap mass spectrometers are presently used for this purpose, because of their sensitivity and selectivity. API-TOF mass spectrometry has also been very attractive due to its enhanced full-scan sensitivity, scan speed, improved resolution and ability to measure the accurate masses for protonated molecules and fragment ions. This review aims to survey the utility of mass spectrometry in drug metabolism and toxicology and to highlight novel applications and future trends in this field.

  14. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

    PubMed Central

    Zuber, Jan; Kroll, Marius M.; Rathsack, Philipp; Otto, Matthias

    2016-01-01

    Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

  15. Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal.

    PubMed

    Zuber, Jan; Kroll, Marius M; Rathsack, Philipp; Otto, Matthias

    2016-01-01

    Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols.

  16. Simultaneous measurement of nitric oxide (NO) and nitrogen dioxide (NO2) in simulated automobile exhaust using medium pressure ionization-mass spectrometry.

    PubMed

    Short, Luke Chandler; Frey, Rüdiger; Benter, Thorsten

    2006-02-01

    In previous papers we have demonstrated two different, two-color resonance-enhanced multiphoton ionization (REMPI) schemes for the simultaneous measurement of trace amounts (ppbV to pptV) of nitrogen monoxide (NO) and nitrogen dioxide (NO(2)). The goal of this study is to provide a laser ionization-mass spectrometric scheme capable of measuring ppmV to ppthV concentrations of NO and NO(2) within vehicle exhaust containing up to ppthV of aromatic hydrocarbons and a time frame of seconds. Two ionization schemes are used here to measure NO and NO(2) in simulated automobile exhaust with three different sources. REMPI Scheme 1 uses broad-bandwidth light and an effusive source to measure NO (limit of detection (LOD) 300 ppmV), NO(2) (LOD 100 ppmV), and aromatic hydrocarbons (via photoionization) along with fragments (via electron impact). REMPI Scheme 2 uses narrow-bandwidth light and a medium pressure laser ionization (MPLI) source to measure NO (LOD 60 ppmV), NO(2) (LOD 3 ppmV), and fragments (via electron impact). The LOD is determined using 10-second sampling times. A newly developed delayed-ion extraction technique for MPLI is then applied to REMPI Scheme 2, dramatically reducing the electron impact signal, so that only NO and NO(2) are observed. We conclude that Scheme 2 with delayed-electron extraction is best suited for measuring in situ NO and NO(2) within engine exhaust.

  17. Analysis of 13 fentanils, including sufentanil and carfentanil, in human urine by liquid chromatography-atmospheric-pressure ionization-tandem mass spectrometry.

    PubMed

    Wang, Lanqing; Bernert, John T

    2006-06-01

    A sensitive, semiautomated method for the analysis of several fentanils and fentanil metabolites in human urine is described. This method uses solid-phase extraction of urine samples followed by liquid chromatography-atmospheric pressure ionization-tandem mass spectrometry. Isotopically labeled internal standards were included for 6 of the 13 analytes in this study. Estimated detection limits ranged from 3 to 27 pg/mL, and good accuracy and long-term precision were observed in most cases. This method should be useful for the rapid and sensitive screening of human urine samples for a number of fentanils and their metabolites as indicators of exposure.

  18. Potential of gas chromatography-atmospheric pressure chemical ionization-time-of-flight mass spectrometry for the determination of sterols in human plasma.

    PubMed

    Matysik, S; Schmitz, G; Bauer, S; Kiermaier, J; Matysik, F-M

    2014-04-11

    The application of Gas Chromatography (GC)-Atmospheric Pressure Chemical Ionization (APCI)-Time-of-Flight Mass Spectrometry (TOF-MS) is presented for sterol analysis in human plasma. A commercial APCI interface was modified to ensure a well-defined humidity which is essential for controlled ionization. In the first step, optimization regarding flow rates of auxiliary gases was performed by using a mixture of model analytes. Secondly, the qualitative and quantitative analysis of sterols including oxysterols, cholesterol precursors, and plant sterols as trimethylsilyl-derivatives was successfully carried out. The characteristics of APCI together with the very good mass accuracy of TOF-MS data enable the reliable identification of relevant sterols in complex matrices. Linear calibration lines and plausible results for healthy volunteers and patients could be obtained whereas all mass signals were extracted with an extraction width of 20 ppm from the full mass data set. One advantage of high mass accuracy can be seen in the fact that from one recorded run any search for m/z can be performed. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    PubMed Central

    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

  20. Continuous Flow Atmospheric Pressure Laser Desorption/Ionization Using a 6–7-µm-Band Mid-Infrared Tunable Laser for Biomolecular Mass Spectrometry

    PubMed Central

    Hiraguchi, Ryuji; Hazama, Hisanao; Senoo, Kenichirou; Yahata, Yukinori; Masuda, Katsuyoshi; Awazu, Kunio

    2014-01-01

    A continuous flow atmospheric pressure laser desorption/ionization technique using a porous stainless steel probe and a 6–7-µm-band mid-infrared tunable laser was developed. This ion source is capable of direct ionization from a continuous flow with a high temporal stability. The 6–7-µm wavelength region corresponds to the characteristic absorption bands of various molecular vibration modes, including O–H, C=O, CH3 and C–N bonds. Consequently, many organic compounds and solvents, including water, have characteristic absorption peaks in this region. This ion source requires no additional matrix, and utilizes water or acetonitrile as the solvent matrix at several absorption peak wavelengths (6.05 and 7.27 µm, respectively). The distribution of multiply-charged peptide ions is extremely sensitive to the temperature of the heated capillary, which is the inlet of the mass spectrometer. This ionization technique has potential for the interface of liquid chromatography/mass spectrometry (LC/MS). PMID:24937686

  1. Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of friction modifier additives analyzed directly from base oil solutions.

    PubMed

    Widder, Lukas; Brennerb, Josef; Huttera, Herbert

    2014-01-01

    To develop new products and to apply measures of quality control quick and simple accessibility of additive composition in automo- tive lubrication is important. The aim of this study was to investigate the possibility of analyzing organic friction modifier additives by means of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry [AP-MALDI-MS] from lubricant solu- tions without the use of additional separation techniques. Analyses of selected friction modifier ethoxylated tallow amines and oleic acid amide were compared using two ionization methods, positive-ion electrospray ionization (ESI) and AP-MALDI, using a LTQ Orbitrap mass spectrometer. Pure additives were characterized from solvent solutions, as well as from synthetic and mineral base oil mixtures. Detected ions of pure additive samples consisted mainly of [M + H]+, but also alkaLi metal adducts [M + Na]+ and [M + K]+ could be seen. Characterizations of blends of both friction modifiers from the base oil mixtures were carried out as well and showed significant inten- sities for several additive peaks. Thus, this work shows a method to directly analyze friction modifier additives used in the automotive industry from an oil blend via the use of AP-MALDI without any further separation steps. The method presented will further simplify the acquisition of data on lubricant composition and additives. Furthermore, it allows the perspective of analyzing additive reaction products directly from formulated oil blends.

  2. Rapid on-site detection of explosives on surfaces by ambient pressure laser desorption and direct inlet single photon ionization or chemical ionization mass spectrometry.

    PubMed

    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.

  3. Determination and characterization of organic explosives using porous graphitic carbon and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Holmgren, Erik; Carlsson, Håkan; Goede, Patrick; Crescenzi, Carlo

    2005-12-16

    A new LC-MS method for the determination and characterization of three groups of commonly used organic explosives (nitroaromatic compounds, cyclic nitroamines and nitrate esters) was developed using a porous graphitic carbon (PGC) (Hypercarb) column. Twenty-one different explosive-related compounds--including 2,4,6-trinitrotoluene, its by-products and its degradation products--were chromatographically separated in a single analysis. This efficient separation facilitates the identification of the manufacturer of the explosive using the identified analytes as a fingerprint. A final, conclusive identification of the analytes can be obtained using LC-MS equipped with an atmospheric pressure chemical ionization (APCI) interface. Solvent effects on chromatographic behaviour were investigated, as were the effects of solvent mixtures and mobile phase additives. The number and the relative positions of the nitro groups within analyte molecules influence their order of elution; these effects were investigated. The data thus generated can be interpreted to support a hypothesis concerning the retention mechanism of nitro-containing compounds when using PGC. Limits of detection ranged from 0.5 to 41.2 ng. The new methodology described herein improves the sensitivity and selectivity of explosive detection. The effectiveness of the method is demonstrated by the analysis of soil samples containing explosives residue from test fields in Sweden and Afghanistan.

  4. Sensitive monitoring of volatile chemical warfare agents in air by atmospheric pressure chemical ionization mass spectrometry with counter-flow introduction.

    PubMed

    Seto, Yasuo; Kanamori-Kataoka, Mieko; Tsuge, Koichiro; Ohsawa, Isaac; Iura, Kazumitsu; Itoi, Teruo; Sekiguchi, Hiroyuki; Matsushita, Koji; Yamashiro, Shigeharu; Sano, Yasuhiro; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Okumura, Akihiko; Takada, Yasuaki; Nagano, Hisashi; Waki, Izumi; Ezawa, Naoya; Tanimoto, Hiroyuki; Honjo, Shigeru; Fukano, Masumi; Okada, Hidehiro

    2013-03-05

    A new method for sensitively and selectively detecting chemical warfare agents (CWAs) in air was developed using counter-flow introduction atmospheric pressure chemical ionization mass spectrometry (MS). Four volatile and highly toxic CWAs were examined, including the nerve gases sarin and tabun, and the blister agents mustard gas (HD) and Lewisite 1 (L1). Soft ionization was performed using corona discharge to form reactant ions, and the ions were sent in the direction opposite to the airflow by an electric field to eliminate the interfering neutral molecules such as ozone and nitrogen oxide. This resulted in efficient ionization of the target CWAs, especially in the negative ionization mode. Quadrupole MS (QMS) and ion trap tandem MS (ITMS) instruments were developed and investigated, which were movable on the building floor. For sarin, tabun, and HD, the protonated molecular ions and their fragment ions were observed in the positive ion mode. For L1, the chloride adduct ions of L1 hydrolysis products were observed in negative ion mode. The limit of detection (LOD) values in real-time or for a 1 s measurement monitoring the characteristic ions were between 1 and 8 μg/m(3) in QMS instrument. Collision-induced fragmentation patterns for the CWAs were observed in an ITMS instrument, and optimized combinations of the parent and daughter ion pairs were selected to achieve real-time detection with LOD values of around 1 μg/m(3). This is a first demonstration of sensitive and specific real-time detection of both positively and negatively ionizable CWAs by MS instruments used for field monitoring.

  5. Trace determination of caffeine in surface water samples by liquid chromatography--atmospheric pressure chemical ionization--mass spectrometry (LC-APCI-MS).

    PubMed

    Gardinali, Piero R; Zhao, Xu

    2002-12-01

    A new method based on liquid-liquid extraction (LLE) coupled to reverse phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) has been applied to determine trace amounts of caffeine (1,3,7-trimethylxanthine) in surface water samples from a near coastal ecosystem such as Biscayne Bay, Florida. The rational behind the development of such method will be to evaluate the use of unmetabolized caffeine as a potential dissolved phase tracer of human waste contamination. The method allows for the determination of caffeine at levels as low as 4.0 ng/l (ppt) in both salt and freshwater by extracting and concentrating a 1-1 water sample to a final volume of 500 microl and using HPLC separation coupled to an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) system operated in selected ion monitoring (SIM) for the protonated molecular ions (M + H(+)). Samples from different portions of Biscayne Bay and the Miami River, one of its major tributaries, were analyzed and caffeine was detected in those areas previously identified for consistently exceeding the water quality criteria for fecal coliform bacteria contamination. The caffeine concentration in the samples with positive detection was generally low at levels equal or lower than 41 ng/l. However, there is a marked difference between samples collected in open bay areas and those collected from the Miami River.

  6. Skeletal muscle fiber analysis by atmospheric pressure scanning microprobe matrix-assisted laser desorption/ionization mass spectrometric imaging at high mass and high spatial resolution.

    PubMed

    Tsai, Yu-Hsuan; Bhandari, Dhaka Ram; Garrett, Timothy J; Carter, Christy S; Spengler, Bernhard; Yost, Richard A

    2016-06-01

    Skeletal muscles are composed of heterogeneous muscle fibers with various fiber types. These fibers can be classified into different classes based on their different characteristics. MALDI mass spectrometric imaging (MSI) has been applied to study and visualize different metabolomics profiles of different fiber types. Here, skeletal muscles were analyzed by atmospheric pressure scanning microprobe MALDI-MSI at high spatial and high mass resolution.

  7. In situ identification of organic components of ink used in books from the 1900s by atmospheric pressure matrix assisted laser desorption ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Giurato, Laura; Candura, Andrea; Grasso, Giuseppe; Spoto, Giuseppe

    2009-11-01

    This paper describes the use of atmospheric pressure/matrix assisted laser desorption ionization-mass spectrometry (AP/MALDI-MS) as a spatially resolved analytical technique for the study of organic components of inks used to print coloured parts of ancient books. The possibility to operate at atmospheric pressure makes MALDI-MS a new in situ micro-destructive diagnostic tool suitable for analysing samples in air, simplifying the investigation of the organic components of artistic and archaeological objects. In this work, several organic dyes and pigments were identified in situ by analysing different coloured areas of books printed in the years 1911 and 1920. The detected colouring materials, which were available since the 1890s, were often identified as a mixture, confirming the typical procedures used in the lithographic printing processes. The matrix deposition and the laser desorption process did not cause visible alteration of the sample surface.

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

    PubMed

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

    2014-05-06

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

  9. Determination of triclosan metabolites by using in-source fragmentation from high-performance liquid chromatography/negative atmospheric pressure chemical ionization ion trap mass spectrometry.

    PubMed

    Wu, Jian-lin; Liu, Jie; Cai, Zongwei

    2010-07-15

    Triclosan is a widely used broad-spectrum antibacterial agent that acts by specifically inhibiting enoyl-acyl carrier protein reductase. An in vitro metabolic study of triclosan was performed by using Sprague-Dawley (SD) rat liver S9 and microsome, while the in vivo metabolism was investigated on SD rats. Twelve metabolites were identified by using in-source fragmentation from high-performance liquid chromatography/negative atmospheric pressure chemical ionization ion trap mass spectrometry (HPLC/APCI-ITMS) analysis. Compared to electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS) that gave little fragmentation for triclosan and its metabolites, the in-source fragmentation under APCI provided intensive fragmentations for the structural identifications. The in vitro metabolic rate of triclosan was quantitatively determined by using HPLC/ESI-ITMS with the monitoring of the selected triclosan molecular ion. The metabolism results indicated that glucuronidation and sulfonation were the major pathways of phase II metabolism and the hydroxylated products were the major phase I metabolites. Moreover, glucose, mercapturic acid and cysteine conjugates of triclosan were also observed in the urine samples of rats orally administrated with triclosan.

  10. Characterization of triacylglycerol and diacylglycerol composition of plant oils using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Holcapek, Michal; Jandera, Pavel; Zderadicka, Petr; Hrubá, Lucie

    2003-08-29

    Triacylglycerols (TGs) and diacylglycerols (DGs) in 16 plant oil samples (hazelnut, pistachio, poppy-seed, almond, palm, Brazil-nut, rapeseed, macadamia, soyabean, sunflower, linseed, Dracocephalum moldavica, evening primrose, corn, amaranth, Silybum arianum) were analyzed by HPLC-MS with atmospheric pressure chemical ionization (APCI) and UV detection at 205 nm on two Nova-Pak C18 chromatographic columns connected in series. A single chromatographic column and non-aqueous ethanol-acetonitrile gradient system was used as a compromise between the analysis time and the resolution for the characterization of TG composition of five plant oils. APCI mass spectra were applied for the identification of all TGs and other acylglycerols. The isobaric positional isomers can be distinguished on the basis of different relative abundances of the fragment ions formed by preferred losses of the fatty acid from sn-1(3) positions compared to the sn-2 position. Excellent chromatographic resolution and broad retention window together with APCI mass spectra enabled positive identification of TGs containing fatty acids with odd numbers of carbon atoms such as margaric (C17:0) and heptadecanoic (C17:1) acids. The general fragmentation patterns of TGs in both APCI and electrospray ionization mass spectra were proposed on the basis of MSn spectra measured with an ion trap analyzer. The relative concentrations of particular TGs in the analyzed plant oils were estimated on the basis of relative peak areas measured with UV detection at 205 nm.

  11. Generation of highly charged peptide and protein ions by atmospheric pressure matrix-assisted infrared laser desorption/ionization ion trap mass spectrometry.

    PubMed

    König, Simone; Kollas, Oliver; Dreisewerd, Klaus

    2007-07-15

    We show that highly charged ions can be generated if a pulsed infrared laser and a glycerol matrix are employed for atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry with a quadrupole ion trap. Already for small peptides like bradykinin, doubly protonated ions form the most abundant analyte signal in the mass spectra. The center of the charge-state distribution increases with the size of the analyte. For example, insulin is detected with a most abundant ion signal corresponding to a charge state of four, whereas for cytochrome c, the 10 times protonated ion species produces the most intense signal. Myoglobin is observed with up to 13 charges. The high m/z ratios allow us to use the Paul trap for the detection of MALDI-generated protein ions that are, owing to their high molecular weight, not amenable in their singly protonated charge state. Formation of multiple charges critically depends on the addition of diluted acid to the analyte-matrix solution. Tandem mass spectra generated by collision-induced dissociation of doubly charged peptides are also presented. The findings allow speculations about the involvement of electrospray ionization processes in these MALDI experiments.

  12. High-throughput walkthrough detection portal for counter terrorism: detection of triacetone triperoxide (TATP) vapor by atmospheric-pressure chemical ionization ion trap mass spectrometry.

    PubMed

    Takada, Yasuaki; Nagano, Hisashi; Suzuki, Yasutaka; Sugiyama, Masuyuki; Nakajima, Eri; Hashimoto, Yuichiro; Sakairi, Minoru

    2011-09-15

    With the aim of improving security, a high-throughput portal system for detecting triacetone triperoxide (TATP) vapor emitted from passengers and luggage was developed. The portal system consists of a push-pull air sampler, an atmospheric-pressure chemical ionization (APCI) ion source, and an explosives detector based on mass spectrometry. To improve the sensitivity of the explosives detector, a novel linear ion trap mass spectrometer with wire electrodes (wire-LIT) is installed in the portal system. TATP signals were clearly obtained 2 s after the subject under detection passed through the portal system. Preliminary results on sensitivity and throughput show that the portal system is a useful tool for preventing the use of TATP-based improvised explosive devices by screening persons in places where many people are coming and going.

  13. Development and validation of sensitive method for determination of serum cotinine in smokers and nonsmokers by liquid chromatography/atmospheric pressure ionization tandem mass spectrometry.

    PubMed

    Bernert, J T; Turner, W E; Pirkle, J L; Sosnoff, C S; Akins, J R; Waldrep, M K; Ann, Q; Covey, T R; Whitfield, W E; Gunter, E W; Miller, B B; Patterson, D G; Needham, L L; Hannon, W H; Sampson, E J

    1997-12-01

    We describe a sensitive and specific method for measuring cotinine in serum by HPLC coupled to an atmospheric pressure chemical ionization tandem mass spectrometer. This method can analyze 100 samples/day on a routine basis, and its limit of detection of 50 ng/L makes it applicable to the analysis of samples from nonsmokers potentially exposed to environmental tobacco smoke. Analytical accuracy has been demonstrated from the analysis of NIST cotinine standards and from comparative analyses by both the current method and gas chromatography/high-resolution mass spectrometry. Precision has been examined through the repetitive analysis of a series of bench and blind QC materials. This method has been applied to the analysis of cotinine in serum samples collected as part of the Third National Health and Nutrition Examination Survey (NHANES III).

  14. Fluid hydrogen at high density - Pressure ionization

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1992-01-01

    The Helmholtz-free-energy model for nonideal mixtures of hydrogen atoms and molecules by Saumon and Chabrier (1991) is extended to describe dissociation and ionization in similar mixtures in chemical equilibrium. A free-energy model is given that describes partial ionization in the pressure and temperature ionization region. The plasma-phase transition predicted by the model is described for hydrogen mixtures including such components as H2, H, H(+), and e(-). The plasma-phase transition has a critical point at Tc = 15,300 K and Pc = 0.614 Mbar, and thermodynamic instability is noted in the pressure-ionization regime. The pressure dissociation and ionization of fluid hydrogen are described well with the model yielding information on the nature of the plasma-phase transition. The model is shown to be valuable for studying dissociation and ionization in astrophysical objects and in high-pressure studies where pressure and temperature effects are significant.

  15. Non-proximate detection of small and large molecules by desorption electrospray ionization and desorption atmospheric pressure chemical ionization mass spectrometry: instrumentation and applications in forensics, chemistry, and biology.

    PubMed

    Cotte-Rodríguez, Ismael; Mulligan, Christopher C; Cooks, R Graham

    2007-09-15

    Ambient surfaces are examined by mass spectrometry at distances of up to 3 m from the instrument without any prior sample preparation. Non-proximate versions of the desorption electrospray ionization (DESI) and desorption atmospheric pressure chemical ionization experiments are shown to allow rapid, sensitive, and selective detection of trace amounts of active ingredients in pharmaceutical drug formulations, illicit drugs (methamphetamine, cocaine, and diacetylmorphine), organic salts, peptides, chemical warfare agent simulants, and other small organic compounds. Utilizing an ion transport tube to transport analyte ions to the mass spectrometer, nonproximate DESI allows one to collect high-quality, largely interference-free spectra with signal-to-noise (S/N) ratios of more than 100. High selectivity is achieved by tandem mass spectrometry and by reactive DESI, a variant experiment in which reagents added into the solvent spray allow bond-forming reactions with the analyte. Ion/molecule reactions were found to selectively suppress the response of mixture components other than the analyte of interest in nonproximate-DESI. Flexible ion transport tubing is also investigated, allowing performance similar to stainless steel tubing in the transport of ions from the sample to the mass spectrometer. Transfer tube temperature effects are examined. A multiple sprayer DESI source capable of analyzing a larger sample area was evaluated to decrease the sampling time and increase sample throughput. Low nanogram detection limits were obtained for the compounds studied from a wide variety of surfaces, even those present in complex matrixes.

  16. Automated Annotation and Evaluation of In-Source Mass Spectra in GC/Atmospheric Pressure Chemical Ionization-MS-Based Metabolomics.

    PubMed

    Jaeger, Carsten; Hoffmann, Friederike; Schmitt, Clemens A; Lisec, Jan

    2016-10-04

    Gas chromatography using atmospheric pressure chemical ionization coupled to mass spectrometry (GC/APCI-MS) is an emerging metabolomics platform, providing much-enhanced capabilities for structural mass spectrometry as compared to traditional electron ionization (EI)-based techniques. To exploit the potential of GC/APCI-MS for more comprehensive metabolite annotation, a major bottleneck in metabolomics, we here present the novel R-based tool InterpretMSSpectrum assisting in the common task of annotating and evaluating in-source mass spectra as obtained from typical full-scan experiments. After passing a list of mass-intensity pairs, InterpretMSSpectrum locates the molecular ion (M0), fragment, and adduct peaks, calculates their most likely sum formula combination, and graphically summarizes results as an annotated mass spectrum. Using (modifiable) filter rules for the commonly used methoximated-trimethylsilylated (MeOx-TMS) derivatives, covering elemental composition, typical substructures, neutral losses, and adducts, InterpretMSSpectrum significantly reduces the number of sum formula candidates, minimizing manual effort for postprocessing candidate lists. We demonstrate the utility of InterpretMSSpectrum for 86 in-source spectra of derivatized standard compounds, in which rank-1 sum formula assignments were achieved in 84% of the cases, compared to only 63% when using mass and isotope information on the M0 alone. We further use, for the first time, automated annotation to evaluate the purity of pseudospectra generated by different metabolomics preprocessing tools, showing that automated annotation can serve as an integrative quality measure for peak picking/deconvolution methods. As an R package, InterpretMSSpectrum integrates flexibly into existing metabolomics pipelines and is freely available from CRAN ( https://cran.r-project.org/ ).

  17. Fast determination of 3-ethenylpyridine as a marker of environmental tobacco smoke at trace level using direct atmospheric pressure chemical ionization tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Jiang, Cheng-Yong; Sun, Shi-Hao; Zhang, Qi-Dong; Liu, Jun-Hui; Zhang, Jian-Xun; Zong, Yong-Li; Xie, Jian-Ping

    2013-03-01

    A method with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) was developed and applied to direct analysis of Environmental Tobacco Smoke (ETS), using 3-ethenylpyridine (3-EP) as a vapour-phase marker. In this study, the ion source of APCI-MS/MS was modified and direct analysis of gas sample was achieved by the modified instrument. ETS samples were directly introduced, via an atmospheric pressure inlet, into the APCI source. Ionization was carried out in positive-ion APCI mode and 3-EP was identified by both full scan mode and daughter scan mode. Quantification of 3-EP was performed by multiple reaction monitoring (MRM) mode. The calibration curve was obtained in the range of 1-250 ng L-1 with a satisfactory regression coefficient of 0.999. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.5 ng L-1 and 1.6 ng L-1, respectively. The precision of the method, calculated as relative standard deviation (RSD), was characterized by repeatability (RSD 3.92%) and reproducibility (RSD 4.81%), respectively. In real-world ETS samples analysis, compared with the conventional GC-MS method, the direct APCI-MS/MS has shown better reliability and practicability in the determination of 3-EP at trace level. The developed method is simple, fast, sensitive and repeatable; furthermore, it could provide an alternative way for the determination of other volatile pollutants in ambient air at low levels.

  18. Does asymmetric charge transfer play an important role as an ionization mode in low power-low pressure glow discharge mass spectrometry?

    NASA Astrophysics Data System (ADS)

    Mushtaq, S.; Steers, E. B. M.; Churchill, G.; Barnhart, D.; Hoffmann, V.; Pickering, J. C.; Putyera, K.

    2016-04-01

    We report results of comprehensive studies using the Nu Instruments Astrum high-resolution glow discharge mass spectrometer (GD-MS) and optical emission spectrometry (OES) to investigate the relative importance of discharge mechanisms, such as Penning ionization (PI) and asymmetric charge transfer (ACT), at low-power/low-pressure discharge conditions. Comparison of the ratios of the ion signals of each constituent element to that of the plasma gas shows that for oxygen, the ratio in krypton is more than ten times higher than in argon (oxygen ground state ions are produced by Kr-ACT). For many elements, the ratios are very similar but that for tungsten is higher with krypton, while for iron, the reverse holds. These effects are linked to the arrangement of ionic energy levels of the elements concerned and the resulting relative importance of ACT and PI. The GD-MS and GD-OES results have shown that the ACT process can play an important role as the ionization mode in low-power/low-pressure discharges. However, OES results have shown that the magnitude of change in spectral intensities of elements studied are dependent on the discharge conditions.

  19. Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-07-01

    An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The determination of carbon dioxide concentration using atmospheric pressure ionization mass spectrometry/isotopic dilution and errors in concentration measurements caused by dryers.

    PubMed

    DeLacy, Brendan G; Bandy, Alan R

    2008-01-01

    An atmospheric pressure ionization mass spectrometry/isotopically labeled standard (APIMS/ILS) method has been developed for the determination of carbon dioxide (CO(2)) concentration. Descriptions of the instrumental components, the ionization chemistry, and the statistics associated with the analytical method are provided. This method represents an alternative to the nondispersive infrared (NDIR) technique, which is currently used in the atmospheric community to determine atmospheric CO(2) concentrations. The APIMS/ILS and NDIR methods exhibit a decreased sensitivity for CO(2) in the presence of water vapor. Therefore, dryers such as a nafion dryer are used to remove water before detection. The APIMS/ILS method measures mixing ratios and demonstrates linearity and range in the presence or absence of a dryer. The NDIR technique, on the other hand, measures molar concentrations. The second half of this paper describes errors in molar concentration measurements that are caused by drying. An equation describing the errors was derived from the ideal gas law, the conservation of mass, and Dalton's Law. The purpose of this derivation was to quantify errors in the NDIR technique that are caused by drying. Laboratory experiments were conducted to verify the errors created solely by the dryer in CO(2) concentration measurements post-dryer. The laboratory experiments verified the theoretically predicted errors in the derived equations. There are numerous references in the literature that describe the use of a dryer in conjunction with the NDIR technique. However, these references do not address the errors that are caused by drying.

  1. Quantification of S-carboxymethyl-(R)-cysteine in human plasma by high-performance ion-exchange liquid chromatography/atmospheric pressure ionization mass spectrometry.

    PubMed

    Anacardio, R; Cantalini, M G; De Angelis, F; Gentile, M

    1997-04-01

    The determination of S-carboxymethyl-(R)-cysteine (SCMC) in human plasma during extended bioequivalence studies demands a rapid, accurate and selective assay technique. A liquid chromatographic/mass spectrometric method was developed which involves rough protein precipitation followed by high-performance liquid chromatographic separation with an ion-exchange column and atmospheric pressure ionization (API) mass spectrometric detection, with the instrument operating with electrospray ionization (ESI) and in the selected-ion monitoring mode. The drug and the internal standard S-[(R)-1-carboxyethyl]-(R)-cysteine (SCEC) are detected by focusing the first quadrupole of the triple stage system on MH+ ions, thus permitting elimination of endogenous interfering substances and allowing a detection limit of 0.05 microgram ml-1. The chromatographic run time is 16 min and the method has sufficient sensitivity, precision, accuracy and selectivity for routine analyses of clinical plasma samples containing SCMC at concentrations in the range 0.2-20 micrograms ml-1. In summary, this LC/MS-based assay of SCMC demonstrates advantages of easy sample preparation, low limit of quantification (200 ng per ml of human plasma) without any derivatization step, high specificity and rapid sample analysis with an overall throughput of more than 60 analyses per day.

  2. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2013-02-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant

  3. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-08-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m-3 for pinonic acid) by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  4. Screening of lake sediments for emerging contaminants by liquid chromatography atmospheric pressure photoionization and electrospray ionization coupled to high resolution mass spectrometry.

    PubMed

    Chiaia-Hernandez, Aurea C; Krauss, Martin; Hollender, Juliane

    2013-01-15

    We developed a multiresidue method for the target and suspect screening of more than 180 pharmaceuticals, personal care products, pesticides, biocides, additives, corrosion inhibitors, musk fragrances, UV light stabilizers, and industrial chemicals in sediments. Sediment samples were freeze-dried, extracted by pressurized liquid extraction, and cleaned up by liquid-liquid partitioning. The quantification and identification of target compounds with a broad range of physicochemical properties (log K(ow) 0-12) was carried out by liquid chromatography followed by electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to high resolution Orbitrap mass spectrometry (HRMS/MS). The overall method average recoveries and precision are 103% and 9% (RSD), respectively. The method detection limits range from 0.010 to 4 ng/g(dw), while limits of quantification range from 0.030 to 14 ng/g(dw). The use of APPI as an alternative ionization source helped to distinguish two isomeric musk fragrances by means of different ionization behavior. The method was demonstrated on sediment cores from Lake Greifensee located in northeastern Switzerland. The results show that biocides, musk fragrances, and other personal care products were the most frequently detected compounds with concentrations ranging from pg/g(dw) to ng/g(dw), whereas none of the targeted pharmaceuticals were found. The concentrations of many urban contaminants originating from wastewater correlate with the highest phosphorus input into the lake as a proxy for treatment efficiency. HRMS enabled a retrospective analysis of the full-scan data acquisition allowing the detection of suspected compounds like quaternary ammonium surfactants, the biocide triclocarban, and the tentative identification of further compounds without reference standards, among others transformation products of triclosan and triclocarban.

  5. Natural products in Glycyrrhiza glabra (licorice) rhizome imaged at the cellular level by atmospheric pressure matrix-assisted laser desorption/ionization tandem mass spectrometry imaging.

    PubMed

    Li, Bin; Bhandari, Dhaka Ram; Janfelt, Christian; Römpp, Andreas; Spengler, Bernhard

    2014-10-01

    The rhizome of Glycyrrhiza glabra (licorice) was analyzed by high-resolution mass spectrometry imaging and tandem mass spectrometry imaging. An atmospheric pressure matrix-assisted laser desorption/ionization imaging ion source was combined with an orbital trapping mass spectrometer in order to obtain high-resolution imaging in mass and space. Sections of the rhizome were imaged with a spatial resolution of 10 μm in the positive ion mode, and a large number of secondary metabolites were localized and identified based on their accurate mass and MS/MS fragmentation patterns. Major tissue-specific metabolites, including free flavonoids, flavonoid glycosides and saponins, were successfully detected and visualized in images, showing their distributions at the cellular level. The analytical power of the technique was tested in the imaging of two isobaric licorice saponins with a mass difference of only 0.02 Da. With a mass resolving power of 140 000 and a bin width of 5 ppm in the image processing, the two compounds were well resolved in full-scan mode, and appeared with different distributions in the tissue sections. The identities of the compounds and their distributions were validated in a subsequent MS/MS imaging experiment, thereby confirming their identities and excluding possible analyte interference. The use of high spatial resolution, high mass resolution and tandem mass spectrometry in imaging experiments provides significant information about the biosynthetic pathway of flavonoids and saponins in legume species, combing the spatially resolved chemical information with morphological details at the microscopic level. Furthermore, the technique offers a scheme capable of high-throughput profiling of metabolites in plant tissues. © 2014 The Authors The Plant Journal © 2014 John Wiley & Sons Ltd.

  6. Potential of atmospheric pressure chemical ionization source in gas chromatography tandem mass spectrometry for the screening of urinary exogenous androgenic anabolic steroids.

    PubMed

    Raro, M; Portolés, T; Pitarch, E; Sancho, J V; Hernández, F; Garrostas, L; Marcos, J; Ventura, R; Segura, J; Pozo, O J

    2016-02-04

    The atmospheric pressure chemical ionization (APCI) source for gas chromatography-mass spectrometry analysis has been evaluated for the screening of 16 exogenous androgenic anabolic steroids (AAS) in urine. The sample treatment is based on the strategy currently applied in doping control laboratories i.e. enzymatic hydrolysis, liquid-liquid extraction (LLE) and derivatization to form the trimethylsilyl ether-trimethylsilyl enol ether (TMS) derivatives. These TMS derivatives are then analyzed by gas chromatography tandem mass spectrometry using a triple quadrupole instrument (GC-QqQ MS/MS) under selected reaction monitoring (SRM) mode. The APCI promotes soft ionization with very little fragmentation resulting, in most cases, in abundant [M + H](+) or [M + H-2TMSOH](+) ions, which can be chosen as precursor ions for the SRM transitions, improving in this way the selectivity and sensitivity of the method. Specificity of the transitions is also of great relevance, as the presence of endogenous compounds can affect the measurements when using the most abundant ions. The method has been qualitatively validated by spiking six different urine samples at two concentration levels each. Precision was generally satisfactory with RSD values below 25 and 15% at the low and high concentration level, respectively. Most the limits of detection (LOD) were below 0.5 ng mL(-1). Validation results were compared with the commonly used method based on the electron ionization (EI) source. EI analysis was found to be slightly more repeatable whereas lower LODs were found for APCI. In addition, the applicability of the developed method has been tested in samples collected after the administration of 4-chloromethandienone. The highest sensitivity of the APCI method for this compound, allowed to increase the period in which its administration can be detected.

  7. Tissue Imaging Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Laskin, Julia; Heath, Brandi S.; Roach, Patrick J.; Cazares, Lisa H.; Semmes, O. John

    2012-01-03

    We present the first results showing the ambient imaging of biological samples in their native environment using nanospray desorption ionization (nanoDESI) mass spectrometry. NanoDESI is an ambient pressure ionization technique that enables precise control of ionization of molecules from substrates. We demonstrate highly sensitive and robust analysis of tissue samples with high spatial resolution (<12 {mu}m) without sample preparation, which will be essential for applications in clinical diagnostics, drug discovery, molecular biology, and biochemistry.

  8. Multianalyte quantification of five sesqui- and ethyl ether oxy-mustard metabolites in human urine by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Ash, Doris H; Lemire, Sharon W; McGrath, Sara C; McWilliams, Lisa G; Barr, John R

    2008-01-01

    Sesqui- and oxy-mustards pose a significant threat to military forces and civilians because they are potent vesicants. We have developed an isotope-dilution high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry method utilizing negative ion multiple reaction monitoring for the analysis of sesqui-mustard metabolites bis(2-hydroxyethylthio)alkanes (n = 1-5) and oxy-mustard metabolite bis(2-hydroxyethylthioethyl)ether in human urine. Relative standard deviations were < 10% and the reportable limits of detection were 1 ng/mL in 0.5 mL of urine. We applied this method to 100 samples collected from individuals with no known exposure to sesqui- or oxy-mustards, and no urines showed detectable levels of any of the analytes, suggesting that these metabolites may be used for monitoring exposure to sesqui- and oxy-mustards.

  9. Determination of testosterone concentrations in rat plasma using liquid chromatography-atmospheric pressure chemical ionization mass spectrometry combined with ethyl oxime and acetyl ester derivatization.

    PubMed

    Niwa, Makoto; Watanabe, Noriko; Ochiai, Hisashi; Yamashita, Kouwa

    2005-09-25

    A quantitative method for measuring testosterone (T) concentrations in rat plasma was developed using ethyl oxime and acetyl ester derivatization and liquid chromatography-atmosphere pressure chemical ionization tandem mass spectrometry (LC-APCI-MS/MS). The method utilizes a solid phase extraction with Varian Bond Elut C18, a derivatization process to form testosterone ethoxime acetate and LC-APCI-MS/MS with a reversed phase LC and a C8 column. This method is capable of detecting testosterone concentrations as low as 0.2 ng/ml in a 0.05 ml sample of rat plasma. This method can be used as a sensitive chromatography-based assay for small sample volumes of rat blood.

  10. Determination of metformin in mouse, rat, dog and human plasma samples by laser diode thermal desorption/atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Swales, John G; Gallagher, Richard; Peter, Raimund M

    2010-11-02

    A simple, rapid and robust high-throughput assay for the quantitative analysis of metformin in plasma from different species using laser diode thermal desorption interfaced with atmospheric chemical pressure ionization tandem mass spectrometry (LDTD-APCI-MSMS) was developed for use in a pharmaceutical discovery environment. In order to minimize sample preparation a generic protein precipitation method was used to extract metformin from the plasma. Laser diode thermal desorption is a relatively new sample introduction method, the optimization of the instrumental parameters are presented. The method was successfully applied to spiked mouse, rat, dog and human plasma samples and was subsequently used to determine the oral pharmacokinetics of metformin after dosing to male rats in order to support drug discovery projects. The deviations for intra-assay accuracy and precision across the four species were less than 30% at all calibration and quality control levels.

  11. Detection of flunixin in equine urine using high-performance liquid chromatography with particle beam and atmospheric pressure ionization mass spectrometry after solid-phase extraction.

    PubMed

    Stanley, S M; Owens, N A; Rodgers, J P

    1995-05-05

    A normal-phase HPLC method combined with particle-beam mass spectrometry (PB-MS) was developed for the analysis of non-steroidal anti-inflammatory drugs (NSAIDs). The forty one NSAIDs analysed responded in one or more (electron impact, positive and negative chemical ionisation) modes and highly characteristic spectra were produced. A mixed-mode solid-phase extraction (SPE) method for isolating acidic NSAIDs was developed using the Bond Elut Certify II cartridge. The average recovery was 88.5%. Flunixin, extracted by SPE from urine of a mare to which the meglumine salt had been administered was positively identified by HPLC-PB-MS and HPLC-atmospheric pressure ionization (API) MS methods.

  12. Confirmation of eprinomectin, moxidectin, abamectin, doramectin, and ivermectin in beef liver by liquid chromatography/positive ion atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Ali, M S; Sun, T; McLeroy, G E; Phillippo, E T

    2000-01-01

    A liquid chromatographic (LC) multiresidue screening procedure was developed for determination of eprinomectin, moxidectin, abamectin, doramectin, and ivermectin in beef liver at 0, 25, 50, and 100 ppb levels. A procedure using low resolution LC/atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) was developed with further purification steps added to the quantitative LC method to confirm residues. Acetonitrile extracts of liver, prior to derivatization for LC analysis, were further purified by using a C8 solid-phase extraction cartridge and an alumina-B cartridge. The purified extract was analyzed by injection into an LC/positive ion APCI MS. Identity of the compound was confirmed by comparison of its retention time and relative intensity data with those of a standard or recovery from a fortified control liver sample. Anthelmintic drugs in acetonitrile extracts of liver containing eprinomectin, moxidectin, abamectin, doramectin, and ivermectin at 25 ppb, the lowest level of fortification used in the LC determinative method, were successfully confirmed.

  13. Highly sensitive and rapid normal-phase chiral screen using high-performance liquid chromatography-atmospheric pressure ionization tandem mass spectrometry (HPLC/MS).

    PubMed

    de la Puente, María Luz

    2004-11-05

    In the last years, there has been an increasing demand on the development of quantitative assays for determination of enantiopurity. Herein, we present a methodology based on a direct linking of an atmospheric pressure ionization mass spectrometer (MS-APCI) with a high-performance liquid chromatography HPLC (DAD) system, operated under normal-phase mode and without post-column addition of MS-compatible solvents, which provides the high specificity/selectivity (identification of isomers in complex mixtures) and accuracy (1-2% area level) required for daily chiral studies. As result of the success of our screen, the preparation of individual enantiomers or the racemic mixture in our Drug Discovery Research Laboratories at Lilly, Spain is usually not required. Therefore, additional non-valuable synthetic work is eliminated.

  14. Analysis of plant sterol and stanol esters in cholesterol-lowering spreads and beverages using high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectroscopy.

    PubMed

    Mezine, Igor; Zhang, Huizhen; Macku, Carlos; Lijana, Robert

    2003-09-10

    Plant sterol and stanol esters were separated on a Luna hexyl-phenyl column using a gradient of acetonitrile (90-100%) in water. The eluted compounds were detected by atmospheric pressure chemical ionization (APCI)-mass spectroscopy (MS) in the positive mode. Sterol and stanol esters produced [M + H - HOOCR](+) ions. Application of the hyphenated technique-LC-MS-allowed differentiation between a number of esters of sitosterol, campesterol, stigmasterol, and (tentatively) avenasterol, as well as sitostanol and campestanol esters. With cholesteryl decanoate used as the internal standard, the method showed good linearity, precision, and reproducibility. The method required minimal sample pretreatment and can be applied to samples with high water content (juices) as well as samples with high oil content (margarine spreads). The method could be useful for the analysis of sterol and stanol esters in fortified food products.

  15. Quantitative real-time monitoring of chemical reactions by autosampling flow injection analysis coupled with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhu, Zhenqian; Bartmess, John E; McNally, Mary Ellen; Hoffman, Ron M; Cook, Kelsey D; Song, Liguo

    2012-09-04

    Although qualitative and/or semiquantitative real-time monitoring of chemical reactions have been reported with a few mass spectrometric approaches, to our knowledge, no quantitative mass spectrometric approach has been reported so far to have a calibration valid up to molar concentrations as required by process control. This is mostly due to the absence of a practical solution that could well address the sample overloading issue. In this study, a novel autosampling flow injection analysis coupled with an atmospheric pressure chemical ionization mass spectrometry (FIA/APCI-MS) system, consisting of a 1 μL automatic internal sample injector, a postinjection splitter with 1:10 splitting ratio, and a detached APCI source connected to the mass spectrometer using a 4.5 in. long, 0.042 in. inner diameter (ID) stainless-steel capillary, was thus introduced. Using this system together with an optional FIA solvent modifier, e.g., 0.05% (v/v) isopropylamine, a linear quantitative calibration up to molar concentration has been achieved with 3.4-7.2% relative standard deviations (RSDs) for 4 replicates. As a result, quantitative real-time monitoring of a model reaction was successfully performed at the 1.63 M level. It is expected that this novel autosampling FIA/APCI-MS system can be used in quantitative real-time monitoring of a wide range of reactions under diverse reaction conditions.

  16. [Isolation and purification of solanesol from potato leaves by high-speed counter-current chromatography and identification by atmospheric pressure chemical ionization mass spectrometry].

    PubMed

    Hu, Jiangyong; Liang, Yong; Xie, Ya; Huang, Zhaofeng; Zhong, Hanzuo

    2007-07-01

    Preparative high-speed counter-current chromatography (HSCCC) was used for the isolation and purification of solanesol from potato leaves. Experimental conditions of the extraction of solanesol from potato leaves have been optimized. An ultrafine extraction method was applied in this study. The efficiency using an ultrafine extraction was found to be improved in the investigation, the yields of solanesol by different extraction methods were 0.083% by ultrafine extraction and 0.050% by ultrasonic extraction. Using n-hexane-methanol (10:7, v/v) as the two-phase solvent system, preparative HSCCC was successfully performed with the yield of 5 mg solanesol at 98.7% of purity from 60 mg of crude extract in the one-step separation. The mobile phase was the lower phase and operated at a flow rate of 1.5 mL/min, while the apparatus rotated at 800 r/min. The solanesol was identified by the atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The ionization and cleavage mechanisms of solanesol in APCI-MS and APCI-MS/MS are discussed.

  17. Characterizing and compensating for matrix effects using atmospheric pressure chemical ionization liquid chromatography-tandem mass spectrometry: analysis of neutral pharmaceuticals in municipal wastewater.

    PubMed

    Zhao, Xiaoming; Metcalfe, Chris D

    2008-03-15

    Matrix effects are a great challenge for the quantitative analysis of environmental samples by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Signal suppression or enhancement can compromise the accuracy of analytical results. While matrix effects have been relatively well studied for applications of LC-MS/MS instrumentation with electrospray ionization, there have been relatively few studies to evaluate matrix effects when using atmospheric pressure chemical ionization (APCI) as the ion source. In this study, we determined the effects of sample matrix on the analysis of six neutral pharmaceuticals (i.e., caffeine, cotinine, carbamazepine and its major metabolite, carbamazepine-10,11-dihydrodiol, trimethoprim, and fluoxetine) in samples of municipal wastewater using LC-APCI-MS/MS and evaluated whether isotope-labeled internal standards can be used to compensate for matrix effects. The matrix effects were measured using postextraction spikes and postcolumn direct infusion, respectively. The results showed that the matrix in the extracts prepared from municipal wastewater enhanced the signals for four of the six analytes when using an APCI source. Without correction for signal enhancement, apparent recoveries of the analytes from wastewater samples were overestimated to levels as high as 178% of the spiked amount. Isotope-labeled compounds corrected for these overestimates that occurred as a result of interferences from the sample matrix.

  18. Determination of LY355703 in dog and mouse plasma by positive ion liquid chromatography/tandem mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Berna, M; Shugert, R; Mullen, J

    1998-02-01

    A liquid chromatographic/mass spectrometric assay was developed for the determination of LY355703, a potent anti-tumor drug, in mouse and dog plasma. Empore (3M) C18 solid-phase extraction cartridges were used for sample preparation in conjunction with a positive pressure manifold. Chromatographic separation was obtained with a cyano high-performance liquid chromatographic column and detection was conducted using atmospheric pressure chemical ionization tandem mass spectrometry in the selected reaction monitoring mode. A structural analog, compound LY354504, was used as the internal standard. The assay was validated for the determination of LY355703 in mouse (ICR and NuNu) and dog (beagle) plasma. The lower and upper limits of quantitation were 2.1 and 527 ng ml-1, respectively, using a 0.1 ml plasma aliquot. The signal-to-noise ratio of a typical 2.1 ng ml-1 standard was approximately 40:1. The inter-day precision (relative standard deviation) and accuracy (relative error) derived from the analysis of validation samples at five concentrations ranged from 2.7 to 7.6% and from 4.8 to 4.5%, respectively. Throughput is approximately one sample every 3 min. This assay is simple, sensitive, accurate, precise and is being used to support toxicokinetic studies in dog and mouse.

  19. Quantitation of triacylglycerols in edible oils by off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column.

    PubMed

    Wei, Fang; Hu, Na; Lv, Xin; Dong, Xu-Yan; Chen, Hong

    2015-07-24

    In this investigation, off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column has been applied for the identification and quantification of triacylglycerols in edible oils. A novel mixed-mode phenyl-hexyl chromatographic column was employed in this off-line two-dimensional separation system. The phenyl-hexyl column combined the features of traditional C18 and silver-ion columns, which could provide hydrophobic interactions with triacylglycerols under acetonitrile conditions and can offer π-π interactions with triacylglycerols under methanol conditions. When compared with traditional off-line comprehensive two-dimensional liquid chromatography employing two different chromatographic columns (C18 and silver-ion column) and using elution solvents comprised of two phases (reversed-phase/normal-phase) for triacylglycerols separation, the novel off-line comprehensive two-dimensional liquid chromatography using a single column can be achieved by simply altering the mobile phase between acetonitrile and methanol, which exhibited a much higher selectivity for the separation of triacylglycerols with great efficiency and rapid speed. In addition, an approach based on the use of response factor with atmospheric pressure chemical ionization mass spectrometry has been developed for triacylglycerols quantification. Due to the differences between saturated and unsaturated acyl chains, the use of response factors significantly improves the quantitation of triacylglycerols. This two-dimensional liquid chromatography-mass spectrometry system was successfully applied for the profiling of triacylglycerols in soybean oils, peanut oils and lord oils. A total of 68 triacylglycerols including 40 triacylglycerols in soybean oils, 50 triacylglycerols in peanut oils and 44 triacylglycerols in lord oils have been identified and quantified. The liquid chromatography-mass spectrometry data were analyzed

  20. Application of pentafluorophenyl hydrazine derivatives to the analysis of nabumetone and testosterone in human plasma by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Sheen, J F; Her, G R

    2004-12-01

    Two carbonyl compounds, nabumetone and testosterone, were derivatized with pentafluorophenyl hydrazine (PFPH) and analyzed by atmospheric-pressure chemical-ionization mass spectrometry. The PFPH derivatives underwent dissociative electron capture in negative-ion APCI (ECAPCI) and gave intense [M-20](-) ions in the mass spectra. In positive-ion APCI, the PFPH derivatives underwent efficient protonation and gave intense [M + H](+) ions in the mass spectra. In CID, the major product ions of the [M-20](-) ions in ECAPCI corresponded to the partial moiety of PFPH. In contrast, the major product ions of [M + H](+) corresponded to the partial moiety of the analyte. By using selected reaction monitoring (SRM) detection, low pg of nabumetone (1 pg) and testosterone (7 pg) could be detected in both ECAPCI and positive-ion APCI. In comparison with the detection limits (SRM) of the underivatized analytes, use of the PFPH derivatives resulted in 2500-fold and 35-fold sensitivity enhancements for nabumetone and testosterone, respectively. The PFPH derivatives were applied to the analysis of nabumetone and testosterone in human plasma by both ECAPCI and positive-ion APCI and were found to enable detection of 0.1 ng mL(-1) nabumetone in spiked plasma. For testosterone, endogenous testosterone in female plasma was detected in both ECAPCI and positive-ion APCI.

  1. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Atmospheric pressure chemical ionization of explosives induced by soft X-radiation in ion mobility spectrometry: mass spectrometric investigation of the ionization reactions of drift gasses, dopants and alkyl nitrates.

    PubMed

    Riebe, Daniel; Erler, Alexander; Ritschel, Thomas; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Beil, Andreas; Blaschke, Michael; Ludwig, Thomas

    2016-08-01

    A promising replacement for the radioactive sources commonly encountered in ion mobility spectrometers is a miniaturized, energy-efficient photoionization source that produce the reactant ions via soft X-radiation (2.8 keV). In order to successfully apply the photoionization source, it is imperative to know the spectrum of reactant ions and the subsequent ionization reactions leading to the detection of analytes. To that end, an ionization chamber based on the photoionization source that reproduces the ionization processes in the ion mobility spectrometer and facilitates efficient transfer of the product ions into a mass spectrometer was developed. Photoionization of pure gasses and gas mixtures containing air, N2 , CO2 and N2 O and the dopant CH2 Cl2 is discussed. The main product ions of photoionization are identified and compared with the spectrum of reactant ions formed by radioactive and corona discharge sources on the basis of literature data. The results suggest that photoionization by soft X-radiation in the negative mode is more selective than the other sources. In air, adduct ions of O2(-) with H2 O and CO2 were exclusively detected. Traces of CO2 impact the formation of adduct ions of O2(-) and Cl(-) (upon addition of dopant) and are capable of suppressing them almost completely at high CO2 concentrations. Additionally, the ionization products of four alkyl nitrates (ethylene glycol dinitrate, nitroglycerin, erythritol tetranitrate and pentaerythritol tetranitrate) formed by atmospheric pressure chemical ionization induced by X-ray photoionization in different gasses (air, N2 and N2 O) and dopants (CH2 Cl2 , C2 H5 Br and CH3 I) are investigated. The experimental studies are complemented by density functional theory calculations of the most important adduct ions of the alkyl nitrates (M) used for their spectrometric identification. In addition to the adduct ions [M + NO3 ](-) and [M + Cl](-) , adduct ions such as [M + N2 O2 ](-) , [M

  3. Initial results of positron ionization mass spectrometry

    NASA Technical Reports Server (NTRS)

    Donohue, D. L.; Hulett, L. D., Jr.; Mcluckey, S. A.; Glish, G. L.; Eckenrode, B. A.

    1990-01-01

    The use of monoenergetic positrons for the ionization of organic molecules in the gas phase is described. The ionic products are analyzed with a time-of-flight mass spectrometer and detected to produce a mass spectrum. The ionization mechanisms which can be studied in this way include positron impact at energies above the ionization limit of the target molecules, positronium formation in the Ore gap energy range, and positron attachment at energies less than 1eV. The technique of positron ionization mass spectrometry (PIMS) may have analytical utility in that chemical selectivity is observed for one or more of these processes.

  4. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa.

  5. Screening of pesticides and polycyclic aromatic hydrocarbons in feeds and fish tissues by gas chromatography coupled to high-resolution mass spectrometry using atmospheric pressure chemical ionization.

    PubMed

    Nácher-Mestre, Jaime; Serrano, Roque; Portolés, Tania; Berntssen, Marc H G; Pérez-Sánchez, Jaume; Hernández, Félix

    2014-03-12

    This paper reports a wide-scope screening for detection and identification of pesticides and polycyclic aromatic hydrocarbons (PAHs) in feeds and fish tissues. QuEChERS sample treatment was applied, using freezing as an additional cleanup. Analysis was carried out by gas chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization (GC-(APCI) QTOF MS). The qualitative validation was performed for over 133 representative pesticides and 24 PAHs at 0.01 and 0.05 mg/kg. Subsequent application of the screening method to aquaculture samples made it possible to detect several compounds from the target list, such as chlorpyrifos-methyl, pirimiphos-methyl, and ethoxyquin, among others. Light PAHs (≤4 rings) were found in both animal and vegetable samples. The reliable identification of the compounds was supported by accurate mass measurements and the presence of at least two representative m/z ions in the spectrum together with the retention time of the peak, in agreement with the reference standard. Additionally, the search was widened to include other pesticides for which standards were not available, thanks to the expected presence of the protonated molecule and/or molecular ion in the APCI spectra. This could allow the detection and tentative identification of other pesticides different from those included in the validated target list.

  6. Quantitation of lysergic acid diethylamide in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry.

    PubMed

    Cui, Meng; McCooeye, Margaret A; Fraser, Catharine; Mester, Zoltán

    2004-12-01

    A quantitative method was developed for analysis of lysergic acid diethylamide (LSD) in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry (AP MALDI-ITMS). Following solid-phase extraction of LSD from urine samples, extracts were analyzed by AP MALDI-ITMS. The identity of LSD was confirmed by fragmentation of the [M + H](+) ion using tandem mass spectrometry. The quantification of LSD was achieved using stable-isotope-labeled LSD (LSD-d(3)) as the internal standard. The [M + H](+) ion fragmented to produce a dominant fragment ion, which was used for a selected reaction monitoring (SRM) method for quantitative analysis of LSD. SRM was compared with selected ion monitoring and produced a wider linear range and lower limit of quantification. For SRM analysis of samples of LSD spiked in urine, the calibration curve was linear in the range of 1-100 ng/mL with a coefficient of determination, r(2), of 0.9917. This assay was used to determine LSD in urine samples and the AP MALDI-MS results were comparable to the HPLC/ ESI-MS results.

  7. Analysis of the enantiomers of VX using normal-phase chiral liquid chromatography with atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Smith, J R

    2004-01-01

    The chemical warfare nerve agent O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate (VX) is a mixture of two enantiomers resulting from the chiral center at the phosphorus atom. Significant differences exist in the reported toxicity and acetylcholinesterase inhibition rates of the two enantiomers. This makes the ability to distinguish between them desirable for either toxicological studies or the development of antidotal therapies. Using a Chiralcel OD-H column with normal-phase liquid chromatography, the enantiomers were baseline resolved in less than 7 min. Atmospheric pressure chemical ionization was utilized as the interface between a liquid chromatograph and mass spectrometer. The mass spectra of the two enantiomers were virtually identical. The protonated molecule was readily observed at m/z 268. VX was incubated with human plasma for 13 min, followed by hexane extraction. The areas of the first and second eluting VX enantiomers decreased by approximately 40% and 6%, respectively, when compared with VX-spiked plasma samples that were not allowed an incubation phase. Currently, research by others has been directed towards the identification, isolation, and possible modification of enzymes capable of hydrolyzing VX. The method presented here provides an analytical tool capable of monitoring the stereospecificity of enzymes that react with VX.

  8. Rapid and sensitive analysis of azadirachtin and related triterpenoids from Neem (Azadirachta indica) by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Schaaf, O; Jarvis, A P; van der Esch, S A; Giagnacovo, G; Oldham, N J

    2000-07-21

    Based on reversed-phase high-performance liquid chromatography (RP-HPLC) and atmospheric pressure chemical ionization (APCI) mass spectrometry, a HPLC-MS method was developed to permit the rapid qualitative and quantitative analysis of azadirachtin and related tetranortriterpenoids from seeds and tissue cultures of Neem (Azadirachta indica). APCI+ standard scanning mass spectra of the major Neem triterpenoids were recorded and utilized to select suitable ions for selected ion monitoring (SIM). Transitions for selective reaction monitoring (SRM) were based on MS-MS experiments. Using SIM, major Neem triterpenoids were detected in callus culture material and seed kernels of A. indica. The limit of detection for azadirachtin in extract samples (approximately 1 ng ml(-1) or 10 pg in SIM mode) was determined to be (with respect to injected absolute amounts) approximately 1000-times lower than values quoted in the literature for existing HPLC methods (approximately 200 ng ml(-1) or 10 ng). In addition to high sensitivity, the HPLC-MS method is able to tolerate minimal sample preparation and purification, dramatically reducing total analysis time.

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

    PubMed

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

    2016-04-15

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

  10. Identification of organic nitrates in the NO3 radical initiated oxidation of alpha-pinene by atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Perraud, Véronique; Bruns, Emily A; Ezell, Michael J; Johnson, Stanley N; Greaves, John; Finlayson-Pitts, Barbara J

    2010-08-01

    The gas-phase reactions of nitrate radicals (NO3) with biogenic organic compounds are a major sink for these organics during night-time. These reactions form secondary organic aerosols, including organic nitrates that can undergo long-range transport, releasing NOx downwind. We report here studies of the reaction of NO3 with alpha-pinene at 1 atm in dry synthetic air (relative humidity approximately 3%) and at 298 K using atmospheric pressure chemical ionization triple quadrupole mass spectrometry (APCI-MS) to identify gaseous and particulate products. The emphasis is on the identification of individual organic nitrates in the particle phase that were obtained by passing the product mixture through a denuder to remove gas-phase reactants and products prior to entering the source region of the mass spectrometer. Filter extracts were also analyzed by GC-MS and by APCI time-of-flight mass spectrometry (APCI-ToF-MS) with methanol as the proton source. In addition to pinonaldehyde and pinonic acid, five organic nitrates were identified in the particles as well as in the gas phase: 3-oxopinane-2-nitrate, 2-hydroxypinane-3-nitrate, pinonaldehyde-PAN, norpinonaldehyde-PAN, and (3-acetyl-2,2-dimethyl-3-nitrooxycyclobutyl)acetaldehyde. Furthermore, there was an additional first-generation organic nitrate product tentatively identified as a carbonyl hydroxynitrate with a molecular mass of 229. These studies suggest that a variety of organic nitrates would partition between the gas phase and particles in the atmosphere, and serve as a reservoir for NOx.

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

    PubMed

    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.

  12. Open Port Probe Sampling Interface for the Direct Coupling of Biocompatible Solid-Phase Microextraction to Atmospheric Pressure Ionization Mass Spectrometry.

    PubMed

    Gómez-Ríos, Germán Augusto; Liu, Chang; Tascon, Marcos; Reyes-Garcés, Nathaly; Arnold, Don W; Covey, Thomas R; Pawliszyn, Janusz

    2017-04-04

    In recent years, the direct coupling of solid phase microextraction (SPME) and mass spectrometry (MS) has shown its great potential to improve limits of quantitation, accelerate analysis throughput, and diminish potential matrix effects when compared to direct injection to MS. In this study, we introduce the open port probe (OPP) as a robust interface to couple biocompatible SPME (Bio-SPME) fibers to MS systems for direct electrospray ionization. The presented design consisted of minimal alterations to the front-end of the instrument and provided better sensitivity, simplicity, speed, wider compound coverage, and high-throughput in comparison to the LC-MS based approach. Quantitative determination of clenbuterol, fentanyl, and buprenorphine was successfully achieved in human urine. Despite the use of short extraction/desorption times (5 min/5 s), limits of quantitation below the minimum required performance levels (MRPL) set by the world antidoping agency (WADA) were obtained with good accuracy (≥90%) and linearity (R(2) > 0.99) over the range evaluated for all analytes using sample volumes of 300 μL. In-line technologies such as multiple reaction monitoring with multistage fragmentation (MRM(3)) and differential mobility spectrometry (DMS) were used to enhance the selectivity of the method without compromising analysis speed. On the basis of calculations, once coupled to high throughput, this method can potentially yield preparation times as low as 15 s per sample based on the 96-well plate format. Our results demonstrated that Bio-SPME-OPP-MS efficiently integrates sampling/sample cleanup and atmospheric pressure ionization, making it an advantageous configuration for several bioanalytical applications, including doping in sports, in vivo tissue sampling, and therapeutic drug monitoring.

  13. Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

    PubMed

    Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

    2016-07-01

    A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Capillary action-supported contactless atmospheric pressure ionization for the combined sampling and mass spectrometric analysis of biomolecules.

    PubMed

    Hsieh, Cheng-Huan; Chang, Chia-Hsien; Urban, Pawel L; Chen, Yu-Chie

    2011-04-15

    It is proposed that a short tapered capillary can be utilized as a nanoliter-volume sampling tool and sample emitter for generation of gas-phase ions in front of the mass spectrometer, without the need for using an additional electric power supply, a gas supply, or a syringe pump. A wide range of molecules can be analyzed in pure solutions and complex matrixes (cell extract, urine, and plant tissue) with no or minimum sample preparation. Singly and multiply charged ions can be detected in either positive or negative-ion mode. Because of the nanoliter-volume sampling and low spectral background, the mass detection limit for bradykinin is in the low attomole range. Other advantages include simplicity, disposability, and low cost. The putative mechanism of the ion formation in this capillary-action supported contactless spray emitter is discussed.

  15. Ionization of EPA contaminants in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

    PubMed

    Kauppila, Tiina J; Kersten, Hendrik; Benter, Thorsten

    2015-06-01

    Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

  16. Ionization of EPA Contaminants in Direct and Dopant-Assisted Atmospheric Pressure Photoionization and Atmospheric Pressure Laser Ionization

    NASA Astrophysics Data System (ADS)

    Kauppila, Tiina J.; Kersten, Hendrik; Benter, Thorsten

    2015-06-01

    Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

  17. Achieving 50% ionization efficiency in sub-ambient pressure ionization with nanoelectrospray

    PubMed Central

    Marginean, Ioan; Page, Jason S.; Tolmachev, Aleksey V.; Tang, Keqi; Smith, Richard D.

    2010-01-01

    Inefficient ionization and poor transmission of the charged species produced by an electrospray from the ambient pressure mass spectrometer source into the high vacuum region required for mass analysis significantly limits achievable sensitivity. Here we present evidence that, when operated at flow rates of 50 nL/min, a new electrospray-based ion source operated at ~20 Torr can deliver ~50% of the analyte ions initially in the solution as charged desolvated species into the rough vacuum region of mass spectrometers. The ion source can be tuned to optimize the analyte signal for readily ionized species while reducing the background contribution. PMID:21028835

  18. Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography-tandem mass spectrometry.

    PubMed

    Wick, Arne; Fink, Guido; Ternes, Thomas A

    2010-04-02

    This paper describes the development of a multi-residue method for the determination of 36 emerging organic pollutants (26 biocides, 5 UV-filters and 5 benzothiazoles) in raw and treated wastewater, activated sludge and surface water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The target analytes were enriched from water samples adjusted to pH 6 by solid-phase extraction (SPE) on Oasis HLB 200mg cartridges and eluted with a mixture of methanol and acetone (60/40, v/v). Extraction of freeze-dried sludge samples was accomplished by pressurized liquid extraction (PLE) using a mixture of methanol and water (50/50, v/v) as extraction solvent followed by SPE. LC-tandem MS detection was compared using electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) in positive and negative ionization mode. ESI exhibited strong ion suppression for most target analytes, while APCI was generally less susceptible to ion suppression but partially leading to ion enhancement of up to a factor of 10. In general, matrix effects could be compensated using stable isotope-labeled surrogate standards, indicated by relative recoveries ranging from 70% to 130%. In wastewater, activated sludge and surface water up to 33 analytes were detected. Maximum concentrations up to 5.1 and 3.9mugL(-1) were found in raw wastewater for the water-soluble UV-filters benzophenone-4 (BZP-4) and phenylbenz-imidazole sulfonic acid (PBSA), respectively. For the first time, the anti-dandruff climbazole was detected in raw wastewater and in activated sludge with concentrations as high as 1.4 microg L(-1) and 1.2 microg gTSS(-1), respectively. Activated sludge is obviously a sink for four benzothiazoles and two isothiazolones, as concentrations were detected in activated sludge between 120 ng gTSS(-1) (2-n-octyl-4-isothiazolin-3-one, OIT) to 330 ng gTSS(-1) (benzothiazole-2-sulfonic acid, BTSA). Copyright (c) 2010 Elsevier B.V. All rights reserved.

  19. 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.

    PubMed

    Portolés, T; Mol, J G J; Sancho, J V; López, Francisco J; Hernández, F

    2014-08-01

    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 acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS(E)). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20mg kg(-1). For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01mg kg(-1) level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01mg kg(-1) for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01mg kg(-1) level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20mg kg(-1) level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Note: Discharging fused silica test masses with ionized nitrogen

    NASA Astrophysics Data System (ADS)

    Ugolini, D.; Funk, Q.; Amen, T.

    2011-04-01

    We have developed a technique for discharging fused silica test masses in a gravitational-wave interferometer with nitrogen ionized by an electron beam. The electrons are produced from a heated filament by thermionic emission in a low-pressure region to avoid contamination and burnout. Some electrons then pass through a small aperture and ionize nitrogen in a higher-pressure region, and this ionized gas is pumped across the test mass surface, neutralizing both polarities of charge. The discharge rate varies exponentially with charge density and filament current, quadratically with filament potential, and has an optimal working pressure of ˜8 mT. Adapting the technique to larger test mass chambers is also discussed.

  1. Differentiation of various kinds of Fructus schisandrae by surface desorption atmospheric pressure chemical ionization mass spectrometry combined with principal component analysis.

    PubMed

    Pi, Zifeng; Yue, Hao; Ma, Li; Ding, Liying; Liu, Zhiqiang; Liu, Shuying

    2011-11-14

    Various kinds of Fructus schisandrae were studied by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS) without any sample pretreatment. The volatile components in F. schisandrae were detected in the ambient environment and the analytical time for each sample was only 30s. F. schisandrae are produced mainly in 5 different geographical regions (Elunchun, Mudanjiang, Tonghua, Tieling and Shangluo), and they could be successfully differentiated according to their chemical markers by Principal Component Analysis (PCA). A total of 8 components which gave more contribution for PCA analysis were unambiguously identified by comparison of the MS(2) data of chemical markers to the data of reference compounds as reported in the literature. Similarly, wild grown and cultivatable species of F. schisandrae were well separated by the above-mentioned method. In addition, raw and processed cultivatable F. schisandrae (steamed by water, alcohol, vinegar, or honey, and fried by honey) were found to be clustered at different location, respectively. Furthermore, the clustered degree of differently processed products was correlated with their clinical effects. Our results demonstrated that DAPCI-MS in combination with PCA was a feasible technique for high-throughput differentiation of various kinds of F. schisandrae. It is also possible that DAPCI-MS could become a powerful technology in the studies of traditional Chinese medicine studies and in situ analysis of Chinese herbs. Copyright © 2011. Published by Elsevier B.V.

  2. Analysis of vitamin K1 in fruits and vegetables using accelerated solvent extraction and liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Jäpelt, Rie Bak; Jakobsen, Jette

    2016-02-01

    The objective of this study was to develop a rapid, sensitive, and specific analytical method to study vitamin K1 in fruits and vegetables. Accelerated solvent extraction and solid phase extraction was used for sample preparation. Quantification was done by liquid chromatography tandem mass spectrometry with atmospheric pressure chemical ionization in selected reaction monitoring mode with deuterium-labeled vitamin K1 as an internal standard. The precision was estimated as the pooled estimate of three replicates performed on three different days for spinach, peas, apples, banana, and beetroot. The repeatability was 5.2% and the internal reproducibility was 6.2%. Recovery was in the range 90-120%. No significant difference was observed between the results obtained by the present method and by a method using the same principle as the CEN-standard i.e. liquid-liquid extraction and post-column zinc reduction with fluorescence detection. Limit of quantification was estimated to 0.05 μg/100g fresh weight. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. A highly specific and sensitive quantification analysis of the sterols in silkworm larvae by high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Igarashi, Fumihiko; Hikiba, Juri; Ogihara, Mari H; Nakaoka, Takayoshi; Suzuki, Minoru; Kataoka, Hiroshi

    2011-12-15

    The biochemical quantification of sterols in insects has been difficult because only small amounts of tissues can be obtained from insect bodies and because sterol metabolites are structurally related. We have developed a highly specific and sensitive quantitative method for determining of the concentrations of seven sterols-7-dehydrocholesterol, desmosterol, cholesterol, ergosterol, campesterol, stigmasterol, and β-sitosterol-using a high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (HPLC/APCI-MS/MS). The sterols were extracted from silkworm larval tissues using the Bligh and Dyer method and were analyzed using HPLC/APCI-MS/MS with selected reaction monitoring, using cholesterol-3,4-(13)C(2) as an internal standard. The detection limits of the method were between 12.1 and 259 fmol. The major sterol in most silkworm larval tissues was cholesterol, whereas only small quantities of the dietary sterols were detected. Thus, a simple, sensitive, and specific method was successfully developed for the quantification of the sterol concentrations in each tissue of an individual silkworm larva. This method will be a useful tool for investigating to molecular basis of sterol physiology in insects, facilitating the quantification of femtomole quantities of sterols in biological samples. Copyright © 2011 Elsevier Inc. All rights reserved.

  4. Determination of pramipexole (U-98,528) in human plasma by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Lau, Y Y; Selenka, J M; Hanson, G D; Talaat, R; Ichhpurani, N

    1996-08-30

    A highly sensitive and selective HPLC-MS-MS method was developed for the determination of pramipexole in human plasma. The analytes, pramipexole and BHT-920 (internal standard), were extracted from plasma at basic pH with methyl tert.-butyl ether (MTBE). MTBE was evaporated to dryness and reconstituted in 100 microliters of (95:5) methanol-water. Chromatographic separation was achieved on a Zorbax SB-CN column with a mobile phase of (15:5:80) water-0.1 M ammonium acetate-methanol. The analytes were detected utilizing HPLC in conjunction with atmospheric pressure chemical ionization (APCI) tandem mass spectrometry (MS-MS). The assay was linear in the concentration ranges of 50 to 5000 pg/ml. The analysis of pooled quality controls (150, 750, and 3000 pg/ml) demonstrated excellent precision with relative standard deviations (R.S.D.) (n = 18) of 7.2%, 5.3% and 5.2%, respectively. The method is accurate with all intra-day (n = 6) and overall (n = 18) mean values being less than 11.7% from theoretical.

  5. Continuous water infusion enhances atmospheric pressure chemical ionization of methyl chloroformate derivatives in gas chromatography coupled to time-of-flight mass spectrometry-based metabolomics.

    PubMed

    Wachsmuth, Christian J; Dettmer, Katja; Lang, Sven A; Mycielska, Maria E; Oefner, Peter J

    2014-09-16

    The effects of continuous water infusion on efficiency and repeatability of atmospheric pressure chemical ionization of both methyl chloroformate (MCF) and methoxime-trimethylsilyl (MO-TMS) derivatives of metabolites were evaluated using gas chromatography-time-of-flight mass spectrometry. Water infusion at a flow-rate of 0.4 mL/h yielded not only an average 16.6-fold increase in intensity of the quasimolecular ion for 20 MCF-derivatized metabolite standards through suppression of in-source fragmentation but also the most repeatable peak area integrals. The impact of water infusion was the greatest for dicarboxylic acids and the least for (hetero-) aromatic compounds. Water infusion also improved the ability to detect reliably fold changes as small as 1.33-fold for the same 20 MCF-derivatized metabolite standards spiked into a human serum extract. On the other hand, MO-TMS derivatives were not significantly affected by water infusion, neither in their fragmentation patterns nor with regard to the detection of differentially regulated compounds. As a proof of principle, we applied MCF derivatization and GC-APCI-TOFMS to the detection of changes in abundance of metabolites in pancreatic cancer cells upon treatment with 17-DMAG. Water infusion increased not only the number of metabolites identified via their quasimolecular ion but also the reproducibility of peak areas, thereby almost doubling the number of significantly regulated metabolites (false discovery rate < 0.05) to a total of 23.

  6. Carbamazepine in municipal wastewater and wastewater sludge: ultrafast quantification by laser diode thermal desorption-atmospheric pressure chemical ionization coupled with tandem mass spectrometry.

    PubMed

    Mohapatra, D P; Brar, S K; Tyagi, R D; Picard, P; Surampalli, R Y

    2012-09-15

    In this study, the distribution of the anti-epileptic drug carbamazepine (CBZ) in wastewater (WW) and aqueous and solid phases of wastewater sludge (WWS) was carried out. A rapid and reliable method enabling high-throughput sample analysis for quicker data generation, detection, and monitoring of CBZ in WW and WWS was developed and validated. The ultrafast method (15s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). The optimization of instrumental parameters and method application for environmental analysis are presented. The performance of the novel method was evaluated by estimation of extraction recovery, linearity, precision and detection limit. The method detection limits was 12 ng L(-1) in WW and 3.4 ng g(-1) in WWS. The intra- and inter-day precisions were 8% and 11% in WW and 6% and 9% in WWS, respectively. Furthermore, three extraction methods, ultrasonic extraction (USE), microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) with three different solvent condition such as methanol, acetone and acetonitrile:ethyle acetate (5:1, v/v) were compared on the basis of procedural blank and method recovery. Overall, ASE showed the best extraction efficiency with methanol as compared to USE and MAE. Furthermore, the quantification of CBZ in WW and WWS samples showed the presence of contaminant in all stages of the treatment plant.

  7. Identification and quantification of antitumor thioproline and methylthioproline in Korean traditional foods by a liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Kim, Sun Hyo; Kim, Hyun-Ji; Shin, Ho-Sang

    2014-11-01

    A liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometric method (LC-APCI-MS/MS) has been developed for the sensitive determination of antitumor thioproline and methylthioproline from fermented foods. Thioproline and methylthioproline were derivatized in one step with ethyl chloroformate at room temperature. These compounds were identified and quantified in various traditional Korean fermented foods by LC-APCI-MS/MS. The concentration range of thioproline of each food was found for doenjang (0.011-0.032mg/kg), gochujang (0.010-0.038mg/kg), and ganjang (0.010-0.038mg/kg). Those of methylthioproline of each food was found for doenjang (0.098-0.632mg/kg), gochujang (0.015-0.112mg/kg), and ganjang (0.023-1.468mg/kg). A prolonged aging time leads to an increase in both the thioproline and methylthioproline contents, suggesting that the storage time plays a key role in the formation of thioproline and methylthioproline in Korean traditional foods. The results here suggest that thioproline and methylthioproline are related to the biological activities of traditional Korean fermented foods.

  8. A method for simultaneous analysis of phytosterols and phytosterol esters in tobacco leaves using non aqueous reversed phase chromatography and atmospheric pressure chemical ionization mass spectrometry detector.

    PubMed

    Ishida, Naoyuki

    2014-05-02

    While numerous analytical methods for phytosterols have been reported, the similar polarity and large molecules of phytosterol esters have made the methods lengthy and complicated. For this reason, an analytical method that could completely separate phytosterol esters including the higher fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid in addition to phytosterols without preliminary separation was developed. The separation was accomplished by non-aqueous reversed phase chromatography technique using only acetone and acetonitrile. An atmospheric pressure chemical ionization/mass spectrometry detector configured at selected ion monitoring mode was hyphenated with the separation system to detect phytosterols and phytosterol esters. Twenty-four types of these were consequently separated and then identified with their authentic components. The calibration curve was drawn in the range of about 5 to 25,000 ng/mL with a regression coefficient over 0.999. The limit of detection and limit of quantification, respectively, ranged from 0.9 to 3.0 ng/mL and from 3.0 to 11.0 ng/mL. Recovery rates ranged from 80 to 120%. The quantification results were subjected to statistical analysis and hierarchical clustering analysis, and were used to determine the differences in the amounts of phytosterols and phytosterol esters across tobacco leaves. The newly developed method succeeded in clarifying the whole composition of phytosterols and phytosterol esters in tobacco leaves and in explaining compositional differences across the variety of tobacco leaves.

  9. Triacylglycerols profiling in plant oils important in food industry, dietetics and cosmetics using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Lísa, Miroslav; Holcapek, Michal

    2008-07-11

    Optimized non-aqueous reversed-phase high-performance liquid chromatography method using acetonitrile-2-propanol gradient elution and the column coupling in the total length of 45 cm has been applied for the high resolution separation of plant oils important in food industry, dietetics and cosmetics. Positive-ion atmospheric pressure chemical ionization mass spectrometry is used for the unambiguous identification and also the reliable quantitation with the response factors approach. Based on the precise determination of individual triacyglycerol concentrations, the calculation of average parameters important in the nutrition is performed, i.e. average carbon number, average double bond number, relative concentrations of essential, saturated, monounsaturated and polyunsaturated fatty acids. Results are reported in the form of both chromatographic fingerprints and tables containing relative concentrations for all triacylglycerols and fatty acids in individual samples. In total, 264 triacylglycerols consisting of 28 fatty acids with the alkyl chain length from 6 to 26 carbon atoms and 0 to 4 double bonds have been identified in 26 industrial important plant oils.

  10. Characterization of major and minor alk(en)ylresorcinols from mango (Mangifera indica L.) peels by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Knödler, Matthias; Berardini, Nicolai; Kammerer, Dietmar R; Carle, Reinhold; Schieber, Andreas

    2007-01-01

    5-Alkyl- and 5-alkenylresorcinols, as well as their hydroxylated derivatives, were extracted from mango (Mangifera indica L.) peels, purified on polyamide and characterized by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (HPLC/APcI-MS) for the first time. Among the 15 compounds analyzed, 3 major and 12 minor C(15)-, C(17)-, and C(19)-substituted resorcinols and related analogues, showing varying degrees of unsaturation, were characterized by their specific fragmentation patterns in collision-induced dissociation experiments. This marks the first report on the occurrence of mono-, di-, and triunsaturated C(15)-homologues, saturated and triunsaturated C(17)-homologues, and mono- and diunsaturated C(19)-homologues in mango peels. Additionally, several hydroxylated C(15)- and C(17)-homologues, also not yet described in mango, and a C(14)-monoene, unique because of its even-numbered side chain, were tentatively identified on the basis of their fragmentation patterns. The results obtained in the present study indicate that HPLC-DAD-APcI-MS(n), combined with the newly developed solid-phase extraction, is a powerful tool for the analysis of alk(en)ylresorcinols and could therefore be used for their determination in various matrices.

  11. Structure-dependent degradation of polar compounds in weathered oils observed by atmospheric pressure photo-ionization hydrogen/deuterium exchange ultrahigh resolution mass spectrometry.

    PubMed

    Islam, Ananna; Kim, Donghwi; Yim, Un Hyuk; Shim, Won Joon; Kim, Sunghwan

    2015-10-15

    The resin fractions of fresh mixtures of three oils spilled during the M/V Hebei Spirit oil spill, as well as weathered oils collected at weathering stages II and IV from the oil spill site were analyzed and compared by atmospheric pressure photo-ionization hydrogen/deuterium exchange mass spectrometry (HDX MS). The significantly decreased abundance of N(+) and [N-H+D](+) ions suggested that secondary and tertiary amine-containing compounds were preferentially degraded during the early stage of weathering. [N+H](+) and [N+D](+) ions previously attributed to pyridine-type compounds degraded more slowly than secondary and tertiary amine-containing compounds. The preferential degradation of nitrogen-containing compounds was confirmed by photo-degradation experiments using 15 standard compounds. In addition, significant increases of [S1O1+H](+) and [S1O1+D](+) ions with higher DBE values were observed from fresh oil mixtures as compared to stages II and IV samples, and that could be linked with the decrease of higher DBE compounds of the S1 class. This study presented convincing arguments and evidence demonstrating that secondary and tertiary amines were more vulnerable to photo-degradation than compounds containing pyridine, and hence, preferential degradation depending on chemical structures must be considered in the production of hazardous or toxic components. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Trace analysis of selected hormones and sterols in river sediments by liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Matić, Ivana; Grujić, Svetlana; Jauković, Zorica; Laušević, Mila

    2014-10-17

    In this paper, development and optimization of new LC-MS method for determination of twenty selected hormones, human/animal and plant sterols in river sediments were described. Sediment samples were prepared using ultrasonic extraction and clean up with silica gel/anhydrous sodium sulphate cartridge. Extracts were analyzed by liquid chromatography-linear ion trap-tandem mass spectrometry, with atmospheric pressure chemical ionization. The optimized extraction parameters were extraction solvent (methanol), weight of the sediment (2 g) and time of ultrasonic extraction (3× 10 min). Successful chromatographic separation of hormones (estriol and estrone, 17α- and 17β-estradiol) and four human/animal sterols (epicoprostanol, coprostanol, α-cholestanol and β-cholestanol) that have identical fragmentation reactions was achieved. The developed and optimized method provided high recoveries (73-118%), low limits of detection (0.8-18 ng g(-1)) and quantification (2.5-60 ng g(-1)) with the RSDs generally lower than 20%. Applicability of the developed method was confirmed by analysis of six river sediment samples. A widespread occurrence of human/animal and plant sterols was found. The only detected hormone was mestranol in just one sediment sample. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. Ion suppression and enhancement effects of co-eluting analytes in multi-analyte approaches: systematic investigation using ultra-high-performance liquid chromatography/mass spectrometry with atmospheric-pressure chemical ionization or electrospray ionization.

    PubMed

    Remane, Daniela; Meyer, Markus R; Wissenbach, Dirk K; Maurer, Hans H

    2010-11-15

    In multi-analyte procedures, sufficient separation is important to avoid interferences, particularly when using liquid chromatography/mass spectrometry (LC/MS) because of possible ion suppression or enhancement. However, even using ultra-high-performance LC, baseline separation is not always possible. For development and validation of an LC/MS/MS approach for quantification of 140 antidepressants, benzodiazepines, neuroleptics, beta-blockers, oral antidiabetics, and analytes measured in the context of brain death diagnosis in plasma, the extent of ion suppression or enhancement of co-eluting analytes within and between the drug classes was investigated using atmospheric-pressure chemical ionization (APCI) or electrospray ionization (ESI). Within the drug classes, five analytes showed ion enhancement of over 25% and six analytes ion suppression of over 25% using APCI and 16 analytes ion suppression of over 25% using ESI. Between the drug classes, two analytes showed ion suppression of over 25% using APCI. Using ESI, one analyte showed ion enhancement of over 25% and five analytes ion suppression of over 25%. These effects may influence the drug quantification using calibrators made in presence of overlapping and thus interfering analytes. Ion suppression/enhancement effects induced by co-eluting drugs of different classes present in the patient sample may also lead to false measurements using class-specific calibrators made in absence of overlapping and thus interfering analytes. In conclusion, ion suppression and enhancement tests are essential during method development and validation in LC/MS/MS multi-analyte procedures, with special regards to co-eluting analytes.

  14. Simultaneous determination of eight underivatized amphetamines in hair by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS).

    PubMed

    Stanaszek, Roman; Piekoszewski, Wojciech

    2004-03-01

    The aim of this study was to develop, optimize, and validate an analytical procedure to determine a group of eight amphetamines, amphetamine (AMP), ephedrine (EP), methcathinone (MTC), paramethoxyamphetamine (PMA), methamphetamine (MA), methylenedioxyamphetamine (MDA), methylenedioxymethamphetamine (MDMA), and methylenedioxyethylamphetamine (MDEA), in hair. The target substances were extracted with 1-chlorobutane after alkaline (1M NaOH) digestion and analyzed underivatized with high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). APCI-MS parameters such as fragmentor and capillary voltage, corona current, drying gas temperature and flow rate, vaporizer temperature, and nebulizer gas pressure were optimized with the application of flow injection analysis. Quantitation was performed using selected ion monitoring of protonated molecular ions of the studied drugs, and their deuterated analogues were used as internal standards. The limits of detection were 0.05 ng/mg for MA, MDA, MDMA, and MDEA; 0.10 ng/mg for EP and AMP; and 0.20 ng/mg for MTC and PMA. A linear response was observed for all drugs from 0 to 20 ng/mg. The method was applied to the determination of amphetamines in 93 authentic hair samples obtained from detoxification and methadone treatment patients, revealing the following concentrations: 0.17-17.28 ng/mg (EP), 0.52-2.08 ng/mg (MTC), 0.15-62.52 ng/mg (AMP), 0.10-16.52 ng/mg (MA), 0.10-0.88 ng/mg (MDMA), and 0.10-0.16 ng/mg (MDEA). MDA and PMA were never detected.

  15. Enantioselective determination of cetirizine in human plasma by normal-phase liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Kang, Seung Woo; Jang, Hae Jong; Moore, Victor S; Park, Ji-Young; Kim, Kyoung-Ah; Youm, Jeong-Rok; Han, Sang Beom

    2010-12-15

    A highly sensitive and enantioselective method has been developed and validated for the determination of levocetirizine [(R)-cetirizine] in human plasma by normal-phase liquid chromatography coupled to tandem mass spectrometry with an atmospheric pressure chemical ionization (APCI) interface in the positive ion mode. Enantioselective separation was achieved on a CHIRALPAK AD-H column using an isocratic mobile phase consisting of a mixture of n-hexane, ethyl alcohol, diethylamine, and acetic acid (60:40:0.1:0.1, v/v/v/v). Levocetirizine-D(8) was used as an internal standard (IS). Levocetirizine and the IS were detected by multiple-reaction monitoring (MRM). Mass transitions of analyte and IS were m/z 389.2→201.1 and 397.2→201.1, respectively. Under optimized analytical conditions, a baseline separation of two enantiomers and IS was obtained in less than 11 min. Samples were prepared by a simple two-step extraction by protein precipitation using acetonitrile followed by liquid-liquid extraction with a n-hexane-dichloromethane mixture (50:50, v/v). The standard curve for levocetirizine was linear (r(2)>0.995) in the concentration range 0.5-300 ng/mL. Recovery was between 97.0 and 102.2% at low, medium, and high concentration. The limit of quantification (LOQ) was 0.5 ng/mL. Other method validation parameters, such as precision, accuracy, and stability, were very satisfactory. Finally, the proposed method was successfully applied to the study of enantioselective oral pharmacokinetics of levocetirizine in healthy Korean volunteers.

  16. Determination of eight nitrosamines in water at the ng L(-1) levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Ripollés, Cristina; Pitarch, Elena; Sancho, Juan V; López, Francisco J; Hernández, Félix

    2011-09-19

    In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d(6) and NDPA-d(14)) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L(-1)) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD<20%). Limits of detection were found to be in the range of 1-8 ng L(-1). The described methodology has been applied to different types of water samples: chlorinated from drinking water and wastewater treatment plants (DWTP and WWTP, respectively), wastewaters subjected to ozonation and tap waters.

  17. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry.

    PubMed

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH(+), MOH(+), and MO(2)H(+), respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH(+) sharply decreased, that of MOH(+) increased once and then decreased, and that of MO(2)H(+) sharply increased until reaching a plateau. The signal intensity of MO(2)H(+) at the plateau was 40 times higher than that of MH(+) and 100 times higher than that of MOH(+) in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO(2)H(+) signal in the concentration range up to 60 μg/m(3), which is high enough for hygiene management. In the low concentration range lower than 3 μg/m(3), which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m(3) vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  18. In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Okumura, Akihiko

    2015-09-01

    A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH+, MOH+, and MO2H+, respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH+ sharply decreased, that of MOH+ increased once and then decreased, and that of MO2H+ sharply increased until reaching a plateau. The signal intensity of MO2H+ at the plateau was 40 times higher than that of MH+ and 100 times higher than that of MOH+ in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO2H+ signal in the concentration range up to 60 μg/m3, which is high enough for hygiene management. In the low concentration range lower than 3 μg/m3, which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m3 vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

  19. Determination of 21-hydroxydeflazacort in human plasma by high-performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry. Application to bioequivalence study.

    PubMed

    Ifa, D R; Moraes, M E; Moraes, M O; Santagada, V; Caliendo, G; de Nucci, G

    2000-03-01

    A liquid chromatographic atmospheric pressure chemical ionization tandem mass spectrometric method is described for the determination of 21-hydroxydeflazacort in human plasma using dexamethasone 21-acetate as an internal standard. The procedure requires a single diethyl ether extraction. After evaporation of the solvent under a nitrogen flow, the analytes are reconstituted in the mobile phase, chromatographed on a C18 reversed-phase column and analyzed by mass spectrometry via a heated nebulizer interface where they are detected by multiple reaction monitoring. The method has a chromatographic run time of less than 5 min and a linear calibration curve with a range of 1-400 ng ml(-1) (r>0.999). The between-run precision, based on the relative standard deviation for replicate quality controls, was < or =5.5% (10 ng ml(-1)), 1.0% (50 ng ml(-1)) and 2.7% (200 ng ml(-1)). The between-run accuracy was +/-7.1, 3.8 and 4.8% for the above concentrations, respectively. This method was employed in a bioequivalence study of two DFZ tablet formulations (Denacen from Marjan Industria e Comercio, Brazil, as a test formulation, and Calcort from Merrell Lepetit, Brazil, as a reference formulation) in 24 healthy volunteers of both sexes who received a single 30 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 7-day washout interval. The 90% confidence interval (CI) of the individual geometric mean ratio for Denacen/Calcort was 89.8-109.5% for area under the curve AUC(0-24 h) and 80.7-98.5% for Cmax. Since both the 90% CI for AUC(0-24 h) and Cmax were included in the 80-125% interval proposed by the US Food and Drug Administration, Denacen was considered bioequivalent to Calcort according to both the rate and extent of absorption.

  20. Forensic applications of ambient ionization mass spectrometry.

    PubMed

    Ifa, Demian R; Jackson, Ayanna U; Paglia, Giuseppe; Cooks, R Graham

    2009-08-01

    This review highlights and critically assesses forensic applications in the developing field of ambient ionization mass spectrometry. Ambient ionization methods permit the ionization of samples outside the mass spectrometer in the ordinary atmosphere, with minimal sample preparation. Several ambient ionization methods have been created since 2004 and they utilize different mechanisms to create ions for mass-spectrometric analysis. Forensic applications of these techniques--to the analysis of toxic industrial compounds, chemical warfare agents, illicit drugs and formulations, explosives, foodstuff, inks, fingerprints, and skin--are reviewed. The minimal sample pretreatment needed is illustrated with examples of analysis from complex matrices (e.g., food) on various substrates (e.g., paper). The low limits of detection achieved by most of the ambient ionization methods for compounds of forensic interest readily offer qualitative confirmation of chemical identity; in some cases quantitative data are also available. The forensic applications of ambient ionization methods are a growing research field and there are still many types of applications which remain to be explored, particularly those involving on-site analysis. Aspects of ambient ionization currently undergoing rapid development include molecular imaging and increased detection specificity through simultaneous chemical reaction and ionization by addition of appropriate chemical reagents.

  1. Screening and quantification of pesticide residues in fruits and vegetables making use of gas chromatography-quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Cervera, M I; Portolés, T; López, F J; Beltrán, J; Hernández, F

    2014-11-01

    An atmospheric pressure chemical ionization source has been used to enhance the potential of gas chromatography coupled with quadrupole time-of-flight (QTOF) mass spectrometry (MS) for screening and quantification purposes in pesticide residue analysis. A screening method developed in our laboratory for around 130 pesticides has been applied to fruit and vegetable samples, including strawberries, oranges, apples, carrots, lettuces, courgettes, red peppers, and tomatoes. Samples were analyzed together with quality control samples (at 0.05 mg/kg) for each matrix and for matrix-matched calibration standards. The screening strategy consisted in first rapid searching and detection, and then a refined identification step using the QTOF capabilities (MS(E) and accurate mass). Identification was based on the presence of one characteristic m/z ion (Q) obtained with the low collision energy function and at least one fragment ion (q) obtained with the high collision energy function, both with mass errors of less than 5 ppm, and an ion intensity ratio (q/Q) within the tolerances permitted. Following this strategy, 15 of 130 pesticides were identified in the samples. Afterwards, the quantitation capabilities were tested by performing a quantitative validation for those pesticides detected in the samples. To this aim, five matrices were selected (orange, apple, tomato, lettuce, and carrot) and spiked at two concentrations (0.01 and 0.1 mg/kg), and quantification was done using matrix-matched calibration standards (relative responses versus triphenyl phosphate used as an internal standard). Acceptable average recoveries and relative standard deviations were obtained for many but not all pesticide-matrix combinations. These figures allowed us to perform a retrospective quantification of positives found in the screening without the need for additional analysis. Taking advantage of the accurate-mass full-spectrum data provided by QTOF MS, we searched for a higher number of compounds

  2. Determination of lycopene, alpha-carotene and beta-carotene in serum by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry with selected-ion monitoring.

    PubMed

    Hagiwara, T; Yasuno, T; Funayama, K; Suzuki, S

    1998-04-24

    A selected-ion monitoring (SIM) determination of serum lycopene, alpha-carotene and beta-carotene by an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was developed. A large amount of serum cholesterols disturbed the SIM determination of carotenoids by contaminating the segment of interface with the LC-MS. Therefore, separation of carotenoids from the cholesterols was performed using a mixed solution of methanol and acetonitrile (70:30) as the mobile phase on a C18 column of mightsil ODS-5 (75 mm x 4.6 mm I.D.). The SIM determination was carried out by introducing only the peak portions of carotenoids and I.S. (squalene) by means of an auto switching valve. In the positive mode of APCI-MS, lycopene, alpha-carotene and beta-carotene were monitored at m/z 537 and I.S. was monitored at m/z 411. This method was linear for all analytes in the range of 15-150 ng for lycopene, 7-70 ng for alpha-carotene and 25-50 ng for beta-carotene. The detection limit of LC-APCI-MS-SIM for carotenoids was about 3 ng per 1 ml of serum (S/N = 3). The repeatabilities, expressed as C.V.s, were 10%, 8.4% and 5.3% for lycopene, alpha-carotene and beta-carotene, respectively. The intermediate precisions, expressed as C.V.s, were 11.2%, 8.8% and 6.5% for lycopene, alpha-carotene and beta-carotene, respectively.

  3. Determination and differentiation of triacylglycerol molecular species in Antarctic and non-Antarctic yeasts by atmospheric pressure-chemical ionization-mass spectrometry.

    PubMed

    Bhuiyan, Mohammad; Tucker, David; Watson, Kenneth

    2013-09-01

    Yeast, particularly Saccharomyces cerevisiae, has long served as a model eukaryotic system for studies on the regulation of lipid metabolism. We developed a high performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry method for the detailed analysis of triacylglycerols (TAGs) in 14 species of yeast consisting of seven Antarctic yeasts (grown at 15°C and 5°C) and seven non-Antarctic yeasts (grown at 25°C and 15°C), the latter including 3 strains of S. cerevisiae. Analysis of TAG molecular species established that the sn-2 position was invariably occupied by an unsaturated fatty acyl moiety. In S. cerevisiae the preference was for oleic acid 18:1>palmitoleic acid 16:1, in Candida albicans, Cryptococcus humicolus and Rhodotorula mucilaginosa 18:1>linoleic acid 18:2 and in Zygosaccharomyces rouxii 18:2>18:1. In the Antarctic yeasts (Cryptococcus watticus, Cryptococcus victoriae, Cryptococcus nyarrowii, Leucosporidium antarcticum, Leucosporidium fellii, Candida psychrophila and Rhodotorula mucilaginosa) the general pattern was for the sn-2 position to be occupied by 18:1, 18:2 or linolenic acid 18:3. A trend towards synthesis of increased unsaturated fatty acid in TAGs was observed as the growth temperature was lowered. The application of principal component analysis demonstrated that the yeasts were differentiated into three distinct groups. One group consisted of the three S. cerevisiae strains, a second the other four non-Antarctic yeasts and the third the seven Antarctic yeasts. The data for the Antarctic yeasts, to the best of our knowledge, have not been previously reported. © 2013 Elsevier B.V. All rights reserved.

  4. Analysis of trimethoprim, lincomycin, sulfadoxin and tylosin in swine manure using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Solliec, Morgan; Massé, Daniel; Sauvé, Sébastien

    2014-10-01

    A new extraction method coupled to a high throughput sample analysis technique was developed for the determination of four veterinary antibiotics. The analytes belong to different groups of antibiotics such as chemotherapeutics, sulfonamides, lincosamides and macrolides. Trimethoprim (TMP), sulfadoxin (SFX), lincomycin (LCM) and tylosin (TYL) were extracted from lyophilized manure using a sonication extraction. McIlvaine buffer and methanol (MeOH) were used as extraction buffers, followed by cation-exchange solid phase extraction (SPE) for clean-up. Analysis was performed by laser diode thermal desorption-atmospheric pressure chemical-ionization (LDTD-APCI) tandem mass spectrometry (MS/MS) with selected reaction monitoring (SRM) detection. The LDTD is a high throughput sample introduction method that reduces total analysis time to less than 15s per sample, compared to minutes when using traditional liquid chromatography (LC). Various SPE parameters were optimized after sample extraction: the stationary phase, the extraction solvent composition, the quantity of sample extracted and sample pH. LDTD parameters were also optimized: solvent deposition, carrier gas, laser power and corona discharge. The method limit of detection (MLD) ranged from 2.5 to 8.3 µg kg(-1) while the method limit of quantification (MLQ) ranged from 8.3 to 28µgkg(-1). Calibration curves in the manure matrix showed good linearity (R(2)≥ 0.996) for all analytes and the interday and intraday coefficients of variation were below 14%. Recoveries of analytes from manure ranged from 53% to 69%. The method was successfully applied to real manure samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Profiling of triacylglycerols in plant oils by high-performance liquid chromatography-atmosphere pressure chemical ionization mass spectrometry using a novel mixed-mode column.

    PubMed

    Hu, Na; Wei, Fang; Lv, Xin; Wu, Lin; Dong, Xu-Yan; Chen, Hong

    2014-12-01

    In this investigation, a rapid and high-throughput method for profiling of TAGs in plant oils by liquid chromatography using a single column coupled with atmospheric pressure chemical ionization (APCI) mass spectrometry was reported. A novel mixed-mode phenyl-hexyl chromatographic column was employed in this separation system. The phenyl-hexyl column could provide hydrophobic interactions as well as π-π interactions. Compared with two traditionally columns used in TAG separation - the C18 column and silver-ion column, this column exhibited much higher selectivity for the separation of TAGs with great efficiency and rapid speed. By comparison with a novel mix-mode column (Ag-HiSep OTS column), which can also provide both hydrophobic interactions as well as π-π interactions for the separation of TAGs, phenyl-hexyl column exhibited excellent stability. LC method using phenyl-hexyl column coupled with APCI-MS was successfully applied for the profiling of TAGs in soybean oils, peanut oils, corn oils, and sesame oils. 29 TAGs in peanut oils, 22 TAGs in soybean oils, 19 TAGs in corn oils, and 19 TAGs in sesame oils were determined and quantified. The LC-MS data was analyzed by barcodes and principal component analysis (PCA). The resulting barcodes constitute a simple tool to display differences between different plant oils. Results of PCA also enabled a clear identification of different plant oils. This method provided an efficient and convenient chromatographic technology for the fast characterization and quantification of complex TAGs in plant oils at high selectivity. It has great potential as a routine analytical method for analysis of edible oil quality and authenticity control.

  6. Quantitative Analysis of Mixed Halogen Dioxins and Furans in Fire Debris Utilizing Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry.

    PubMed

    Organtini, Kari L; Myers, Anne L; Jobst, Karl J; Reiner, Eric J; Ross, Brian; Ladak, Adam; Mullin, Lauren; Stevens, Douglas; Dorman, Frank L

    2015-10-20

    Residential and commercial fires generate a complex mixture of volatile, semivolatile, and nonvolatile compounds. This study focused on the semi/nonvolatile components of fire debris to better understand firefighter exposure risks. Using the enhanced sensitivity of gas chromatography coupled to atmospheric pressure ionization-tandem mass spectrometry (APGC-MS/MS), complex fire debris samples collected from simulation fires were analyzed for the presence of potentially toxic polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs and PBDD/Fs). Extensive method development was performed to create multiple reaction monitoring (MRM) methods for a wide range of PXDD/Fs from dihalogenated through hexa-halogenated homologue groups. Higher halogenated compounds were not observed due to difficulty eluting them off the long column used for analysis. This methodology was able to identify both polyhalogenated (mixed bromo-/chloro- and polybromo-) dibenzo-p-dioxins and dibenzofurans in the simulated burn study samples collected, with the dibenzofuran species being the dominant compounds in the samples. Levels of these compounds were quantified as total homologue groups due to the limitations of commercial congener availability. Concentration ranges in household simulation debris were observed at 0.01-5.32 ppb (PXDFs) and 0.18-82.11 ppb (PBDFs). Concentration ranges in electronics simulation debris were observed at 0.10-175.26 ppb (PXDFs) and 0.33-9254.41 ppb (PBDFs). Samples taken from the particulate matter coating the firefighters' helmets contained some of the highest levels of dibenzofurans, ranging from 4.10 ppb to 2.35 ppm. The data suggest that firefighters and first responders at fire scenes are exposed to a complex mixture of potentially hundreds to thousands of different polyhalogenated dibenzo-p-dioxins and dibenzofurans that could negatively impact their health.

  7. High performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry for sensitive determination of bioactive amines in donkey milk.

    PubMed

    La Torre, Giovanna Loredana; Saitta, Marcello; Giorgia Potortì, Angela; Di Bella, Giuseppa; Dugo, Giacomo

    2010-08-06

    In the present study we report on the optimization and validation of a sensitive high performance liquid chromatography atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS) method for the determination of 8 bioactive amines (histamine, tyramine, tryptamine, 2-phenylethylamine, cadaverine, putrescine, spermidine and spermine) in donkey milk samples. The method involves donkey milk pre-treatment to remove proteins and pre-column dansylation of the amines. HPLC in reversed phase mode has been used for bioactive amines separation and the operating condition of the APCI-MS system proved to be powerful and very efficient for peak assignment. The separation was accomplished in a short time with an excellent resolution for all the amine peaks. Quantification was carried out by monitoring the characteristic [M+H](+) ion of each amine derivative. The method sensitivity, linearity and repeatability were assayed with satisfactory results. The detection limits of the analysed amines ranged from 0.5 microg L(-1) to 15 microg L(-1); the highest LOD was for spermine. Also remarkably good recovery values were obtained; at the lowest spiking level (1 microg L(-1)) the percent mean recoveries ranged from 77.7 to 109.7. Furthermore, as the investigations relate to a complex matrix as donkey milk, suitable studies on matrix effect were performed. Finally, the developed and validated method was applied to analyse 13 donkey milk samples. Among the identified bioactive amines, putrescine, spermine and spermidine proved to be the main amines in donkey milk. Their concentration levels in the present study were lower than the values determined in mature human, cow and sow milk.

  8. Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

    PubMed Central

    Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M.

    2008-01-01

    We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

  9. Characterization of the atmospheric pressure ionization mass spectrometric process obtained using a fused-silica emitter with the high voltage applied upstream

    PubMed

    Sjoberg; Nyholm; Markides

    2000-03-01

    The atmospheric pressure ionization process obtained when a mixture of methanol and water (90:10, v/v) also containing 50 microM sodium hydroxide is dispersed from a fused-silica emitter was studied. A combination of a high electric field and a nebulizer gas with the high voltage applied upstream in the liquid flow was utilized to facilitate the spray process. By comparing the dependences of the spray current and ion signals on the spray potential, it was found that electrical corona discharges were obtained for potentials higher than about 2.6 kV, which resulted in a mixed electrospray and chemical ionization process. By introducing vapour from a solvent, such as benzene or toluene, with a low ionization energy into the nebulizing gas, it was found that the appearance of the corresponding molecular ion was correlated with a change in the slope of the spray current-potential curve. This indicates that the breakpoints in the spray current-potential curves observed were correlated with the onsets of corona discharges. It was shown that the mixed ionization process gives rise to increased amounts of protonated solvent molecules and assists in the formation of sodiated adduct ions from an uncharged fatty acid methyl ester.

  10. Comparing Laser Desorption Ionization and Atmospheric Pressure Photoionization Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry To Characterize Shale Oils at the Molecular Level

    USGS Publications Warehouse

    Cho, Yunjo; Jin, Jang Mi; Witt, Matthias; Birdwell, Justin E.; Na, Jeong-Geol; Roh, Nam-Sun; Kim, Sunghwan

    2013-01-01

    Laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to analyze shale oils. Previous work showed that LDI is a sensitive ionization technique for assessing aromatic nitrogen compounds, and oils generated from Green River Formation oil shales are well-documented as being rich in nitrogen. The data presented here demonstrate that LDI is effective in ionizing high-double-bond-equivalent (DBE) compounds and, therefore, is a suitable method for characterizing compounds with condensed structures. Additionally, LDI generates radical cations and protonated ions concurrently, the distribution of which depends upon the molecular structures and elemental compositions, and the basicity of compounds is closely related to the generation of protonated ions. This study demonstrates that LDI FT-ICR MS is an effective ionization technique for use in the study of shale oils at the molecular level. To the best of our knowledge, this is the first time that LDI FT-ICR MS has been applied to shale oils.

  11. Laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry applied for the ultra-fast quantitative analysis of BKM120 in human plasma.

    PubMed

    Lanshoeft, Christian; Heudi, Olivier; Leuthold, Luc Alexis; Schlotterbeck, Götz; Elbast, Walid; Picard, Franck; Kretz, Olivier

    2014-09-01

    A sensitive and ultra-fast method utilizing the laser diode thermal desorption ion source using atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS) was developed for the quantitative analysis of BKM120, an investigational anticancer drug in human plasma. Samples originating from protein precipitation (PP) followed by salting-out assisted liquid-liquid extraction (SALLE) were spotted onto the LazWell™ plate prior to their thermal desorption and detection by tandem mass spectrometry in positive mode. The validated method described in this paper presents a high absolute extraction recovery (>90 %) for BKM120 and its internal standard (ISTD) [D8]BKM120, with precision and accuracy meeting the acceptance criteria. Standard curves were linear over the range of 5.00 to 2000 ng mL(-1) with a coefficient of determination (R (2)) >0.995. The method specificity was demonstrated in six different batches of human plasma. Intra- and inter-run precision as well as accuracy within ±20 % at the lower limit of quantification (LLOQ) and ±15 % (other levels) were achieved during a three-run validation for quality control (QC) samples. The post-preparative stability on the LazWell™ plate at room temperature was 72 h and a 200-fold dilution of spiked samples was demonstrated. The method was applied successfully to three clinical studies (n = 847) and cross-checked with the validated LC-ESI-MS/MS reference method. The sample analysis run time was 10 s as compared to 4.5 min for the current validated LC-ESI-MS/MS method. The resultant data were in agreement with the results obtained using the validated reference LC-ESI-MS/MS assay and the same pharmacokinetic (PK) parameters were calculated for both analytical assays. This work demonstrates that LDTD-APCI-MS/MS is a reliable method for the ultra-fast quantitative analysis of BKM120 which can be used to speed-up and support its bioanalysis in the frame of the clinical trials.

  12. Determination of benzoylurea insecticide residues in tomatoes by high-performance liquid chromatography with ultraviolet-diode array and atmospheric pressure chemical ionization-mass spectrometry detection.

    PubMed

    Markoglou, Anastasios N; Bempelou, Eleftheria D; Liapis, Konstantinos S; Ziogas, Basil N

    2007-01-01

    A simple and sensitive method using high-performance liquid chromatography/ mass spectrometry (LC/MS) was developed and validated for simultaneous determination of 5 benzoylurea insecticides-diflubenzuron, triflumuron, teflubenzuron, lufenuron, and flufenoxuron-in tomatoes. Residues were successfully separated on a C18 column by methanol-water isocratic elution. Detection was carried out by an ultraviolet diode array detector (UV-DAD) coupled with a quadrupole mass spectrometer, using atmospheric pressure chemical ionization (APCI) in negative-ion mode. The main ions were the deprotonated molecules [M-H]- for triflumuron, and the anions formed by elimination of hydrofluoric acid [M-H-HF]- for diflubenzuron and flufenoxuron, and [M-2H-HF] for lufenuron and teflubenzuron. The calibration plots were linear for both detectors over the range 0.05 to 10 microg/mL, and the method presented good quality parameters. The limits of detection for standard solutions were 0.008-0.01 mg/L (equivalent to 0.08-0.1 ng injected) for both detectors, and the limits of quantification (LOQs) were approximately 10 times lower than national maximum residue levels (MRLs). Depending on the compound and the detector, the LOQ values ranged from 0.2 to 0.4 ng injected. The optimum LC-UV-DAD/APCI-MS conditions were applied to the analysis of benzoylureas in tomatoes. The obtained recoveries from fortified tomato samples (50 g), extracted with ethyl acetate and purified by solid-phase extraction on silica sorbent, were 88-100 and 92.9-105% for the UV-DAD and MS detectors, respectively, with precision values (relative standard deviations) of 2.9-11 and 3.7-14%, respectively. The method was applied to 12 tomato samples from local markets, and diflubenzuron and lufenuron were detected in only one sample at concentrations lower than the MRLs. The results indicate that the developed LC/MS method is accurate, precise, and sensitive for quantitative and qualitative analysis at low levels of benzoylureas

  13. Online profiling of triacylglycerols in plant oils by two-dimensional liquid chromatography using a single column coupled with atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Wei, Fang; Ji, Shu-Xian; Hu, Na; Lv, Xin; Dong, Xu-Yan; Feng, Yu-Qi; Chen, Hong

    2013-10-18

    The complexity of natural triacylglycerols (TAGs) in various edible oils is high because of the hundreds of TAG compositions, which makes the profiling of TAGs quite difficult. In this investigation, a rapid and high-throughput method for online profiling of TAGs in plant oils by two-dimensional (2D) liquid chromatography using a single column coupled with atmospheric pressure chemical ionization (APCI) mass spectrometry was reported. A novel mixed-mode 2D chromatographic column packed with silver-ion-modified octyl and sulfonic co-bonded silica was employed in this online 2D separation system. This novel 2D column combined the features of C8 column and silver-ion. In comparison with the traditional C18 column and silver-ion column, which are the two main columns used for the separation of complex TAGs in natural oil samples, this novel 2D column, could provide hydrophobic interactions as well as π-complexation interactions. It exhibited much higher selectivity for the separation of TAGs, and the separation was rapid. This online 2D separation system was successful in the separation of a large number of TAG solutes, and the TAG structures were evaluated by analyzing their APCI mass spectra information. This system was applied for the profiling of TAGs in peanut oils, corn oils, and soybean oils. 30 TAGs in peanut oils, 18 TAGs in corn oils, and 21 TAGs in soybean oils were determined and quantified. The highest relative content of TAGs was LLL, which was found in corn oil with the relative content up to 45.43 (%, w/w), and the lowest relative content of TAGs was LLS and OSS, which was found in soybean oil and corn oil respectively, with the relative content only 0.01 (%, w/w). In addition, the TAG data were analyzed by principal component analysis (PCA). Results of PCA enabled a clear identification of different plant oils. This method provided an efficient and convenient chromatographic technology for the fast characterization and quantification of complex TAGs

  14. A mechanism for ionization of nonvolatile compounds in mass spectrometry: considerations from MALDI and inlet ionization.

    PubMed

    Trimpin, Sarah; Wang, Beixi; Inutan, Ellen D; Li, Jing; Lietz, Christopher B; Harron, Andrew; Pagnotti, Vincent S; Sardelis, Diana; McEwen, Charles N

    2012-10-01

    Mechanistic arguments relative to matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) address observations that predominately singly charged ions are detected. However, recently a matrix assisted laser ablation method, laserspray ionization (LSI), was introduced that can use the same sample preparation and laser as MALDI, but produce highly charged ions from proteins. In MALDI, ions are generated from neutral molecules by the photon energy provided to a matrix, while in LSI ions are produced inside a heated inlet tube linking atmospheric pressure and the first vacuum region of the mass spectrometer. Some LSI matrices also produce highly charged ions with MALDI ion sources operated at intermediate pressure or high vacuum. The operational similarity of LSI to MALDI, and the large difference in charge states observed by these methods, provides information of fundamental importance to proposed ionization mechanisms for LSI and MALDI. Here, we present data suggesting that the prompt and delayed ionization reported for vacuum MALDI are both fast processes relative to producing highly charged ions by LSI. The energy supplied to produce these charged clusters/droplets as well as their size and time available for desolvation are determining factors in the charge states of the ions observed. Further, charged droplets/clusters may be a common link for ionization of nonvolatile compounds by a variety of MS ionization methods, including MALDI and LSI.

  15. Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS).

    PubMed

    Benigni, Paolo; DeBord, J Daniel; Thompson, Christopher J; Gardinali, Piero; Fernandez-Lima, Francisco

    2016-01-21

    Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100-450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation.

  16. Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

    2017-02-01

    A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed.

  17. Non-polar lipids characterization of Quinoa (Chenopodium quinoa) seed by comprehensive two-dimensional gas chromatography with flame ionization/mass spectrometry detection and non-aqueous reversed-phase liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection.

    PubMed

    Fanali, Chiara; Beccaria, Marco; Salivo, Simona; Tranchida, Peter; Tripodo, Giusy; Farnetti, Sara; Dugo, Laura; Dugo, Paola; Mondello, Luigi

    2015-07-08

    A chemical characterization of major lipid components, namely, triacylglycerols, fatty acids and the unsaponifiable fraction, in a Quinoa seed lipids sample is reported. To tackle such a task, non-aqueous reversed-phase high-performance liquid chromatography with mass spectrometry detection was employed. The latter was interfaced with atmospheric pressure chemical ionization for the analysis of triacylglycerols. The main triacylglycerols (>10%) were represented by OLP, OOL and OLL (P = palmitoyl, O = oleoyl, L = linoleoyl); the latter was present in the oil sample at the highest percentage (18.1%). Furthermore, fatty acid methyl esters were evaluated by gas chromatography with flame ionization detection. 89% of the total fatty acids was represented by unsaturated fatty acid methyl esters with the greatest percentage represented by linoleic and oleic acids accounting for approximately 48 and 28%, respectively. An extensive characterization of the unsaponifiable fraction of Quinoa seed lipids was performed for the first time, by using comprehensive two-dimensional gas chromatography with dual mass spectrometry/flame ionization detection. Overall, 66 compounds of the unsaponifiable fraction were tentatively identified, many constituents of which (particularly sterols) were confirmed by using gas chromatography with high-resolution time-of-flight mass spectrometry.

  18. Capillary electrophoresis electrospray ionization mass spectrometry interface

    DOEpatents

    Smith, Richard D.; Severs, Joanne C.

    1999-01-01

    The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an anolyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

  19. The ionization mechanisms in direct and dopant-assisted atmospheric pressure photoionization and atmospheric pressure laser ionization.

    PubMed

    Kauppila, Tiina J; Kersten, Hendrik; Benter, Thorsten

    2014-11-01

    A novel, gas-tight API interface for gas chromatography-mass spectrometry was used to study the ionization mechanism in direct and dopant-assisted atmospheric pressure photoionization (APPI) and atmospheric pressure laser ionization (APLI). Eight analytes (ethylbenzene, bromobenzene, naphthalene, anthracene, benzaldehyde, pyridine, quinolone, and acridine) with varying ionization energies (IEs) and proton affinities (PAs), and four common APPI dopants (toluene, acetone, anisole, and chlorobenzene) were chosen. All the studied compounds were ionized by direct APPI, forming mainly molecular ions. Addition of dopants suppressed the signal of the analytes with IEs above the IE of the dopant. For compounds with suitable IEs or Pas, the dopants increased the ionization efficiency as the analytes could be ionized through dopant-mediated gas-phase reactions, such as charge exchange, proton transfer, and other rather unexpected reactions, such as formation of [M + 77](+) in the presence of chlorobenzene. Experiments with deuterated toluene as the dopant verified that in case of proton transfer, the proton originated from the dopant instead of proton-bound solvent clusters, as in conventional open or non-tight APPI sources. In direct APLI using a 266 nm laser, a narrower range of compounds was ionized than in direct APPI, because of exceedingly high IEs or unfavorable two-photon absorption cross-sections. Introduction of dopants in the APLI system changed the ionization mechanism to similar dopant-mediated gas-phase reactions with the dopant as in APPI, which produced mainly ions of the same form as in APPI, and ionized a wider range of analytes than direct APLI.

  20. Advanced Quantification of Plutonium Ionization Potential to Support Nuclear Forensic Evaluations by Resonance Ionization Mass Spectrometry

    DTIC Science & Technology

    2015-06-01

    QUANTIFICATION OF PLUTONIUM IONIZATION POTENTIAL TO SUPPORT NUCLEAR FORENSIC EVALUATIONS BY RESONANCE IONIZATION MASS SPECTROMETRY by Craig T...PLUTONIUM IONIZATION POTENTIAL TO SUPPORT NUCLEAR FORENSIC EVALUATIONS BY RESONANCE IONIZATION MASS SPECTROMETRY 5. FUNDING NUMBERS 6. AUTHOR(S...mass spectrometry (RIMS) to problems related to nuclear forensics and, in particular, to the analysis and quantification of the debris from nuclear

  1. Liquid chromatography-atmospheric pressure laser ionization-mass spectrometry (LC-APLI-MS) analysis of polycyclic aromatic hydrocarbons with 6-8 rings in the environment.

    PubMed

    Thiäner, Jan B; Achten, Christine

    2017-03-01

    A method has been developed for the sensitive and rapid analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples using liquid chromatography time-of-flight mass spectrometry as well as the selective atmospheric pressure laser ionization (APLI) process (LC-APLI-MS). Upon analyzing 34 PAHs, the limits of detection of this method were found to range from 0.008 to 1.824 pg (0.024 pg for benzo[a]pyrene). The method therefore provides 30-fold to 5,400-fold increased sensitivity compared with the established GC-MS technique. This LC-APLI-MS method was optimized for higher molecular weight PAHs (C24-C30 PAHs with 6-8 rings), which are difficult to detect or cannot be detected by GC-MS. Using the LC-APLI-MS method, various 6- to 8-ring PAHs were detected in environmental samples for the first time. After developing the method, it was successfully validated in ruggedness tests. The concentrations determined by the LC-APLI-MS method were in good accord with the certified concentrations in three certified reference materials (contaminated soils and sediments). Upon applying the method to environmental samples, it was found that (1) the presence of dibenzo[a,i]pyrene and dibenzo[a,h]pyrene in urban soil samples could only be detected using LC-APLI-MS (i.e., not GC-MS) due to its high sensitivity, (2) a bituminous coal sample yielded 211 tentative peaks from aromatic compounds in the C24-C30 range, and (3) eleven of those compounds occurred in different environmental samples in similar patterns. Hence, 6- to 8-ring PAHs occur in solid environmental samples in which other 6-ring PAHs such as indeno[1,2,3-cd]pyrene or benzo[ghi]perylene may also be present. Some of these numerous higher molecular weight PAH compounds could have very high carcinogenic potential, which will need to be elucidated to ensure the reliability of PAH risk assessments.

  2. Profiling of acylcarnitines and sterols from dried blood or plasma spot by atmospheric pressure thermal desorption chemical ionization (APTDCI) tandem mass spectrometry.

    PubMed

    Corso, Gaetano; D'Apolito, Oceania; Garofalo, Daniela; Paglia, Giuseppe; Dello Russo, Antonio

    2011-11-01

    Free carnitine and acylcarnitines play an important role in the metabolism of fatty acids. Sterols are structural lipids found in the membranes of many eukaryotic cells, and they also have functional roles such as the regulation of membrane permeability and fluidity, activity of membrane-bound enzymes and signals transduction. Abnormal profiles of these compounds in biological fluids may be useful markers of metabolic changes. In this review, we describe the subset of the lipidome represented by acylcarnitines and sterols, and we summarize how these compounds have been analyzed in the past. Over the last 50years, lipid mass spectrometry (MS) has evolved to become one of the most useful techniques for metabolic analysis. Today, the introduction of new ambient ionization techniques coupled to MS (AMS), which are characterized by the direct desorbing/ionizing of molecules from solid samples, is generating new possibilities for in situ analysis. Recently, we developed an AMS approach called APTDCI to desorb/ionize using a heated gas flow and an electrical discharge to directly analyze sterols and indirectly investigate acylcarnitines in dried blood or plasma spot samples. Here, we also describe the APTDCI method and some of its clinical applications, and we underline the common complications and issues that remain to be resolved. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Comparison of Atmospheric Pressure Ionization Gas Chromatography-Triple Quadrupole Mass Spectrometry to Traditional High-Resolution Mass Spectrometry for the Identification and Quantification of Halogenated Dioxins and Furans.

    PubMed

    Organtini, Kari L; Haimovici, Liad; Jobst, Karl J; Reiner, Eric J; Ladak, Adam; Stevens, Douglas; Cochran, Jack W; Dorman, Frank L

    2015-08-04

    The goal of this study was to qualify gas chromatography coupled to atmospheric pressure ionization tandem mass spectrometry (APGC-MS/MS) as a reliable and valid technique for analysis of halogenated dioxins and furans that could be used in place of more traditional gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS) analysis. A direct comparison of the two instrumental techniques was performed. APGC-MS/MS system sensitivity was demonstrated to be on the single femtogram level. The APGC-MS/MS analysis also demonstrated method detection limits (MDLs) in both sediment and fish that were 2-18 times lower than those determined for the GC-HRMS. Inlet conditions were established to prevent issues with sample carry-over, due largely to the enhanced sensitivity of this technique. Additionally, this work utilized direct injection for sample introduction through the split/splittless inlet. Finally, quantification of both sediment and fish certified reference materials were directly compared between the APGC-MS/MS and GC-HRMS. The APGC-MS/MS performed similarly to, if not better than, the GC-HRMS instrument in the analysis of these samples. This data is intended to substantiate APGC-MS/MS as a comparable technique to GC-HRMS for the analysis of dioxins and furans.

  4. Multifunctional Carbon Fiber Ionization Mass Spectrometry.

    PubMed

    Wu, Meng-Xi; Wang, Hao-Yang; Zhang, Jun-Ting; Guo, Yin-Long

    2016-10-04

    A carbon fiber ionization (CFI) technique was developed for the mass spectrometric analysis of various organic compounds with different polarities. The design of the CFI technique was based on the good compatibility and dispersion of samples and solutions in different solvents on carbon fiber. As a fast, convenient, and versatile ionization method, CFI-MS is especially efficient for analyzing many low/nonpolar organic compounds, such as polycyclic aromatic hydrocarbons, long-chain aliphatic aldehydes, sensitive steroids, terpenoids, and organometallic compounds. Some of these compounds may not be well-analyzed by electrospray ionization or electron ionization mass spectrometry. On the basis of our experimental results, the major ion formation mechanism of CFI-MS was suggested to involve desorption in a steam-distillation-like process, and then, ionization occurred mainly via corona discharge under high voltage. CFI-MS could not only work alone but also be coupled with separation techniques. It works well when coupled with supercritical fluid chromatography (SFC) as well as in the analysis of exhaled human air. The high flexibility and versatility of CFI-MS has extended its applications in many areas, such as fast chemical screening, clinical testing, and forensic analysis.

  5. Comparison of electrospray ionization and atmospheric pressure photoionization liquid chromatography mass spectrometry methods for analysis of ergot alkaloids from endophyte-infected sleepygrass (Achnatherum robustum).

    PubMed

    Jarmusch, Alan K; Musso, Ashleigh M; Shymanovich, Tatsiana; Jarmusch, Scott A; Weavil, Miranda J; Lovin, Mary E; Ehrmann, Brandie M; Saari, Susanna; Nichols, David E; Faeth, Stanley H; Cech, Nadja B

    2016-01-05

    Ergot alkaloids are mycotoxins with an array of biological effects. With this study, we investigated for the first time the application of atmospheric pressure photoionization (APPI) as an ionization method for LC-MS analysis of ergot alkaloids, and compared its performance to that of the more established technique of electrospray ionization (ESI). Samples of the grass Achnatherum robustum infected with the ergot producing Epichloë fungus were extracted using cold methanol and subjected to reserved-phase HPLC-ESI-MS and HPLC-APPI-MS analysis. The ergot alkaloids ergonovine and lysergic acid amide were detected in these samples, and quantified via external calibration. Validation parameters were recorded in accordance with ICH guidelines. A triple quadrupole MS operated in multiple reaction monitoring yielded the lowest detection limits. The performance of APPI and ESI methods was comparable. Both methods were subject to very little matrix interference, with percent recoveries ranging from 82% to 100%. As determined with HPLC-APPI-MS quantification, lysergic acid amide and ergonovine were extracted from an A. robustum sample infected with the Epichloë fungus at concentrations of 1.143±0.051 ppm and 0.2822±0.0071 ppm, respectively. There was no statistically significant difference between these concentrations and those determined using ESI for the same samples.

  6. Preparative mass-spectrometry profiling of bioactive metabolites in Saudi-Arabian propolis fractionated by high-speed countercurrent chromatography and off-line atmospheric pressure chemical ionization mass-spectrometry injection.

    PubMed

    Jerz, Gerold; Elnakady, Yasser A; Braun, André; Jäckel, Kristin; Sasse, Florenz; Al Ghamdi, Ahmad A; Omar, Mohamed O M; Winterhalter, Peter

    2014-06-20

    Propolis is a glue material collected by honeybees which is used to seal cracks in beehives and to protect the bee population from infections. Propolis resins have a long history in medicinal use as a natural remedy. The multiple biological properties are related to variations in their chemical compositions. Geographical settings and availability of plant sources are important factors for the occurrence of specific natural products in propolis. A propolis ethylacetate extract (800mg) from Saudi Arabia (Al-Baha region) was separated by preparative scale high-speed countercurrent chromatography (HSCCC) using a non-aqueous solvent system n-hexane-ACN (1:1, v/v). For multiple metabolite detection, the resulting HSCCC-fractions were sequentially injected off-line into an atmospheric pressure chemical ionization mass-spectrometry (APCI-MS/MS) device, and a reconstituted mass spectrometry profile of the preparative run was visualized by selected ion traces. Best ion-intensities for detected compounds were obtained in the negative APCI mode and monitored occurring co-elution effects. HSCCC and successive purification steps resulted in the isolation and characterization of various bioactive natural products such as (12E)- and (12Z)-communic acid, sandaracopimaric acid, (+)-ferruginol, (+)-totarol, and 3β-acetoxy-19(29)-taraxasten-20a-ol using EI-, APCI-MS and 1D/2D-NMR. Cycloartenol-derivatives and triterpene acetates were isolated in mixtures and elucidated by EI-MS and 1D-NMR. Free fatty acids, and two labdane fatty acid esters were identified by APCI-MS/MS. In total 19 metabolites have been identified. The novel combination of HSCCC fractionation, and APCI-MS-target-guided molecular mass profiling improve efficiency of lead-structure identification.

  7. Technical note: Detection of dimethylamine in the low pptv range using nitrate Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry

    NASA Astrophysics Data System (ADS)

    Simon, M.; Heinritzi, M.; Herzog, S.; Leiminger, M.; Bianchi, F.; Praplan, A.; Dommen, J.; Curtius, J.; Kürten, A.

    2015-12-01

    Amines are potentially important for atmospheric new particle formation and therefore the demand for highly sensitive gas phase amine measurements has emerged in the last several years. Nitrate Chemical Ionization Mass Spectrometry (CIMS) is routinely used for the measurement of gas phase-sulfuric acid in the sub-pptv range. Furthermore, Extremely Low Volatile Organic Compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine ((CH3)2NH, DMA) using the NO3-(HNO3)1-2(DMA) cluster ion signals. This observation was made at the CLOUD aerosol chamber, which was also used for calibration measurements. Good linearity between 0 and ~120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

  8. Determination of azolic fungicides in wine by solid-phase extraction and high-performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Nozal, Maria J; Bernal, J L; Jiménez, J J; Martín, Maria T; Bernal, J

    2005-05-27

    A method for simultaneous analysis of eight azolic fungicides: cyproconazole, diniconazole, tetraconazole, thiabendazole, flusilazole, triadimenol, triadimefon, carbendazim and the degradation product 2-aminobenzimidazole in wine samples is described. The compounds are isolated from the samples and concentrated by solid-phase extraction on polymeric cartridges. The determination is carried out by liquid chromatography with mass spectrometric detection in positive ionization and selected ion monitoring modes. The influence of parameters such as the mobile phase composition, column temperature, corona current and fragmentor voltage is studied and the proposed method is validated. Recoveries of the nine compounds added to wine samples range from 83 to 109%, with relative standard deviations below 10%. The quantitation limits are between 9 and 31 microg/L. Real wine samples are analyzed by the proposed method, also.

  9. The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

    PubMed

    Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail А; Pod'yachev, Sergey P

    2014-06-01

    A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Laser desorption lamp ionization source for ion trap mass spectrometry.

    PubMed

    Wu, Qinghao; Zare, Richard N

    2015-01-01

    A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds. Copyright © 2015 John Wiley & Sons, Ltd.

  11. Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners.

    PubMed

    Portolés, Tania; Sales, Carlos; Gómara, Belén; Sancho, Juan Vicente; Beltrán, Joaquim; Herrero, Laura; González, María José; Hernández, Félix

    2015-10-06

    The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low

  12. Liquid chromatography coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry and post-column addition of metal salt solutions as a powerful tool for the metabolic profiling of Fusarium oxysporum.

    PubMed

    Cirigliano, Adriana M; Rodriguez, M Alejandra; Gagliano, M Laura; Bertinetti, Brenda V; Godeas, Alicia M; Cabrera, Gabriela M

    2016-03-25

    Fusarium oxysporum L11 is a non-pathogenic soil-borne fungal strain that yielded an extract that showed antifungal activity against phytopathogens. In this study, reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry (API-QTOF-MS) was applied for the comprehensive profiling of the metabolites from the extract. The employed sources were electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI). Post-column addition of metal solutions of Ca, Cu and Zn(II) was also tested using ESI. A total of 137 compounds were identified or tentatively identified by matching their accurate mass signals, suggested molecular formulae and MS/MS analysis with previously reported data. Some compounds were isolated and identified by NMR. The extract was rich in cyclic peptides like cyclosporins, diketopiperazines and sansalvamides, most of which were new, and are reported here for the first time. The use of post-column addition of metals resulted in a useful strategy for the discrimination of compound classes since specific adducts were observed for the different compound families. This technique also allowed the screening for compounds with metal binding properties. Thus, the applied methodology is a useful choice for the metabolic profiling of extracts and also for the selection of metabolites with potential biological activities related to interactions with metal ions.

  13. Ionization pattern obtained in electrospray ionization or atmospheric pressure chemical ionization interfaces for authorized antidepressants in Romania

    NASA Astrophysics Data System (ADS)

    Grecu, Iulia; Ionicǎ, Mihai; Vlǎdescu, Marian; Truţǎ, Elena; Sultan, Carmen; Viscol, Oana; Horhotǎ, Luminiţa; Radu, Simona

    2016-12-01

    Antidepressants were found in 1950. In the 1990s there was a new generation of antidepressants. They act on the level of certain neurotransmitters extrasinpatic by its growth. After their mode of action antidepressants may be: SSRIs (Selective Serotonin Reuptake Inhibitors); (Serotonin-Norepinephrine Reuptake Inhibitors); SARIs (Serotonin Antagonist Reuptake Inhibitors); NRIs (Norepinephrine Reuptake Inhibitors); NDRIs (Norepinephrine-Dopamine Reuptake Inhibitors) NDRAs (Norepinephrine-Dopamine Releasing Agents); TCAs (Tricyclic Antidepressants); TeCAs (Tetracyclic Antidepressants); MAOIs (Monoamine Oxidase Inhibitors); agonist receptor 5-HT1A (5- hydroxytryptamine); antagonist receptor 5-HT2; SSREs (Selective Serotonin Reuptake Enhancers) and Sigma agonist receptor. To determine the presence of antidepressants in biological products, it has been used a system HPLC-MS (High Performance Liquid Chromatography - Mass Spectrometry) Varian 12001. The system is equipped with APCI (Atmospheric Pressure Chemical Ionization) or ESI (ElectroSpray Ionization) interface. To find antidepressants in unknown samples is necessary to recognize them after mass spectrum. Because the mass spectrum it is dependent on obtaining private parameters work of HPLC-MS system, and control interfaces, the mass spectra library was filled with the mass spectra of all approved antidepressants in Romania. The paper shows the mass spectra obtained in the HPLCMS system.

  14. Infrared laser-assisted desorption electrospray ionization mass spectrometry.

    PubMed

    Rezenom, Yohannes H; Dong, Jianan; Murray, Kermit K

    2008-02-01

    We have used an infrared laser for desorption of material and ionization by interaction with electrosprayed solvent. Infrared laser-assisted desorption electrospray ionization (IR LADESI) mass spectrometry was used for the direct analysis of water-containing samples under ambient conditions. An ion trap mass spectrometer was modified to include a pulsed Er:YAG laser at 2.94 microm wavelength coupled into a germanium oxide optical fiber for desorption at atmospheric pressure and a nanoelectrospray source for ionization. Analytes in aqueous solution were placed on a stainless steel target and irradiated with the pulsed IR laser. Material desorbed and ablated from the target was ionized by a continuous stream of charged droplets from the electrosprayed solvent. Peptide and protein samples analyzed using this method yield mass spectra similar to those obtained by conventional electrospray. Blood and urine were analyzed without sample pretreatment to demonstrate the capability of IR LADESI for direct analysis of biological fluids. Pharmaceutical products were also directly analyzed. Finally, the role of water as a matrix in the IR LADESI process is discussed.

  15. Picosecond ionization dynamics in femtosecond filaments at high pressures

    NASA Astrophysics Data System (ADS)

    Gao, Xiaohui; Patwardhan, Gauri; Schrauth, Samuel; Zhu, Daiwei; Popmintchev, Tenio; Kapteyn, Henry C.; Murnane, Margaret M.; Romanov, Dmitri A.; Levis, Robert J.; Gaeta, Alexander L.

    2017-01-01

    We investigate the plasma dynamics inside a femtosecond-pulse-induced filament generated in an argon gas for a wide range of pressures up to 60 bar. At higher pressures, we observe ionization immediately following a pulse, with up to a threefold increase in the electron density within 30 ps after the filamentary propagation of a femtosecond pulse. Our study suggests that this picosecond evolution can be attributed to collisional ionization including Penning and associative ionizations and electron-impact ionization of excited atoms generated during the pulse. The dominance of excited atoms over ionized atoms at the end of the pulse also indicates an intrapulse inhibition of avalanche ionization. This delayed ionization dynamics provides evidence for diagnosing atomic and molecular excitation and ionization in intense laser interaction with high-pressure gases.

  16. On-chip solid-phase extraction pre-concentration/focusing substrates coupled to atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry for high sensitivity biomolecule analysis.

    PubMed

    Navare, Arti; Nouzova, Marcela; Noriega, Fernando G; Hernández-Martínez, Salvador; Menzel, Christoph; Fernández, Facundo M

    2009-02-01

    Atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) has proven a convenient and rapid method for ion production in the mass spectrometric (MS) analysis of biomolecules. AP-MALDI and electrospray ionization (ESI) sources are easily interchangeable in most mass spectrometers. However, AP-MALDI suffers from less-than-optimal sensitivity due to ion losses during transport from the atmosphere into the vacuum of the mass spectrometer. Here, we study the signal-to-noise ratio (S/N) gains observed when an on-chip dynamic pre-concentration/focusing approach is coupled to AP-MALDI for the MS analysis of neuropeptides and protein digests. It was found that, in comparison with conventional AP-MALDI targets, focusing targets showed (1) a sensitivity enhancement of approximately two orders of magnitude with S/N gains of 200-900 for hydrophobic substrates, and 150-400 for weak cation-exchange (WCX) substrates; (2) improved detection limits as low as 5 fmol/microL for standard peptides; (3) significantly reduced matrix background; and (4) higher inter-day reproducibility. The improved sensitivity allowed successful tandem mass spectrometric (MS/MS) sequencing of dilute solutions of a derivatized tryptic digest of a protein standard, and enabled the first reported AP-MALDI MS detection of neuropeptides from Aedes aegypti mosquito heads.

  17. Detection of dimethylamine in the low pptv range using nitrate chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

    NASA Astrophysics Data System (ADS)

    Simon, Mario; Heinritzi, Martin; Herzog, Stephan; Leiminger, Markus; Bianchi, Federico; Praplan, Arnaud; Dommen, Josef; Curtius, Joachim; Kürten, Andreas

    2016-05-01

    Amines are potentially important for atmospheric new particle formation, but their concentrations are usually low with typical mixing ratios in the pptv range or even smaller. Therefore, the demand for highly sensitive gas-phase amine measurements has emerged in the last several years. Nitrate chemical ionization mass spectrometry (CIMS) is routinely used for the measurement of gas-phase sulfuric acid in the sub-pptv range. Furthermore, extremely low volatile organic compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine (DMA, (CH3)2NH) using the NO3-•(HNO3)1 - 2• (DMA) cluster ion signal. Calibration measurements were made at the CLOUD chamber during two different measurement campaigns. Good linearity between 0 and ˜ 120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

  18. Transmission geometry laserspray ionization vacuum using an atmospheric pressure inlet.

    PubMed

    Lutomski, Corinne A; El-Baba, Tarick J; Inutan, Ellen D; Manly, Cory D; Wager-Miller, James; Mackie, Ken; Trimpin, Sarah

    2014-07-01

    This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples.

  19. LASER DESORPTION IONIZATION MASS SPECTROMETRY ON SILICON NANOWELL ARRAYS

    PubMed Central

    Gulbakan, Basri; Park, Dooho; Kang, Myungchan; Kececi, Kaan; Martin, Charles R.; Powell, David H.; Tan, Weihong

    2010-01-01

    This paper describes a new technique for fabrication of nanostructured porous silicon (pSi) for laser desorption ionization mass spectrometry. Porous silicon nanowell arrays were prepared by argon plasma etching through an alumina mask. Porous silicon prepared in this way proved to be an excellent substrate for desorption/ionization on silicon (DIOS) mass spectrometry (MS) using adenosine, Pro-Leu-Gly tripeptide and [Des-Arg9]-bradykinin as the model compounds. It also allows the analyses of complex biological samples such as a tryptic digest of bovine serum albumin, and a carnitine standard mixture. Nanowell array surfaces were also used for direct quantification of the illicit drug fentanyl in red blood cell extracts. This method also allows full control of the surface features. MS results suggested that the pore depth has significant effect on the ion signals. Significant improvement in the ionization was observed by increasing the pore depth from 10 nm to 50 nm. These substrates are useful for laser desorption ionization in both the atmospheric pressure and vacuum regimes. PMID:20731384

  20. Laser desorption ionization mass spectrometry on silicon nanowell arrays.

    PubMed

    Gulbakan, Basri; Park, Dooho; Kang, Myungchan; Kececi, Kaan; Martin, Charles R; Powell, David H; Tan, Weihong

    2010-09-15

    This paper describes a new technique for fabrication of nanostructured porous silicon (pSi) for laser desorption ionization mass spectrometry. Porous silicon nanowell arrays were prepared by argon plasma etching through an alumina mask. Porous silicon prepared in this way proved to be an excellent substrate for desorption/ionization on silicon (DIOS) mass spectrometry (MS) using adenosine, Pro-Leu-Gly tripeptide, and [Des-Arg(9)]-bradykinin as the model compounds. It also allows the analyses of complex biological samples such as a tryptic digest of bovine serum albumin and a carnitine standard mixture. Nanowell array surfaces were also used for direct quantification of the illicit drug fentanyl in red blood cell extracts. This method also allows full control of the surface features. MS results suggested that the pore depth has a significant effect on the ion signals. Significant improvement in the ionization was observed by increasing the pore depth from 10 to 50 nm. These substrates are useful for laser desorption ionization in both the atmospheric pressure and vacuum regimes.

  1. Oxidative Ionization Under Certain Negative-Ion Mass Spectrometric Conditions

    NASA Astrophysics Data System (ADS)

    Hassan, Isra; Pavlov, Julius; Errabelli, Ramu; Attygalle, Athula B.

    2017-02-01

    1,4-Hydroquinone and several other phenolic compounds generate (M - 2) -• radical-anions, rather than deprotonated molecules, under certain negative-ion mass spectrometric conditions. In fact, spectra generated under helium-plasma ionization (HePI) conditions from 1,4-hydroquinone and 1,4-benzoquinone (by electron capture) were practically indistinguishable. Because this process involves a net loss of H• and H+, it can be termed oxidative ionization. The superoxide radical-anion (O2 -•), known to be present in many atmospheric-pressure plasma ion sources operated in the negative mode, plays a critical role in the oxidative ionization process. The presence of a small peak at m/z 142 in the spectrum of 1,4-hydroquinone, but not in that of 1,4-benzoquinone, indicated that the initial step in the oxidative ionization process is the formation of an O2 -• adduct. On the other hand, under bona fide electrospray ionization (ESI) conditions, 1,4-hydroquinone generates predominantly an (M - 1) - ion. It is known that at sufficiently high capillary voltages, corona discharges begin to occur even in an ESI source. At lower ESI capillary voltages, deprotonation predominates; as the capillary voltage is raised, the abundance of O2 -• present in the plasma increases, and the source in turn increasingly behaves as a composite ESI/APCI source. While maintaining post-ionization ion activation to a minimum (to prevent fragmentation), and monitoring the relative intensities of the m/z 109 (due to deprotonation) and 108 (oxidative ionization) peaks recorded from 1,4-hydroquinone, a semiquantitative estimation of the APCI contribution to the overall ion-generation process can be obtained.

  2. Oxidative Ionization Under Certain Negative-Ion Mass Spectrometric Conditions.

    PubMed

    Hassan, Isra; Pavlov, Julius; Errabelli, Ramu; Attygalle, Athula B

    2017-02-01

    1,4-Hydroquinone and several other phenolic compounds generate (M - 2) (-•) radical-anions, rather than deprotonated molecules, under certain negative-ion mass spectrometric conditions. In fact, spectra generated under helium-plasma ionization (HePI) conditions from 1,4-hydroquinone and 1,4-benzoquinone (by electron capture) were practically indistinguishable. Because this process involves a net loss of H(•) and H(+), it can be termed oxidative ionization. The superoxide radical-anion (O2(-•)), known to be present in many atmospheric-pressure plasma ion sources operated in the negative mode, plays a critical role in the oxidative ionization process. The presence of a small peak at m/z 142 in the spectrum of 1,4-hydroquinone, but not in that of 1,4-benzoquinone, indicated that the initial step in the oxidative ionization process is the formation of an O2(-•) adduct. On the other hand, under bona fide electrospray ionization (ESI) conditions, 1,4-hydroquinone generates predominantly an (M - 1) (-) ion. It is known that at sufficiently high capillary voltages, corona discharges begin to occur even in an ESI source. At lower ESI capillary voltages, deprotonation predominates; as the capillary voltage is raised, the abundance of O2(-•) present in the plasma increases, and the source in turn increasingly behaves as a composite ESI/APCI source. While maintaining post-ionization ion activation to a minimum (to prevent fragmentation), and monitoring the relative intensities of the m/z 109 (due to deprotonation) and 108 (oxidative ionization) peaks recorded from 1,4-hydroquinone, a semiquantitative estimation of the APCI contribution to the overall ion-generation process can be obtained. Graphical Abstract ᅟ.

  3. Ion thermalization using pressure transients in a quadrupole ion trap coupled to a vacuum matrix-assisted laser desorption ionization source and a reflectron time-of-flight mass analyzer.

    PubMed

    Papanastasiou, D; Belgacem, O; Sudakov, M; Raptakis, E

    2008-05-01

    Efficient trapping and detection of intact peptide ions is demonstrated in a quadrupole ion trap (QIT) coupled to an external vacuum matrix-assisted laser desorption ionization (MALDI) source. Deactivation of metastable ions generated by MALDI is achieved in a pressure transient environment inside the QIT established by pulsing gas to access the higher pressures required for fast thermalization, without affecting vacuum conditions in the ion source and time-of-flight (TOF) mass analyzer. Pressure transients are experimentally determined and a threshold of approximately 10 mTorr is identified where internally excited ions, which commonly observed to dissociate upon injection in a QIT, are stabilized. Fragment-free spectra are presented for a set of peptides by using 2,5-dihydroxybenzoic acid (DHB) as a matrix, and significantly reduced fragmentation is observed by using a-cyano-4-hydroxycinnamic acid (CHCA). Intact peptide spectra of a protein tryptic digest are also recorded with CHCA. The process of translational cooling for externally injected ions in a dynamic pressure environment is visualized by using ion trajectory simulations that employ hard sphere collisions. Statistical theory of dynamic equilibrium of ions stored in rf fields is applied to our QIT to characterize a translationally thermalized ion cloud, to explain observed ejection efficiency into the TOF mass analyzer, and to further discuss collisional deactivation of metastable ions.

  4. High-sensitivity detection of polycyclic aromatic hydrocarbons adsorbed onto soot particles using laser desorption/laser ionization/time-of-flight mass spectrometry: An approach to studying the soot inception process in low-pressure flames

    SciTech Connect

    Faccinetto, Alessandro; Desgroux, Pascale; Therssen, Eric; Ziskind, Michael; Focsa, Cristian

    2011-02-15

    Species adsorbed at the surfaces of soot particles sampled at different locations in a low-pressure methane flame have been analyzed. The analysis method is laser desorption/laser ionization/time-of-flight mass spectrometry (LD/LI/TOF-MS) applied to soot particles deposited on a filter after probe extraction in the flame. In order to fully characterize the experimental apparatus, a strategy of systematic investigations has been adopted, beginning with the study of less complex systems constituted by model soot (standard polycyclic aromatic hydrocarbons, PAHs, adsorbed on black carbon), and then natural soot sampled from a literature reference ethylene flame. This characterization allowed a good understanding of the analytical response of PAHs to the desorption and ionization processes and the definition of the optimal experimental conditions. The soot PAH content was then investigated on a low-pressure methane/oxygen/nitrogen premixed flat flame ({phi} = 2.32) as a function of the sampling height above the burner (HAB). The obtained mass spectra are reproducible, fragment-free, well resolved in the analyzed m/z range and they are characterized by an excellent signal-to-noise ratio. They all feature regular peak sequences, where each signal peak has been assigned to the most stable high-temperature-formed PAHs. The structure of the mass spectra depends on the sampling HAB into the flame, i.e., on the reaction time. An original contribution to the data interpretation comes from the development of a new sampling method that makes it possible to infer hypotheses about the PAH partition between the gas phase and the soot particles. This method highlights the presence of high-mass PAHs in the soot nucleation zone, and it suggests the importance of heterogeneous reactions occurring between flame PAHs and soot particles. (author)

  5. Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

    PubMed

    Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

    2016-09-21

    The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices.

  6. Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

    PubMed

    Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

    2014-03-01

    We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

  7. Mass Analyzed Threshold Ionization of Lutetium Dimer

    NASA Astrophysics Data System (ADS)

    Wu, Lu; Roudjane, Mourad; Liu, Yang; Yang, Dong-Sheng

    2013-06-01

    Lu_2 is produced in a pulsed laser-vaporization metal-cluster source and studied by mass-analyzed threshold ionization (MATI) spectroscopy. The MATI spectrum displays several long progressions from the transitions between various vibrational levels of the neutral and ion electronic states. From the spectrum, the upper limit of the ionization energy of the dimer is determined to be 43996 cm^{-1}, and the vibrational frequencies are measured to be 121 cm^{-1} in the neutral state and 90 cm^{-1} in the ion state. By combining with ab initio calculations at CASPT2 level, the ground state of Lu_2 is identified as ^3Σ_g^-. The ^3Σ_g^- state has an electron configuration of 6sσ_g^25dπ_u^15dπ_u^16sσ_u^2, which is formed by the interactions of two Lu atoms in the ^2D(5d6s^2) ground state. Ionization of the neutral state removes a 5dπ_u bonding electron and yields a ion state with a considerably longer bond distance. Lu_2 has a very different bonding feature from La_2, for which a ^1Σ_g^+ ground state was previously identified with an electron configuration of 5dπ_u^46sσ_g^2 formed by the interactions of two La atoms in the ^4F(5d^26s) excited state. Yang Liu, Lu Wu, Chang-Hua Zhang, Serge A. Krasnokutski, and Dong-Sheng Yang, J. Chem. Phys. 135, 034309 (2011).

  8. Analysis of secondary organic aerosol using a Micro-Orifice Volatilization Impactor (MOVI) coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS)

    NASA Astrophysics Data System (ADS)

    Brueggemann, M.; Vogel, A.; Hoffmann, T.

    2012-04-01

    We describe the development and characterization of a Micro-Orifice Volatilization Impactor (MOVI) which is coupled to an ion trap mass spectrometer with atmospheric pressure chemical ionization (APCI-IT/MS), and its application in laboratory and field measurements. The MOVI-APCI-IT/MS allows the quantification of organic acids and other oxidation products of volatile organic compounds (VOCs) in secondary organic aerosols (SOA) on a semi-continuous basis. Furthermore, the vapor pressure and saturation concentration of the particle components can be estimated. The MOVI was first described in 2010 by Yatavelli and Thornton (Yatavelli and Thornton, 2010). It is a single stage, multi-nozzle impactor with 100 nozzles, each having a diameter of 150 μm. At a flow-rate of 10 L·min-1 air is drawn through the MOVI and particles are collected on a deposition plate. The cut-point diameter (d50, diameter of 50% collection efficiency) is at 130 nm. A low pressure-drop of only 5.3% of atmospheric pressure behind the nozzles allows collecting not only low-volatile but even semi-volatile compounds, which are an important part of SOA. After collecting particles hydrocarbon-free synthetic air is led over the collection surface into the APCI-IT/MS and the collection surface is heated up to 120 ° C in less than 200 s, volatilizing the sampled SOA. The vaporized compounds are transferred into the ion source and subsequently analyzed by mass spectrometry. Due to the soft ionization at atmospheric pressure the obtained mass spectra show only low fragmentations and can easily be interpreted. In laboratory experiments the MOVI-APCI-IT/MS was used for the chemical analysis of SOA generated from α-pinene-ozonolysis in a smog chamber. The limit of detection was found at 7.3 ng for pinic acid. The vapor pressure log p0 and the saturation concentration C25* for pinic acid were calculated from the desorption temperature using the method presented by Faulhaber et al. (Faulhaber et al., 2009

  9. Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tian, Hua; Wucher, Andreas; Winograd, Nicholas

    2016-02-01

    Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

  10. Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

    PubMed Central

    Wucher, Andreas; Winograd, Nicholas

    2015-01-01

    Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn+ (n = 1000–10,000) to form a mixed cluster. The ‘tailored beam’ has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl−, allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. Protonation and H–D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1–8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield. PMID:26463238

  11. Miniature quadrupole mass spectrometer having a cold cathode ionization source

    DOEpatents

    Felter, Thomas E.

    2002-01-01

    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.

  12. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer.

    PubMed

    Hoegg, Edward D; Barinaga, Charles J; Hager, George J; Hart, Garret L; Koppenaal, David W; Marcus, R Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs. Graphical Abstract ᅟ.

  13. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    SciTech Connect

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-04-14

    ABSTRACT In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Due to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for orbitrap analyzers are very well documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LSAPGD microplasma and the inherent IR measurement qualities of orbitrap analyzers. Important to the IR performance, the various operating parameters of the orbitrap sampling interface, HCD dissociation stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1 %RSD can be achieved, with values of 1-3 %RSD observed for low-abundance species. The results suggest that the LSAPGD is a very good candidate for field deployable MS analysis and that the high resolving powers of the orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision isotope ratios.

  14. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  15. The thermodynamical instability induced by pressure ionization in fluid helium

    NASA Astrophysics Data System (ADS)

    Li, Qiong; Liu, Hai-Feng; Zhang, Gong-Mu; Zhao, Yan-Hong; Lu, Guo; Tian, Ming-Feng; Song, Hai-Feng

    2016-11-01

    A systematic study of pressure ionization is carried out in the chemical picture by the example of fluid helium. By comparing the variants of the chemical model, it is demonstrated that the behavior of pressure ionization depends on the construction of the free energy function. In the chemical model with the Coulomb free energy described by the Padé interpolation formula, thermodynamical instability induced by pressure ionization is found to be manifested by a discontinuous drop or a continuous fall and rise along the pressure-density curve as well as the pressure-temperature curve, which is very much like the first order liquid-liquid phase transition of fluid hydrogen from the first principles simulations. In contrast, in the variant chemical model with the Coulomb free energy term empirically weakened, no thermodynamical instability is induced when pressure ionization occurs, and the resulting equation of state achieves a good agreement with the first principles simulations of fluid helium.

  16. Mass separation of deuterium and helium with conventional quadrupole mass spectrometer by using varied ionization energy

    SciTech Connect

    Yu, Yaowei; Hu, Jiansheng Wan, Zhao; Wu, Jinhua; Wang, Houyin; Cao, Bin

    2016-03-15

    Deuterium pressure in deuterium-helium mixture gas is successfully measured by a common quadrupole mass spectrometer (model: RGA200) with a resolution of ∼0.5 atomic mass unit (AMU), by using varied ionization energy together with new developed software and dedicated calibration for RGA200. The new software is developed by using MATLAB with the new functions: electron energy (EE) scanning, deuterium partial pressure measurement, and automatic data saving. RGA200 with new software is calibrated in pure deuterium and pure helium 1.0 × 10{sup −6}–5.0 × 10{sup −2} Pa, and the relation between pressure and ion current of AMU4 under EE = 25 eV and EE = 70 eV is obtained. From the calibration result and RGA200 scanning with varied ionization energy in deuterium and helium mixture gas, both deuterium partial pressures (P{sub D{sub 2}}) and helium partial pressure (P{sub He}) could be obtained. The result shows that deuterium partial pressure could be measured if P{sub D{sub 2}} > 10{sup −6} Pa (limited by ultimate pressure of calibration vessel), and helium pressure could be measured only if P{sub He}/P{sub D{sub 2}} > 0.45, and the measurement error is evaluated as 15%. This method is successfully employed in EAST 2015 summer campaign to monitor deuterium outgassing/desorption during helium discharge cleaning.

  17. High-efficiency electron ionizer for a mass spectrometer array

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara (Inventor); Darrach, Murray R. (Inventor); Orient, Otto J. (Inventor)

    2001-01-01

    The present invention provides an improved electron ionizer for use in a quadrupole mass spectrometer. The improved electron ionizer includes a repeller plate that ejects sample atoms or molecules, an ionizer chamber, a cathode that emits an electron beam into the ionizer chamber, an exit opening for excess electrons to escape, at least one shim plate to collimate said electron beam, extraction apertures, and a plurality of lens elements for focusing the extracted ions onto entrance apertures.

  18. Metabolite localization by atmospheric pressure high-resolution scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging in whole-body sections and individual organs of the rove beetle Paederus riparius.

    PubMed

    Bhandari, Dhaka Ram; Schott, Matthias; Römpp, Andreas; Vilcinskas, Andreas; Spengler, Bernhard

    2015-03-01

    Mass spectrometry imaging provides for non-targeted, label-free chemical imaging. In this study, atmospheric pressure high-resolution scanning microprobe matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-SMALDI MSI) was used for the first time to describe the chemical distribution of the defensive compounds pederin, pseudopederin, and pederon in tissue sections (16 μm thick) of the rove beetle Paederus riparius. The whole-insect tissue section was scanned with a 20-μm step size. Mass resolution of the orbital trapping mass spectrometer was set to 100,000 at m/z 200. Additionally, organ-specific compounds were identified for brain, nerve cord, eggs, gut, ovaries, and malpighian tubules. To confirm the distribution of the specific compounds, individual organs from the insect were dissected, and MSI experiments were performed on the dissected organs. Three ganglia of the nerve cord, with a dimension of 250-500 μm, were measured with 10-μm spatial resolution. High-quality m/z images, based on high spatial resolution and high mass accuracy were generated. These features helped to assign mass spectral peaks with high confidence. Mass accuracy of the imaging experiments was <3 ppm root mean square error, and mapping of different compound classes from a single experiment was possible. This approach improved the understanding of the biochemistry of P. riparius. Concentration differences and distributions of pederin and its analogues could be visualized in the whole-insect section. Without any labeling, we assigned key lipids for specific organs to describe their location in the body and to identify morphological structures with a specificity higher than with staining or immunohistology methods.

  19. Comparison of reversed-phase liquid chromatography-mass spectrometry with electrospray and atmospheric pressure chemical ionization for analysis of dietary tocopherols.

    PubMed

    Lanina, Svetlana A; Toledo, Patricia; Sampels, Sabine; Kamal-Eldin, Afaf; Jastrebova, Jelena A

    2007-07-20

    ESI and APCI ionization techniques in both negative and positive ion modes were evaluated for simultaneous LC-MS analysis of the four tocopherol homologues (alpha, beta, gamma and delta). The ESI and APCI ionization of tocopherols in positive ion mode was not efficient and proceeded via two competitive mechanisms, with the formation of protonated pseudo-molecular ions and molecular ions, which adversely influenced the repeatability of MS signal. Ionization in negative ion mode in both ESI and APCI was more efficient as it only produced target deprotonated pseudo-molecular ions. The APCI in negative ion mode showed larger linearity range, lower detection limits and was less sensitive to the differences in chemical structure of analytes and nature of applied solvents than negative ion ESI. Negative ion APCI was, therefore, chosen for the development of LC-MS method for simultaneous determination of the four tocopherols in foods. A baseline separation of the tocopherols was achieved on novel pentafluorophenyl silica-based column Fluophase PFP. The use of methanol-water (95:5, v/v) as a mobile phase was preferable to the use of acetonitrile-water due to considerable gain in MS signal. The limits of quantifications were 9 ng/mL for alpha-tocopherol, 8 ng/mL for beta- and gamma- and 7.5 ng/mL for delta-tocopherol when 2 microL was injected. This method was successfully applied to determination of tocopherols in sunflower oil and milk.

  20. Ionization energy of acetone by vacuum ultraviolet mass-analyzed threshold ionization spectrometry

    NASA Astrophysics Data System (ADS)

    Kim, Jae Han; Kang, Do Won; Hong, Yong Jun; Hwang, Hyonseok; Kim, Hong Lae; Kwon, Chan Ho

    2013-04-01

    Mass-analyzed threshold ionization (MATI) time-of-flight mass spectrometer using coherent vacuum ultraviolet (VUV) laser generated by four-wave difference frequency mixing (FWDFM) in Kr has been constructed and utilized to obtain the accurate ionization energy of acetone. From the MATI onsets measured from various applied pulsed fields, the ionization energy to the ionic ground state of acetone has been determined to be 9.7074 ± 0.0019 eV.

  1. Systematic investigation of ion suppression and enhancement effects of fourteen stable-isotope-labeled internal standards by their native analogues using atmospheric-pressure chemical ionization and electrospray ionization and the relevance for multi-analyte liquid chromatographic/mass spectrometric procedures.

    PubMed

    Remane, Daniela; Wissenbach, Dirk K; Meyer, Markus R; Maurer, Hans H

    2010-04-15

    In clinical and forensic toxicology, multi-analyte procedures are very useful to quantify drugs and poisons of different classes in one run. For liquid chromatographic/tandem mass spectrometric (LC/MS/MS) multi-analyte procedures, often only a limited number of stable-isotope-labeled internal standards (SIL-ISs) are available. If an SIL-IS is used for quantification of other analytes, it must be excluded that the co-eluting native analyte influences its ionization. Therefore, the effect of ion suppression and enhancement of fourteen SIL-ISs caused by their native analogues has been studied. It could be shown that the native analyte concentration influenced the extent of ion suppression and enhancement effects leading to more suppression with increasing analyte concentration especially when electrospray ionization (ESI) was used. Using atmospheric-pressure chemical ionization (APCI), methanolic solution showed mainly enhancement effects, whereas no ion suppression and enhancement effect, with one exception, occurred when plasma extracts were used under these conditions. Such differences were not observed using ESI. With ESI, eleven SIL-ISs showed relevant suppression effects, but only one analyte showed suppression effects when APCI was used. The presented study showed that ion suppression and enhancement tests using matrix-based samples of different sources are essential for the selection of ISs, particularly if used for several analytes to avoid incorrect quantification. In conclusion, only SIL-ISs should be selected for which no suppression and enhancement effects can be observed. If not enough ISs are free of ionization interferences, a different ionization technique should be considered.

  2. Analysis of chirality by femtosecond laser ionization mass spectrometry.

    PubMed

    Horsch, Philipp; Urbasch, Gunter; Weitzel, Karl-Michael

    2012-09-01

    Recent progress in the field of chirality analysis employing laser ionization mass spectrometry is reviewed. Emphasis is given to femtosecond (fs) laser ionization work from the author's group. We begin by reviewing fundamental aspects of determining circular dichroism (CD) in fs-laser ionization mass spectrometry (fs-LIMS) discussing an example from the literature (resonant fs-LIMS of 3-methylcyclopentanone). Second, we present new data indicating CD in non-resonant fs-LIMS of propylene oxide.

  3. Desorption and ionization mechanisms in desorption atmospheric pressure photoionization.

    PubMed

    Luosujärvi, Laura; Arvola, Ville; Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Franssila, Sami; Kotiaho, Tapio; Kostiainen, Risto; Kauppila, Tiina J

    2008-10-01

    The factors influencing desorption and ionization in newly developed desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) were studied. Redirecting the DAPPI spray was observed to further improve the versatility of the technique: for dilute samples, parallel spray with increased analyte signal was found to be the best suited, while for more concentrated samples, the orthogonal spray with less risk for contamination is recommended. The suitability of various spray solvents and sampling surface materials was tested for a variety of analytes with different polarities and molecular weights. As in atmospheric pressure photoionization, the analytes formed [M + H](+), [M - H](-), M(+*), M(-*), [M - H + O](-), or [M - 2H + 2O](-) ions depending on the analyte, spray solvent, and ionization mode. In positive ion mode, anisole and toluene as spray solvents promoted the formation of M(+*) ions and were therefore best suited for the analysis of nonpolar compounds (anthracene, benzo[a]pyrene, and tetracyclone). Acetone and hexane were optimal spray solvents for polar compounds (MDMA, testosterone, and verapamil) since they produced intensive [M + H](+) ion peaks of the analytes. In negative ion mode, the type of spray solvent affected the signal intensity, but not the ion composition. M(-*) ions were formed from 1,4-dinitrobenzene, and [M - H + O](-) and [M - 2H + 2O](-) ions from 1,4-naphthoquinone, whereas acidic compounds (naphthoic acid and paracetamol) formed [M - H](-) ions. The tested sampling surfaces included various materials with different thermal conductivities. The materials with low thermal conductivity, i.e., polymers like poly(methyl methacrylate) and poly(tetrafluoroethylene) (Teflon) were found to be the best, since they enable localized heating of the sampling surface, which was found to be essential for efficient analyte desorption. Nevertheless, the sampling surface material did not affect the ionization mechanisms.

  4. Photoelectron emission as an alternative electron impact ionization source for ion trap mass spectrometry.

    PubMed

    Gamez, Gerardo; Zhu, Liang; Schmitz, Thomas A; Zenobi, Renato

    2008-09-01

    Electron impact ionization has several known advantages; however, heated filament electron sources have pressure limitations and their power consumption can be significant for certain applications, such as in field-portable instruments. Herein, we evaluate a VUV krypton lamp as an alternative source for ionization inside the ion trap of a mass spectrometer. The observed fragmentation patterns are more characteristic of electron impact ionization than photoionization. In addition, mass spectra of analytes with ionization potentials higher than the lamp's photon energy (10.6 eV) can be easily obtained. A photoelectron impact ionization mechanism is suggested by the observed data allowed by the work function of the ion trap electrodes (4.5 eV), which is well within the lamp's photon energy. In this case, the photoelectrons emitted at the surface of the ion trap end-cap electrode are accelerated by the applied rf field to the ring electrode. This allows the photoelectrons to gain sufficient energy to ionize compounds with high ionization potentials to yield mass spectra characteristic of electron impact. In this manner, electron impact ionization can be used in ion trap mass spectrometers at low powers and without the limitations imposed by elevated pressures on heated filaments.

  5. High-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry and gas chromatography-flame ionization detection characterization of Delta5-polyenoic fatty acids in triacylglycerols from conifer seed oils.

    PubMed

    Lísa, Miroslav; Holcapek, Michal; Rezanka, Tomás; Kabátová, Nadezda

    2007-03-30

    Edible conifer seeds can serve as a source of triacylglycerols (TGs) with unusual Delta5 unsaturated polymethylene interrupted fatty acids (UPIFAs), such as cis-5,9-octadecadienoic (taxoleic), cis-5,9,12-octadecatrienoic (pinolenic), cis-5,11-eicosadienoic (keteleeronic) and cis-5,11,14-eicosatrienoic acids (sciadonic). Conifer seed oils from European Larch (Larix decidua), Norway Spruce (Picea abies) and European Silver Fir (Abies alba) have been analyzed by non-aqueous reversed-phase high-performance liquid chromatography (NARP-HPLC) with atmospheric pressure chemical ionisation (APCI)-MS detection. The influence of different positions of double bonds in Delta5-UPIFAs on the retention and fragmentation behavior is described and used for the successful identification of TGs in each oil. TGs containing Delta5-UPIFAs have a higher retention in comparison with common TGs found in plant oils with single methylene interrupted Delta6(9)-FAs and also significantly changed relative abundances of fragment ions in APCI mass spectra. Results obtained from HPLC/MS analyses are supported by validated GC/FID analyses of fatty acid methyl esters after the transesterification. The total content of Delta5-UPIFAs is about 32% for European Larch, 27% for Norway Spruce and 20% for European Silver Fir. In total, 20 FAs with acyl chain lengths from 16 to 24 carbon atoms and from 0 to 3 double bonds have been identified in 64 triacylglycerols from 3 conifer seed oils.

  6. Multiphoton Ionization Mass and Photoelectron Spectroscopy.

    DTIC Science & Technology

    1984-07-01

    narro , band. tunable. frequency doubled dye laser Their relative importance depend% on the sample being studied ha- led to an cnormou, improcment in...block number) Mult iphoton Ionization Photoelectron Spectroscopy Laser Induced Ionization Ultraviolet Laser Radiation ft ArITAcr (camthIe i rvee ehl N...molecular ions generated by laser ionization have been monitored. Using a time of flight photoelectron spectrometer, the kinetic energy distribution of the

  7. Electron ionization mass spectrum of tellurium hexafluoride.

    PubMed

    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 electron ionization mass spectrum of tellurium hexafluoride (TeF6) is reported for the first time. 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 odd fluoride bearing ions, TeF1(+) < TeF3(+) < TeF5(+), and a decreasing abundance was observed for the even fragment series, Te(F0)(+) > 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(+).

  8. Electron Ionization Mass Spectrum of Tellurium Hexafluoride

    SciTech Connect

    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+.

  9. A validated method for the determination of nicotine, cotinine, trans-3'-hydroxycotinine, and norcotinine in human plasma using solid-phase extraction and liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Kim, Insook; Huestis, Marilyn A

    2006-06-01

    A liquid chromatographic-mass spectrometric method for the simultaneous determination of nicotine, cotinine, trans-3'-hydroxycotinine, and norcotinine in human plasma was developed and validated. Analytes and deuterated internal standards were extracted from human plasma using solid-phase extraction and analyzed by liquid chromatography/atmospheric pressure chemical ionization-mass spectrometric detection with selected ion monitoring (SIM). Limits of detection and quantification were 1.0 and 2.5 ng/ml, respectively, for all analytes. Linearity ranged from 2.5 to 500 ng/ml of human plasma using a weighting factor of 1/x; correlation coefficients for the calibration curves were > 0.99. Intra- and inter-assay precision and accuracy were < 15.0%. Recoveries were 108.2-110.8% nicotine, 95.8-108.7% cotinine, 90.5-99.5% trans-3'-hydroxycotinine, and 99.5-109.5% norcotinine. The method was also partially validated in bovine serum, owing to the difficulty of obtaining nicotine-free human plasma for the preparation of calibrators and quality control (QC) samples. This method proved to be robust and accurate for the quantification of nicotine, cotinine, trans-3'-hydroxycotinine, and norcotinine in human plasma collected in clinical studies of acute nicotine effects on brain activity and on the development of neonates of maternal smokers.

  10. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  11. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

  12. Method to reduce chemical background interference in atmospheric pressure ionization liquid chromatography-mass spectrometry using exclusive reactions with the chemical reagent dimethyl disulfide.

    PubMed

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

    2007-06-01

    The interference of chemical background ions (chemical noise) has been a problem since the inception of mass spectrometry. We present here a novel method to reduce the chemical noise in LC-MS based on exclusive gas-phase reactions with a reactive collision gas in a triple-quadrupole mass spectrometer. Combined with the zero neutral loss (ZNL) scan of a triple-quadrupole mass spectrometer, the reactive chemical noise ions can be removed because of shifts of mass-to-charge ratios from the original background ions. The test on various classes of compounds with different functional groups indicates a generic application of this technique in LC-MS. The preliminary results show that a reduction of the level of LC-MS base-peak chromatographic baseline by a factor up to 40 and an improvement of the signal-to-noise ratio by a factor up to 5-10 are achieved on both commercial and custom-modified triple-quadrupole LC-MS systems. Application is foreseen in both quantitative and qualitative trace analysis. It is expected that this chemical noise reduction technique can be optimized on a dedicated mass spectrometric instrumentation which incorporates both a chemical reaction cell for noise reduction and a collision stage for fragmentation.

  13. Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

    2010-02-01

    Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

  14. Collison nebulizer as a new soft ionization source for mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pervukhin, V. V.; Sheven', D. G.; Kolomiets, Yu. N.

    2016-08-01

    We have proposed that a Collison-type nebulizer be used as an ionization source for mass spectrometry with ionization under atmospheric pressure. This source does not require the use of electric voltage, radioactive sources, heaters, or liquid pumps. It has been shown that the number of ions produced by the 63Ni radioactive source is three to four times larger than the number of ions produced by acoustic ionization sources. We have considered the possibility of using a Collison-type nebulizer in combination with a vortex focusing system as an ion source for extractive ionization of compounds under atmospheric pressure. The ionization of volatile substances in crossflows of a charged aerosol and an analyte (for model compounds of the amine class, viz., diethylaniline, triamylamine, and cocaine) has been investigated. It has been shown that the limit of detecting cocaine vapor by this method is on the level of 4.6 × 10-14 g/cm3.

  15. Utility of spatially-resolved atmospheric pressure surface sampling and ionization techniques as alternatives to mass spectrometric imaging (MSI) in drug metabolism

    SciTech Connect

    Blatherwick, Eleanor Q.; Van Berkel, Gary J; Pickup, Kathryn; Johansson, Maria K.; Beaudoin, Marie-Eve; Cole, Roderic; Day, Jennifer M.; Iverson, Suzanne; Wilson, Ian D.; Scrivens, James H.; Weston, Daniel J.

    2011-01-01

    1. Tissue distribution studies of drug molecules play an essential role in the pharmaceutical industry and are commonly undertaken using quantitative whole body autoradiography (QWBA) methods. 2. The growing need for complementary methods to address some scientific gaps around radiography methods has led to increased use of mass spectrometric imaging (MSI) technology over the last 5 to 10 years. More recently, the development of novel mass spectrometric techniques for ambient surface sampling has redefined what can be regarded as fit-for-purpose for MSI in a drug metabolism and disposition arena. 3. Together with a review of these novel alternatives, this paper details the use of two liquid microjunction (LMJ)- based mass spectrometric surface sampling technologies. These approaches are used to provide qualitative determination of parent drug in rat liver tissue slices using liquid extraction surface analysis (LESA) and to assess the performance of a LMJ surface sampling probe (LMJ-SSP) interface for quantitative assessment of parent drug in brain, liver and muscle tissue slices. 4. An assessment of the utility of these spatially-resolved sampling methods is given, showing interdependence between mass spectrometric and QWBA methods, in particular there emerges a reason to question typical MSI workflows for drug metabolism; suggesting the expedient use of profile or region analysis may be more appropriate, rather than generating time-intensive molecular images of the entire tissue section.

  16. Utility of spatially-resolved atmospheric pressure surface sampling and ionization techniques as alternatives to mass spectrometric imaging (MSI) in drug metabolism.

    PubMed

    Blatherwick, Eleanor Q; Van Berkel, Gary J; Pickup, Kathryn; Johansson, Maria K; Beaudoin, Marie-Eve; Cole, Roderic O; Day, Jennifer M; Iverson, Suzanne; Wilson, Ian D; Scrivens, James H; Weston, Daniel J

    2011-08-01

    Tissue distribution studies of drug molecules play an essential role in the pharmaceutical industry and are commonly undertaken using quantitative whole body autoradiography (QWBA) methods. The growing need for complementary methods to address some scientific gaps around radiography methods has led to increased use of mass spectrometric imaging (MSI) technology over the last 5 to 10 years. More recently, the development of novel mass spectrometric techniques for ambient surface sampling has redefined what can be regarded as "fit-for-purpose" for MSI in a drug metabolism and disposition arena. Together with a review of these novel alternatives, this paper details the use of two liquid microjunction (LMJ)-based mass spectrometric surface sampling technologies. These approaches are used to provide qualitative determination of parent drug in rat liver tissue slices using liquid extraction surface analysis (LESA) and to assess the performance of a LMJ surface sampling probe (LMJ-SSP) interface for quantitative assessment of parent drug in brain, liver and muscle tissue slices. An assessment of the utility of these spatially-resolved sampling methods is given, showing interdependence between mass spectrometric and QWBA methods, in particular there emerges a reason to question typical MSI workflows for drug metabolism; suggesting the expedient use of profile or region analysis may be more appropriate, rather than generating time-intensive molecular images of the entire tissue section.

  17. Real-time air monitoring of mustard gas and Lewisite 1 by detecting their in-line reaction products by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow ion introduction.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2015-01-20

    A new method enabling sensitive real-time air monitoring of highly reactive chemical warfare agents, namely, mustard gas (HD) and Lewisite 1 (L1), by detecting ions of their in-line reaction products instead of intact agents, is proposed. The method is based on corona discharge-initiated atmospheric pressure chemical ionization coupled with ion trap tandem mass spectrometry (MS(n)) via counterflow ion introduction. Therefore, it allows for highly sensitive and specific real-time detection of a broad range of airborne compounds. In-line chemical reactions, ionization reactions, and ion fragmentations of these agents were investigated. Mustard gas is oxygenated in small quantity by reactive oxygen species generated in the corona discharge. With increasing air humidity, the MS(2) signal intensity of protonated molecules of mono-oxygenated HD decreases but exceeds that of dominantly existing intact HD. This result can be explained in view of proton affinity. Lewisite 1 is hydrolyzed and oxidized. As the humidity increases from zero, the signal of the final product, namely, didechlorinated, dihydroxylated, and mono-oxygenated L1, quickly increases and reaches a plateau, giving the highest MS(2) and MS(3) signals among those of L1 and its reaction products. The addition of minimal moisture gives the highest signal intensity, even under low humidity. The method was demonstrated to provide sufficient analytical performance to meet the requirements concerning hygienic management and counter-terrorism. It will be the first practical method, in view of sensitivity and specificity, for real-time air monitoring of HD and L1 without sample pretreatment.

  18. Ghost peaks observed after atmospheric pressure matrix-assisted laser desorption/ionization experiments may disclose new ionization mechanism of matrix-assisted hypersonic velocity impact ionization.

    PubMed

    Moskovets, Eugene

    2015-08-30

    Understanding the mechanisms of matrix-assisted laser desorption/ionization (MALDI) promises improvements in the sensitivity and specificity of many established applications in the field of mass spectrometry. This paper reports a serendipitous observation of a significant ion yield in a post-ionization experiment conducted after the sample had been removed from a standard atmospheric pressure (AP)-MALDI source. This post-ionization is interpreted in terms of collisions of microparticles moving with a hypersonic velocity into a solid surface. Calculations show that the thermal energy released during such collisions is close to that absorbed by the top matrix layer in traditional MALDI. The microparticles, containing both the matrix and analytes, could be detached from a film produced inside the inlet capillary during the sample ablation and accelerated by the flow rushing through the capillary. These observations contribute some new perspective to ion formation in both laser and laser-less matrix-assisted ionization. An AP-MALDI ion source hyphenated with a three-stage high-pressure ion funnel system was utilized for peptide mass analysis. After the laser had been turned off and the MALDI sample removed, ions were detected during a gradual reduction of the background pressure in the first funnel. The constant-rate pressure reduction led to the reproducible appearance of different singly and doubly charged peptide peaks in mass spectra taken a few seconds after the end of the MALDI analysis of a dried-droplet spot. The ion yield as well as the mass range of ions observed with a significant delay after a completion of the primary MALDI analysis depended primarily on the background pressure inside the first funnel. The production of ions in this post-ionization step was exclusively observed during the pressure drop. A lower matrix background and significant increase in relative yield of double-protonated ions are reported. The observations were partially consistent

  19. Pressure-assisted capillary electrochromatography with electrospray ionization-mass spectrometry based on silica-based monolithic column for rapid analysis of narcotics.

    PubMed

    Lu, Minghua; Zhang, Lan; Feng, Qiang; Xia, Shifei; Chi, Yuwu; Tong, Ping; Chen, Guonan

    2008-02-01

    A pressure-assisted CEC (pCEC) with ESI-MS based on silica-based monolithic column was developed for rapid analysis of narcotics. Combining the extremely high permeability and separation efficiency of silica-based monolithic column with the high selectivity and sensitivity of pCEC-ESI-MS, the developed system exhibited its prominent advantages in separation and detection. A systematic investigation of the pCEC separation and ESI-MS detection parameters was performed. Experiment results showed that the optimized separation efficiency could be obtained at 8 bar assisted pressure with 25 kV separation voltage, using the solution containing 65% ACN v/v and 20 mmol/L ammonium acetate with pH 6.0 as running buffer. 3 microL/min of sheath liquid was considered as the optimized flow rate since it could provide the maximum signal intensity. Under the optimum conditions, the tested five narcotics could be completely separated within 10 min with the detection limit in the range of 2.0-80 nmol/L. The proposed method has been successfully used for detection of narcotics in real urine samples.

  20. Fundamentals of Biomolecule Analysis by Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Weinecke, Andrea; Ryzhov, Victor

    2005-01-01

    Electrospray ionization (ESI) is a soft ionization technique that allows transfer of fragile biomolecules directly from solution into the gas phase. An instrumental analysis laboratory experiment is designed that would introduce the students to the ESI technique, major parameters of the ion trap mass spectrometers and some caveats in…

  1. Fundamentals of Biomolecule Analysis by Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Weinecke, Andrea; Ryzhov, Victor

    2005-01-01

    Electrospray ionization (ESI) is a soft ionization technique that allows transfer of fragile biomolecules directly from solution into the gas phase. An instrumental analysis laboratory experiment is designed that would introduce the students to the ESI technique, major parameters of the ion trap mass spectrometers and some caveats in…

  2. Thorium resonance ionization mass spectrometry for geochronological and geochemical applications

    SciTech Connect

    Fearey, B.L.; Johnson, S.G.; Nogar, N.; Murrell, M.T.; Miller, C.M.

    1990-01-01

    Resonance Ionization Mass Spectrometry (RIMS) is being developed to measure thorium isotopics from geological samples. These measurements, in conjunction with uranium measurements by thermal ionization, permit geochronological dating in the timescale of 10,000 to 350,000 years. 15 refs., 2 figs.

  3. Systematic screening and characterization of glycosides in tobacco leaves by liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry using neutral loss scan and product ion scan.

    PubMed

    Ding, Li; Wang, Xiaoyu; Wang, Sheng; Yu, Jingjing; Qin, Yaqiong; Zhang, Xiaobing; Xie, Fuwei

    2015-12-01

    Glycosides in tobacco leaves are highly important aromatic precursors. It is necessary to reveal glycosides in tobacco leaves to improve tobacco planting and processing. This study describes a method for the systematic screening of glycosides in tobacco leaves by liquid chromatography with tandem mass spectrometry. Although glycosides contain numerous aglycones, the number of glycans is limited. Based on a screening table of glycans designed for neutral loss scan, glycosides with different aglycones were systematically screened out. Then, the MS(2) fragment spectra of scanned glycosides were further obtained using product ion scan. By comparison with the spectra in online tandem mass spectral databases, reported references, and verification by commercial standards, 64 glycosides were detected, including 39 glycosides linked with monosaccharides, 18 glycosides linked with disaccharides and 7 glycosides linked with trisaccharides. It is noteworthy that glycosides linked with trisaccharides have previously been rarely reported in tobacco. This method appears to be a useful tool for the systematic screening and characterization of glycosides in tobacco and can potentially be applied to other plants.

  4. [Determination of homocysteine by tandem mass spectrometry with chemical ionization].

    PubMed

    Miroshnichenko, I I; Platova, A I; Safarova, T P; Iakovleva, O B

    2014-01-01

    Homocysteine (Hcy) is an intermediate of methionine metabolism. High plasma Hcy concentrations are an independent risk factor for stroke, peripheral vascular disease, deep venous thrombosis, coronary disease, and cognitive deficiency. Apparently, it is a great importance to measure Hcy levels in human blood. A new method for the quantification of Hcy by means of reversed-phase LC/atmospheric pressure chemical ionization mass spectrometry has been developed. The MRM ion transition, m/z 136.0 ® 90.0 was used for Hcy quantification. The limit of detection was 0.4 mM, quantification was performed from 1 mM to 40 mM with coefficient of determination of R2=0,997. The method was applied successfully to Hcy determination in human blood.

  5. Variable pressure ionization detector for gas chromatography

    DOEpatents

    Buchanan, Michelle V.; Wise, Marcus B.

    1988-01-01

    Method and apparatus for differentiating organic compounds based on their electron affinity. An electron capture detector cell (ECD) is operated at pressures ranging from atmospheric to less than 1 torr. Through variation of the pressure within the ECD cell, the organic compounds are induced to either capture or emit electrons. Differentiation of isomeric compounds can be obtianed when, at a given pressure, one isomer is in the emission mode and the other is in the capture mode. Output of the ECD is recorded by chromatogram. The invention also includes a method for obtaining the zero-crossing pressure of a compound, defined as the pressure at which the competing emission and capture reactions are balanced and which may be correlated to the electron affinity of a compound.

  6. Quantitative determination of cholesterol, sitosterol, and sitostanol in cultured Caco-2 cells by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Palmgrén, Joni J; Töyräs, Anu; Mauriala, Timo; Mönkkönen, Jukka; Auriola, Seppo

    2005-07-25

    In this study, we describe a simple liquid extraction (methanol/choloroform, 1:1, v/v) method for endogenous free cholesterol and administered sterols extracted from cultured Caco-2 cells. To quantify sterol contents in Caco-2 cells, a new HPLC-APCI-MS method was developed. All the sterols were baseline separated using reversed-phase column (C8, 2.1 mm x 150 mm, 3.5 microm) and isocratic conditions (90%, v/v, methanol-water mixture containing 0.2 mM ammonium acetate). The full scan mass spectra of sterols were measured by an ion trap mass spectrometer equipped with an APCI ion source. The intense fragment ions resulting from the loss of water [M+H-H2O]+ (m/z 369, 395, 397 and 399 for cholesterol, stigmasterol, sitosterol, and sitostanol, respectively) were used for determinations. The absolute extraction recovery of sterols from the spiked cell samples were 109.7+/-26.2, 105.7+/-5.1, 109.8+/-5.0 and 99.0+/-7.0% for cholesterol, stigmasterol, sitosterol, and sitostanol, respectively. Furthermore, no significant matrix effect was observed for the sterols in the cell samples. The sample assay was based on the internal standard method using stigmasterol as an internal standard. The method was linear over the concentration ranges of 0.45-9.0 microM (cholesterol) and 0.225-7.2 microM (sitosterol and sitostanol). The within- and between-day precision was less than 7% and accuracy ranged from 93.51 to 101.77%. The lowest limit of quantitation (LLOQ) was 0.225 microM for sitosterol and sitostanol, and 0.45 microM for cholesterol. The accuracy range was 95-106% and precision was lower than 9% for all LLOQ values.

  7. Comparison of microbial communities in Lake Tahoe surface sample with Tonga Trench water column samples using High Pressure Liquid Chromatography - Electrospray Ionization - Mass Spectroscopy (HPLC - ESI - MS) and Global Natural Products Social Molecular Network (GNPS)

    NASA Astrophysics Data System (ADS)

    Belmonte, M. A.

    2015-12-01

    Intact polar lipids (IPLs) are lipids composed of a head group, a glycerol, and a fatty acid chain that make up the lipid bilayer of cell membranes in living cells; and the varying head groups can be indicative of the type of microbes present in the environment (Van Mooy 2010). So by distinguishing and identifying the IPL distribution in an environment one can make inferences about the microbial communities in the said environment. In this study, we used High Pressure Liquid Chromatography-Electrospray Ionization- Mass Spectroscopy (HPLC-ESI-MS) and Global Natural Products Social Molecular Networking (GNPS) to compare the IPL distributions of two oligotrophic environments: surface waters of Lake Tahoe in the Sierra Nevada Mountains, and the water column of the Tonga Trench in the South Pacific. We hypothesized that the similar nutrient dynamics of the two oligotrophic environments would result in similar eukaryotic and prokaryotic communities, which would be reflected in the IPL composition of suspended particulate organic matter (POM). For simplicity we focused on the classes of IPLs most commonly observed in the marine environment: phosphotidylglycerol (PG), phosphotidylethanolamine (PE), diacylglyceryl-trimethyl-homoserine (DGTS), diacylglyceryl-hydroxymethyl-trimethylalanine (DGTA), sulfoquinovosyldiacylglycerol (SQDG), monoglycosyldiacylglycerol (MGDG) and diglycosyldiacylglycerol (DGDG). Our results showed that all of the marine IPLs of interest were present in Lake Tahoe which confirms that there are many of the same microbial communities in the fresh waters of Lake Tahoe and the salt waters Tonga Trench.

  8. Liquid Microjunction Surface Sampling Coupled with High-Pressure Liquid Chromatography-Electrospray Ionization-Mass Spectrometry for Analysis of Drugs and Metabolites in Whole-Body Thin Tissue Sections

    SciTech Connect

    Kertesz, Vilmos; Van Berkel, Gary J

    2010-01-01

    In this work, a commercially available autosampler was adapted to perform direct liquid microjunction (LMJ) surface sampling followed by a high-pressure liquid chromatography (HPLC) separation of the extract components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the utility of coupling a separation with this direct liquid extraction based surface sampling approach, four different organs (brain, lung, kidney, and liver) from whole-body thin tissue sections of propranolol dosed and control mice were examined. The parent drug was observed in the chromatograms of the surface sampling extracts from all the organs of the dosed mouse examined. In addition, two isomeric phase II metabolites of propranolol (an aliphatic and an aromatic hydroxypropranolol glucuronide) were observed in the chromatograms of the extracts from lung, kidney, and liver. Confirming the presence of one or the other or both of these glucuronides in the extract from the various organs was not possible without the separation. These drug and metabolite data obtained using the LMJ surface sampling/HPLC-MS method and the results achieved by analyzing similar samples by conventional extraction of the tissues and subsequent HPLC-MS analysis were consistent.

  9. Analysis of aldehydes in beer by gas-diffusion microextraction: characterization by high-performance liquid chromatography-diode-array detection-atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Gonçalves, Luís Moreira; Magalhães, Paulo Jorge; Valente, Inês Maria; Pacheco, João Grosso; Dostálek, Pavel; Sýkora, David; Rodrigues, José António; Barros, Aquiles Araújo

    2010-06-11

    In this work, a recently developed extraction technique for sample preparation aiming the analysis of volatile and semi-volatile compounds named gas-diffusion microextraction (GDME) is applied in the chromatographic analysis of aldehydes in beer. Aldehydes-namely acetaldehyde (AA), methylpropanal (MA) and furfural (FA)-were simultaneously extracted and derivatized with 2,4-dinitrophenylhydrazine (DNPH), then the derivatives were separated and analyzed by high-performance liquid chromatography with spectrophotometric detection (HPLC-UV). The identity of the eluted compounds was confirmed by high-performance liquid chromatography-atmospheric pressure chemical ionization-mass-spectrometry detection in the negative ion mode (HPLC-APCI-MS). The developed methodology showed good repeatability (ca. 5%) and linearity as well as good limits of detection (AA-12.3, FA-1.5 and MA 5.4microgL(-1)) and quantification (AA-41, FA-4.9 and MA 18microgL(-1)); it also appears to be competitive in terms of speed and cost of analysis.

  10. Identification of organic hydroperoxides and hydroperoxy acids in secondary organic aerosol formed during the ozonolysis of different monoterpenes and sesquiterpenes by on-line analysis using atmospheric pressure chemical ionization ion trap mass spectrometry.

    PubMed

    Reinnig, Marc-Christopher; Warnke, Jörg; Hoffmann, Thorsten

    2009-06-01

    On-line ion trap mass spectrometry (ITMS) enables the real-time characterization of reaction products of secondary organic aerosol (SOA). The analysis was conducted by directly introducing the aerosol particles into the ion source. Positive-ion chemical ionization at atmospheric pressure (APCI(+)) ITMS was used for the characterization of constituents of biogenic SOA produced in reaction-chamber experiments. APCI in the positive-ion mode usually enables the detection of [M+H](+) ions of the individual SOA components. In this paper the identification of organic peroxides from biogenic volatile organic compounds (VOCs) by on-line APCI-ITMS is presented. Organic peroxides containing a hydroperoxy group, generated by gas-phase ozonolysis of monoterpenes (alpha-pinene and beta-pinene) and sesquiterpenes (alpha-cedrene and alpha-copaene), could be detected via on-line APCI(+)-MS/MS experiments. A characteristic neutral loss of 34 Da (hydrogen peroxide, H(2)O(2)) in the on-line MS/MS spectra is a clear indication for the existence of an organic peroxide, containing a hydroperoxy functional group.

  11. Quantitative method for analysis of monensin in soil, water, and urine by direct combination of single-drop microextraction with atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Sekar, Ramaiyan; Wu, Hui-Fen

    2006-09-15

    A simple and selective analytical method for the quantitative determination of low concentrations of monensin in soil, surface water, and human urine has been developed. Prior to atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI-MS) analysis, the samples were preconcentrated by using the single-drop microextraction (SDME) technique. Several factors that affect the analyte's extraction, including selection of solvent, microdrop volume, extraction time, and ionic strength, were investigated. Chloroform-toluene (1:1, v/v) was selected as the extraction solvent. Reliable results were obtained using dibenzo-30-crown-10-ether as an internal standard. The proposed method has been successfully applied for the determination of monensin in soil, surface water, and human urine spiked samples. Under the optimized conditions, the limits of quantification of the analyte in surface water, soil, and human urine were 6.7, 12.4 and 7.8 ng/mL, respectively. The intraday and interday precision variation and accuracy of the present method is within the acceptable ranges. The present method avoids the pre- and postderivatization of weak UV absorbing monensin determination using high performance liquid chromatography-ultraviolet detection (HPLC-UV). Furthermore, these techniques are time-consuming, nonreproducible at trace levels, and form undesirable products. The proposed SDME combined with AP-MALDI-MS is simple, fast, and selective for the determination of monensin in environmental and urine samples.

  12. Method development for the determination of 24S-hydroxycholesterol in human plasma without derivatization by high-performance liquid chromatography with tandem mass spectrometry in atmospheric pressure chemical ionization mode.

    PubMed

    Sugimoto, Hiroshi; Kakehi, Masaaki; Satomi, Yoshinori; Kamiguchi, Hidenori; Jinno, Fumihiro

    2015-10-01

    We developed a highly sensitive and specific high-performance liquid chromatography with tandem mass spectrometry method with an atmospheric pressure chemical ionization interface to determine 24S-hydroxycholesterol, a major metabolite of cholesterol formed by cytochrome P450 family 46A1, in human plasma without any derivatization step. Phosphate buffered saline including 1% Tween 80 was used as the surrogate matrix for preparation of calibration curves and quality control samples. The saponification process to convert esterified 24S-hydroxycholesterol to free sterols was optimized, followed by liquid-liquid extraction using hexane. Chromatographic separation of 24S-hydroxycholesterol from other isobaric endogenous oxysterols was successfully achieved with gradient mobile phase comprised of 0.1% propionic acid and acetonitrile using L-column2 ODS (2 μm, 2.1 mm id × 150 mm). This assay was capable of determining 24S-hydroxycholesterol in human plasma (200 μL) ranging from 1 to 100 ng/mL with acceptable intra- and inter-day precision and accuracy. The potential risk of in vitro formation of 24S-hydroxycholesterol by oxidation from endogenous cholesterol in human plasma was found to be negligible. The stability of 24S-hydroxycholesterol in relevant solvents and human plasma was confirmed. This method was successfully applied to quantify the plasma concentrations of 24S-hydroxycholesterol in male and female volunteers.

  13. Liquid microjunction surface sampling coupled with high-pressure liquid chromatography-electrospray ionization-mass spectrometry for analysis of drugs and metabolites in whole-body thin tissue sections.

    PubMed

    Kertesz, Vilmos; Van Berkel, Gary J

    2010-07-15

    In this work, a commercially available autosampler was adapted to perform direct liquid microjunction (LMJ) surface sampling followed by a high-pressure liquid chromatography (HPLC) separation of the extract components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the utility of coupling a separation with this direct liquid extraction based surface sampling approach, four different organs (brain, lung, kidney, and liver) from whole-body thin tissue sections of propranolol dosed and control mice were examined. The parent drug was observed in the chromatograms of the surface sampling extracts from all the organs of the dosed mouse examined. In addition, two isomeric phase II metabolites of propranolol (an aliphatic and an aromatic hydroxypropranolol glucuronide) were observed in the chromatograms of the extracts from lung, kidney, and liver. Confirming the presence of one or the other or both of these glucuronides in the extract from the various organs was not possible without the separation. These drug and metabolite data obtained using the LMJ surface sampling/HPLC-MS method and the results achieved by analyzing similar samples by conventional extraction of the tissues and subsequent HPLC-MS analysis were consistent. The ability to directly and efficiently sample from thin tissue sections via a liquid extraction and then perform a subsequent liquid phase separation increases the utility of this liquid extraction surface sampling approach.

  14. Quantitative analysis of selegiline and three metabolites (N-desmethylselegiline, methamphetamine, and amphetamine) in human plasma by high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Slawson, Matthew H; Taccogno, James L; Foltz, Rodger L; Moody, David E

    2002-10-01

    This report describes a sensitive and specific high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry method for the detection of subnanogram concentrations of selegiline and its three principle metabolites, N-desmethylselegiline, methamphetamine, and amphetamine, in human plasma. The assay has a dynamic range of 0.1-20 ng/mL for selegiline and N-desmethylselegiline (norselegiline) and 0.2-20 ng/mL for methamphetamine and amphetamine. The inter- and intra-assay precision and accuracy varied by less than 11% for all analytes at 0.3, 2.5, and 15 ng/mL and less than 16% at the lower limit of quantitation (0.1 ng/mL for selegiline and norselegiline; and 0.2 ng/mL for methamphetamine and amphetamine). Selegiline and its metabolites showed no significant loss in quantitative accuracy after three freeze/thaw cycles or after up to 6 h at room temperature prior to extraction. Extracted plasma samples retained quantitative accuracy after storage for at least 7 days at -20 degrees C or up to 70 h at room temperature. Methanolic stock solutions were stable for at least 6 h when kept at room temperature or at least 90 days when kept at -20 degrees C.

  15. Mass resolved resonance ionization spectroscopy of combustion radicals

    SciTech Connect

    Not Available

    1992-06-23

    This report discusses the following topics: REMPI spectroscopy of HCO and DCO; Rempi spectroscopy of the ethynyl radical; REMPI spectroscopy of new electronic states of C{sub 2}; and a flame sampling laser ionization mass spectrometer.

  16. Mass resolved resonance ionization spectroscopy of combustion radicals

    SciTech Connect

    Not Available

    1992-06-23

    This report discusses the following topics: REMPI spectroscopy of HCO and DCO; Rempi spectroscopy of the ethynyl radical; REMPI spectroscopy of new electronic states of C{sub 2}; and a flame sampling laser ionization mass spectrometer.

  17. Real-time monitoring of volatile organic compounds using chemical ionization mass spectrometry

    DOEpatents

    Mowry, Curtis Dale; Thornberg, Steven Michael

    1999-01-01

    A system for on-line quantitative monitoring of volatile organic compounds (VOCs) includes pressure reduction means for carrying a gaseous sample from a first location to a measuring input location maintained at a low pressure, the system utilizing active feedback to keep both the vapor flow and pressure to a chemical ionization mode mass spectrometer constant. A multiple input manifold for VOC and gas distribution permits a combination of calibration gases or samples to be applied to the spectrometer.

  18. A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

    PubMed

    Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

    2016-06-01

    In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples.

  19. Resonance ionization mass spectrometry for isotopic abundance measurements

    NASA Technical Reports Server (NTRS)

    Miller, C. M.

    1986-01-01

    Resonance ionization mass spectrometry (RIMS) is a relatively new laser-based technique for the determination of isotopic abundances. The resonance ionization process depends upon the stepwise absorption of photons from the laser, promoting atoms of the element of interest through progressively higher electronic states until an ion is formed. Sensitivity arises from the efficiency of the resonant absorption process when coupled with the power available from commercial laser sources. Selectivity derives naturally from the distinct electronic structure of different elements. This isobaric discrimination has provided the major impetus for development of the technique. Resonance ionization mass spectrometry was used for analysis of the isotopic abundances of the rare earth lutetium. Isobaric interferences from ytterbium severely effect the ability to measure small amounts of the neutron-deficient Lu isotopes by conventional mass spectrometric techniques. Resonance ionization for lutetium is performed using a continuous-wave laser operating at 452 nm, through a sequential two-photon process, with one photon exciting the intermediate resonance and the second photon causing ionization. Ion yields for microgram-sized quantities of lutetium lie between 10(6) and 10(7) ions per second, at overall ionization efficiencies approaching 10(-4). Discrimination factors against ytterbium greater than 10(6) have been measured. Resonance ionization for technetium is also being explored, again in response to an isobaric interference, molybdenum. Because of the relatively high ionization potential for Tc, three-photon, two-color RIMS processes are being developed.

  20. Mass analyzed threshold ionization (MATI) with VUV radiation

    NASA Astrophysics Data System (ADS)

    Kostko, Oleg; Kim, Sang Kyu; Wilson, Kevin R.; Leone, Stephen R.; Ahmed, Musahid

    2009-05-01

    Mass analyzed threshold ionization is a combination of threshold ionization spectroscopy with mass spectrometry. Similar to zero electron kinetic energy (ZEKE), MATI spectroscopy takes advantage of the field ionization of long lived high Rydberg states to obtain an ionization threshold and perform spectroscopy on the resulting cation. MATI at the synchrotron utilizing tunable VUV light opens up a novel way to perform spectroscopy on ions and improve the resolution in ionization energy determination in comparison with conventional photoionization efficiency curve measurements. This method is implemented at the Advanced Light Source and vibrationally-resolved MATI spectra for simple di- and polyatomic molecules (O2, N2, H2O, N2O, C2H2, and C6H6) are measured. This preliminary work allows us to test the applicability of MATI at a synchrotron and prepare for investigation of more complex systems such as mixtures of molecules, isomers and clusters.

  1. Quantitative determination of perfluorooctanoic acid ammonium salt in human serum by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

    Sottani, Cristina; Minoia, Claudio

    2002-01-01

    A sensitive, specific, accurate and reproducible analytical method was developed and validated to quantify perfluorooctanoic acid (PFOA) in human serum. After initial extraction with an ion-paring reagent, the procedure for quantifying PFOA is based on high-performance liquid chromatography (HPLC) interfaced to negative ion tandem mass spectrometry, operating in selected ion monitoring mode. The retention times of PFOA and its internal standard (D,L-malic acid) were 5.85 and 1.70 min, respectively. The assay was linear over the range 0-500 ng/mL, with a lower limit of quantification (LOQ) of 25 ng/mL, and with a coefficient of variation (CV) of 7.3%. The lower limit of detection (LOD) was assessed as 10 ng/mL. The overall precision and accuracy were assessed on three different days. The within- and between-day precision was < or =9.7 and 6.8%, respectively, and the accuracy was in the range 96-114%. The mean extracted recovery assessed at three different concentrations (100, 250, and 500 ng/mL) was always more than 85%. With this method no derivatization procedure was needed, thus avoiding possible thermal and chemical decomposition reactions of PFOA. The assay was applied to quantify perfluorooctanoic acid in serum from employees exposed to fluorochemicals commonly used in industrial applications for polymer production. The quantitative results for PFOA blood levels were found to vary between 100 and 982 ng/mL. Copyright 2002 John Wiley & Sons, Ltd.

  2. HPLC-atmospheric pressure chemical ionization mass spectrometric method for enantioselective determination of R,S-propranolol and R,S-hyoscyamine in human plasma.

    PubMed

    Siluk, Danuta; Mager, Donald E; Gronich, Naomi; Abernethy, Darrell; Wainer, Irving W

    2007-11-15

    A method for the simultaneous determination of R- and S-propranolol and R- and S-hyoscyamine in human plasma was developed, validated and applied to the analysis of samples from a clinical study. Sample preparation was performed by solid-phase extraction of 2 ml of human plasma using Oasis MCX cartridges and the enantioselective separations were achieved using a Chirobiotic V chiral stationary phase. The chromatography was carried out using gradient elution with a mobile phase composed of methanol:acetic acid:triethylamine which was varied from 100:0.05:0.04 to 100:0.05:0.1 (v/v/v) over 30 min and delivered at a flow rate 1 ml/min. The internal standard was R,S-propranolol-d7 and the analytes were quantified using a single quadrupole mass spectrometer employing APCI interface operated in the positive ion mode with single ion monitoring. The enantioselective separation factors, alpha, were 1.15 and 1.07 for S- and R-propranolol and R- and S-hyoscyamine, respectively. The standard curves were linear for all target compounds with coefficients of determination (r2) ranging from 0.9977 to 0.9999. The intra- and inter-day precision and accuracy were

  3. New ionization processes and applications for use in mass spectrometry.

    PubMed

    Trimpin, Sarah; Wang, Beixi; Lietz, Christopher B; Marshall, Darrell D; Richards, Alicia L; Inutan, Ellen D

    2013-01-01

    Mass spectrometry (MS) continues to improve at a rapid pace as most prominently witnessed for mass analyzers and fragmentation technology. Ionization methods have also seen resurgence with ambient ionization approaches gaining a foothold because they often provide a convenient and direct means of sample analysis. Nevertheless, a vast majority of biological analyses using MS apply electrospray ionization or matrix-assisted laser desorption/ionization, methods introduced in the 1980s, or variants thereof. To further advance applications by MS such as protein characterization, and, for example, addressing their location within specific cell types, the progress in mass analyzer and fragmentation technology needs to be matched with similar advances in ionization technology. It is imperative to seek ionization methods that more efficiently convert molecules, to gas-phase ions in a way that allows high transfer efficiency to the mass analyzer and subsequently the detector to achieve a more complete picture of sample composition. This review provides a snapshot of fundamental aspects of new ionization methods and potential biological and medical applications.

  4. Development of a new multi-residue laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry method for the detection and quantification of pesticides and pharmaceuticals in wastewater samples.

    PubMed

    Boisvert, Michel; Fayad, Paul B; Sauvé, Sébastien

    2012-11-19

    A new solid phase extraction (SPE) method coupled to a high throughput sample analysis technique was developed for the simultaneous determination of nine selected emerging contaminants in wastewater (atrazine, desethylatrazine, 17β-estradiol, ethynylestradiol, norethindrone, caffeine, carbamazepine, diclofenac and sulfamethoxazole). We specifically included pharmaceutical compounds from multiple therapeutic classes, as well as pesticides. Sample pre-concentration and clean-up was performed using a mixed-mode SPE cartridge (Strata ABW) having both cation and anion exchange properties, followed by analysis by laser diode thermal desorption atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). The LDTD interface is a new high-throughput sample introduction method, which reduces total analysis time to less than 15s per sample as compared to minutes with traditional liquid-chromatography coupled to tandem mass spectrometry (LC-MS/MS). Several SPE parameters were evaluated in order to optimize recovery efficiencies when extracting analytes from wastewater, such as the nature of the stationary phase, the loading flow rate, the extraction pH, the volume and composition of the washing solution and the initial sample volume. The method was successfully applied to real wastewater samples from the primary sedimentation tank of a municipal wastewater treatment plant. Recoveries of target compounds from wastewater ranged from 78% to 106%, the limit of detection ranged from 30 to 122ng L(-1) while the limit of quantification ranged from 90 to 370ng L(-1). Calibration curves in the wastewater matrix showed good linearity (R(2)≥0.991) for all target analytes and the intraday and interday coefficient of variation was below 15%, reflecting a good precision.

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

    DOEpatents

    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.

  6. Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

    USGS Publications Warehouse

    Thurman, E.M.; Ferrer, I.; Barcelo, D.

    2001-01-01

    An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

  7. Electrospray Ionization Mass Spectrometry of hexanitrohexaazaisowurtzitane (CL-20)

    SciTech Connect

    Campbell, James A.; Szecsody, Jim E.; Devary, Brooks J.; Valenzuela, Blandina R.

    2007-09-03

    Hexanitrohexaazaisowurtzitane, (C6H6N12O12, MW 438) {CL-20}, is a high-energy propellent that has been recently developed and successfully tested (Nielsen et al. 1998). CL-20 releases more energy on ignition and is more stable to accidental detonation than currently used energetic materials. It is expected to replace many of the energetic materials currently being used by the Department of Defense (DoD). The EPA method 8330 (EPA 1997) for the analysis of explosives and metabolites in soils calls for the use of UV/Vis detection. High performance liquid chromatography has been used to quantify CL-20 and precursor concentration (Bazaki et al. 1998`) at relatively high concentrations. Fourier transform infrared (FTIR) spectroscopy has been used to identify different crystal forms of CL-20 (4 isomers; Kim et al. 1998). Campbell et al. (1997) utilized particle beam mass spectrometry for the analysis of enzymatic degradation of explosives. Introduction and recent improvements of ionization techniques such as electrospray (ES) have allowed the mass spectrometer to become more widely used in liquid chromatography. Schilling(1996) also examined explosive components and metabolites using electrospray (ES) and atmospheric pressure chemical ionization (APCI) liquid chromatography/mass spectrometry (LC/MS). Schilling’s results showed that compared to thermospray LC/MS, APCI and ES were more sensitive than thermospray by at least an order of magnitude. 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 10 nitroso-RDX metabolites, and other munitions in ground water have been analyzed using solid phase extraction and isotope dilution liquid chromatography-APCI mass spectrometry (Cassada et al. 1999). The method detection limits indicate that nitramine and nitroaromatic compounds can be routinely determined in ground water samples using electrospray LC/MS with concentration techniques utilizing solid-phase extraction. Miller et al. (1996) studied nitrated explosives with mobile phase

  8. Low pressure electrospray ionization system and process for effective transmission of ions

    DOEpatents

    Tang, Keqi [Richland, WA; Page, Jason S [Kennewick, WA; Kelly, Ryan T [West Richland, WA; Smith, Richard D [Richland, WA

    2012-05-08

    Systems and methods that provide up to complete transmission of ions between coupled stages with low effective ion losses. An "interfaceless" electrospray ionization system is further described that operates an electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer. Furthermore, chambers maintained at different pressures can allow for more optimal operating conditions for an electrospray emitter and an ion guide.

  9. Characterization of Nitrogen-Containing Species in Coal and Petroleum-Derived Products by Ammonia Chemical Ionization-High Resolution Mass Spectrometry

    SciTech Connect

    Veloski, Garret A.; Lynn, Ronald J.; Sprecher, Richard F.

    1997-01-01

    A coal-derived light distillate and a petroleum-derived residuum have been studied by high resolution mass spectrometry using both low-pressure ammonia chemical ionization and low-voltage electron impact ionization. A mass calibration mixture for use with ammonia chemical ionization has been developed. Selective ionization of the basic nitrogen-containing compounds by ammonia chemical ionization and compound type characterization of the resulting quasi-molecular species has been demonstrated. Several homologous series of nitrogen-containing compounds were identified in a basic extract by electron impact ionization and compared with quasimolecular analogs identified by ammonia chemical ionization.

  10. Pressurized rf cavities in ionizing beams

    DOE PAGES

    Freemire, B.; Tollestrup, A.  V.; Yonehara, K.; ...

    2016-06-20

    A muon collider or Higgs factory requires significant reduction of the six dimensional emittance of the beam prior to acceleration. One method to accomplish this involves building a cooling channel using high pressure gas filled radio frequency cavities. The performance of such a cavity when subjected to an intense particle beam must be investigated before this technology can be validated. To this end, a high pressure gas filled radio frequency (rf) test cell was built and placed in a 400 MeV beam line from the Fermilab linac to study the plasma evolution and its effect on the cavity. Hydrogen, deuterium, helium and nitrogen gases were studied. Additionally, sulfur hexafluoride and dry air were used as dopants to aid in the removal of plasma electrons. Measurements were made using a variety of beam intensities, gas pressures, dopant concentrations, and cavity rf electric fields, both with and without a 3 T external solenoidal magnetic field. In conclusion, energy dissipation per electron-ion pair, electron-ion recombination rates, ion-ion recombination rates, and electron attachment times to SFmore » $$_6$$ and O$$_2$$ were measured.« less

  11. Pressurized rf cavities in ionizing beams

    NASA Astrophysics Data System (ADS)

    Freemire, B.; Tollestrup, A. V.; Yonehara, K.; Chung, M.; Torun, Y.; Johnson, R. P.; Flanagan, G.; Hanlet, P. M.; Collura, M. G.; Jana, M. R.; Leonova, M.; Moretti, A.; Schwarz, T.

    2016-06-01

    A muon collider or Higgs factory requires significant reduction of the six dimensional emittance of the beam prior to acceleration. One method to accomplish this involves building a cooling channel using high pressure gas filled radio frequency cavities. The performance of such a cavity when subjected to an intense particle beam must be investigated before this technology can be validated. To this end, a high pressure gas filled radio frequency (rf) test cell was built and placed in a 400 MeV beam line from the Fermilab linac to study the plasma evolution and its effect on the cavity. Hydrogen, deuterium, helium and nitrogen gases were studied. Additionally, sulfur hexafluoride and dry air were used as dopants to aid in the removal of plasma electrons. Measurements were made using a variety of beam intensities, gas pressures, dopant concentrations, and cavity rf electric fields, both with and without a 3 T external solenoidal magnetic field. Energy dissipation per electron-ion pair, electron-ion recombination rates, ion-ion recombination rates, and electron attachment times to SF6 and O2 were measured.

  12. Desorption electrospray ionization mass spectrometry of intact bacteria

    USDA-ARS?s Scientific Manuscript database

    Desorption electrospray ionization (DESI) mass spectrometry (MS) was used to differentiate 7 bacterial species based on their measured DESI-mass spectral profile. Both Gram positive and Gram negative bacteria were tested and included Escherichia coli, Staphyloccocus aureus, Enterococcus sp., Bordete...

  13. Single drop microextraction as a concentrating probe for rapid screening of low molecular weight drugs from human urine in atmospheric-pressure matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Shrivas, Kamlesh; Wu, Hui-Fen

    2007-01-01

    The present work reports the development of a new analytical procedure for simple and rapid screening of low molecular weight drugs (<500 Da) from human urine samples by atmospheric-pressure matrix-assisted laser desorption/ionization mass spectrometry (AP-MALDI-MS) combined with single drop microextraction (SDME). The success of the proposed method is due to the use of methyltrioctylammonium chloride (MTOAC) as additive to avoid the noise arising from the matrix ions (alpha-cyano-4-hydroxycinnamic acid (CHCA)). SDME also aided in alleviating the interferences arising from other matrix ions present in the urine samples prior to AP-MALDI-MS analysis. Factors affecting the extraction efficiency of drugs, such as selection of solvent, stirring speed, extraction time, exposure volume of extraction phase and salt addition, have been optimized. The optimum molar ratio of CHCA/MTOAC that gave the minimum background noise of CHCA ions was 700:1. The limit of detection (LOD) and relative standard deviation (RSD) of the method were in the ranges 0.3-1.6 microM and 7.8-11.4%, respectively. The SDME method was compared with liquid-liquid extraction (LLE) and hollow fiber liquid-phase microextraction (HF-LPME) to evaluate the compatibility of the present method in the extraction of drugs from urine samples. The role of MTOAC as matrix ion signal suppressor and SDME as analyte-separating device in the rapid screening of low molecular weight drugs from human urine samples using AP-MALDI/MS has been reported. Copyright (c) 2007 John Wiley & Sons, Ltd.

  14. A novel derivatization method for the determination of Fosfomycin in human plasma by liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometric detection via phase transfer catalyzed derivatization.

    PubMed

    Papakondyli, Theodora A; Gremilogianni, Aikaterini M; Megoulas, Nikolaos C; Koupparis, Michael A

    2014-03-07

    An analytical method employing novel sample preparation and liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometric detection (LC-APCI/MS) was developed for the determination of fosfomycin in human plasma. Sample preparation involves derivatization through phase transfer catalysis (PTC) which offers multiple advantages due to the simultaneous extraction, preconcentration and derivatization of the analyte. Using a PT catalyst, fosfomycin was extracted from plasma in an organic phase and, then converted to a pentafluorobenzyl ester with the use of pentafluorobenzyl bromide (PFBBr) derivatization reagent. The method was fully optimized by taking into account both PTC and derivatization parameters. Several catalysts, in a wide range of concentrations, with different counter ions and polarities were tested along with different extraction solvents and pH values. Thereafter, the derivatization procedure was optimized by altering the amount of the derivatization reagent, the temperature of the reaction and finally, the derivatization duration. As internal standard (I.S.) ethylphosphonic acid was chosen and underwent the same pretreatment. The derivatives were separated on a pentafluorophenyl (PFP)-C18 analytical column, which provides unique selectivity, using an isocratic elution with acetonitrile-water (70-30, v/v). The method was validated according to US Food and Drug Administration (FDA) guidelines and can be used for a bioequivalence study of fosfomycin in human plasma. The correlation coefficient (r(2)) of the calibration curve of spiked plasma solutions in the range of 50-12000 ng/mL was found greater than 0.999 with a limit of quantitation (LOQ) equal to 50 ng/ml (for 500 μL plasma sample). Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Quantification of β-carotene, retinol, retinyl acetate and retinyl palmitate in enriched fruit juices using dispersive liquid-liquid microextraction coupled to liquid chromatography with fluorescence detection and atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Hernández-Córdoba, Manuel

    2013-02-01

    A detailed optimization of dispersive liquid-liquid microextraction (DLLME) was carried out for developing liquid chromatographic (HPLC) techniques, using both fluorescence and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of preforms of vitamin A: retinol (R), retinyl acetate (RA), retinyl palmitate (RP) and β-carotene (β-C). The HPLC analyses were carried out using a mobile phase composed of methanol and water, with gradient elution. The APCI-MS and fluorescence spectra permitted the correct identification of compounds in the analyzed samples. Parameters affecting DLLME were optimized using 2 mL of methanol (disperser solvent) containing 150 μL carbon tetrachloride (extraction solvent). The precision ranged from 6% to 8% (RSD) and the limits of detection were between 0.03 and 1.4 ng mL(-1), depending on the compound. The enrichment factor values were in the 21-44 range. Juice samples were analyzed without saponification and no matrix effect was found when using fluorescence detection, so calibration was possible with aqueous standards. However, a matrix effect appeared with APCI-MS, in which case it was necessary to apply matrix-matched calibration. There was great variability in the forms of vitamin A present in the juices, the most abundant ester being retinyl acetate (0.04 to 3.4 μg mL(-1)), followed by the amount of retinol (0.01 to 0.16 μg mL(-1)), while retinyl palmitate was not detected, except in the milk-containing juice, in which RP was the main form. The representative carotenoid β-carotene was present in the orange, peach, mango and multifruit juices in high amounts. The method was validated using two certified reference materials. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. A rapid and simple method for the simultaneous determination of four endogenous monoamine neurotransmitters in rat brain using hydrophilic interaction liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry.

    PubMed

    Zhou, Wenbin; Zhu, Bangjie; Liu, Feng; Lyu, Chunming; Zhang, Shen; Yan, Chao; Cheng, Yu; Wei, Hai

    2015-10-01

    Endogenous monoamine neurotransmitters play an essential role in neural communication in mammalians. Many quantitative methods for endogenous monoamines have been developed during recent decades. Yet, matrix effect was usually a challenge in the quantification, in many cases asking for tedious sample preparation or sacrificing sensitivity. In this work, a simple, fast and sensitive method with no matrix effect was developed to simultaneously determine four endogenous monoamines including serotonin, dopamine, epinephrine and norepinephrine in rat brain tissues, using hydrophilic interaction liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry. Various conditions, including columns, chromatographic conditions, ion source, MS/MS conditions, and brain tissue preparation methods, were optimized and validated. Pre-weighed 20mg brain sample could be effectively and reproducibly homogenized and protein-precipitated by 20 times value of 0.2% formic acid in cold organic solvents (methanol-acetonitrile, 10:90, v/v). This method exhibited excellent linearity for all analytes (regression coefficients>0.998 or 0.999). The precision, expressed as coefficients of variation, was less than 3.43% for intra-day analyses and ranged from 4.17% to 15.5% for inter-day analyses. Good performance was showed in limit of detection (between 0.3nM and 3.0nM for all analytes), recovery (90.8-120%), matrix effect (84.4-107%), accuracy (89.8-100%) and stability (88.3-104%). The validated method was well applied to simultaneously determine the endogenous serotonin, dopamine, epinephrine and norepinephrine in four brain sections of 18 Wistar rats. The quantification of four endogenous monoamines in rat brain performed excellently in the sensitivity, high throughput, simple sample preparation and matrix effect. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. An improved high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry method for determination of chlorophylls and their derivatives in freeze-dried and hot-air-dried Rhinacanthus nasutus (L.) Kurz.

    PubMed

    Kao, Tsai Hua; Chen, Chia Ju; Chen, Bing Huei

    2011-10-30

    Rhinacanthus nasutus (L.) Kurz, a traditional Chinese herb possessing antioxidant and anti-cancer activities, has been reported to contain functional components like carotenoids and chlorophylls. However, the variety and amount of chlorophylls remain uncertain. The objectives of this study were to develop a high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry (HPLC-DAD-APCI-MS) method for determination of chlorophylls and their derivatives in hot-air-dried and freeze-dried R. nasutus. An Agilent Eclipse XDB-C18 column and a gradient mobile phase composed of methanol/N,N-dimethylformamide (97:3, v/v), acetonitrile and acetone were employed to separate internal standard zinc-phthalocyanine plus 12 cholorophylls and their derivatives within 21 min, including chlorophyll a, chlorophyll a', hydroxychlorophyll a, 15-OH-lactone chlorophyll a, chlorophyll b, chlorophyll b', hydroxychlorophyll b, pheophytin a, pheophytin a', hydroxypheophytin a, hydroxypheophytin a' and pheophytin b in hot-air-dried R. nasutus with flow rate at 1 mL/min and detection at 660 nm. But, in freeze-dried R. nasutus, only 4 chlorophylls and their derivatives, including chlorophyll a, chlorophyll a', chlorophyll b and pheophytin a were detected. Zinc-phthalocyanine was found to be an appropriate internal standard to quantify all the chlorophyll compounds. After quantification by HPLC-DAD, both chlorophyll a and pheophytin a were the most abundant in hot-air-dried R. nasutus, while in freeze-dried R. nasutus, chlorophyll a and chlorophyll b dominated.

  18. Direct and Convenient Mass Spectrometry Sampling with Ambient Flame Ionization

    PubMed Central

    Liu, Xiao-Pan; Wang, Hao-Yang; Zhang, Jun-Ting; Wu, Meng-Xi; Qi, Wan-Shu; Zhu, Hui; Guo, Yin-Long

    2015-01-01

    Recent innovations in ambient ionization technology for the direct analysis of various samples in their native environment facilitate the development and applications of mass spectrometry in natural science. Presented here is a novel, convenient and flame-based ambient ionization method for mass spectrometric analysis of organic compounds, termed as the ambient flame ionization (AFI) ion source. The key features of AFI ion source were no requirement of (high) voltages, laser beams and spray gases, but just using small size of n-butane flame (height approximately 1 cm, about 500 oC) to accomplish the rapid desorption and ionization for direct analysis of gaseous-, liquid- and solid-phase organic compounds, as well as real-world samples. This method has high sensitivity with a limit of detection of 1 picogram for propyphenazone, which allows consuming trace amount of samples. Compared to previous ionization methods, this ion source device is extremely simple, maintain-free, low-cost, user–friendly so that even an ordinary lighter (with n-butane as fuel) can achieve efficient ionization. A new orientation to mass spectrometry ion source exploitation might emerge from such a convenient, easy and inexpensive AFI ion source. PMID:26582511

  19. Direct and Convenient Mass Spectrometry Sampling with Ambient Flame Ionization

    NASA Astrophysics Data System (ADS)

    Liu, Xiao-Pan; Wang, Hao-Yang; Zhang, Jun-Ting; Wu, Meng-Xi; Qi, Wan-Shu; Zhu, Hui; Guo, Yin-Long

    2015-11-01

    Recent innovations in ambient ionization technology for the direct analysis of various samples in their native environment facilitate the development and applications of mass spectrometry in natural science. Presented here is a novel, convenient and flame-based ambient ionization method for mass spectrometric analysis of organic compounds, termed as the ambient flame ionization (AFI) ion source. The key features of AFI ion source were no requirement of (high) voltages, laser beams and spray gases, but just using small size of n-butane flame (height approximately 1 cm, about 500 oC) to accomplish the rapid desorption and ionization for direct analysis of gaseous-, liquid- and solid-phase organic compounds, as well as real-world samples. This method has high sensitivity with a limit of detection of 1 picogram for propyphenazone, which allows consuming trace amount of samples. Compared to previous ionization methods, this ion source device is extremely simple, maintain-free, low-cost, user-friendly so that even an ordinary lighter (with n-butane as fuel) can achieve efficient ionization. A new orientation to mass spectrometry ion source exploitation might emerge from such a convenient, easy and inexpensive AFI ion source.

  20. Improving N-Glycan Coverage using HPLC-MS with Electrospray Ionization at Subambient Pressure

    SciTech Connect

    Marginean, Ioan; Kronewitter, Scott R.; Moore, Ronald J.; Slysz, Gordon W.; Monroe, Matthew E.; Anderson, Gordon A.; Tang, Keqi; Smith, Richard D.

    2012-10-01

    Human serum glycan profiling with mass spectrometry (MS) has been employed to study several disease conditions and is demonstrating promise for e.g. clinical biomarker discovery. However, the poor glycan ionization efficiency and the large dynamic range of glycan concentrations in human sera hinder comprehensive profiling. In particular, large glycans are problematic because they are present at low concentrations and prone to fragmentation. Here we show that the sub-ambient pressure ionization with nanoelectrospray (SPIN)-MS can expand the serum glycome profile when compared with the conventional atmospheric pressure electrospray ionization (ESI)-MS with a heated capillary inlet. Notably, the ions generated by the SPIN interface were observed at higher charge states for 50% of the annotated glycans. Out of a total of 130 detected glycans, 34 were only detected with the SPIN-MS, resulting in improved coverage of glycan families as well as of glycans with larger numbers of labile monosaccharides.

  1. Determination of the first ionization potential of berkelium and californium by resonance ionization mass spectroscopy

    SciTech Connect

    Nunnemann, M.; Eberhardt, K.; Erdmann, N.; Herrmann, G.; Huber, G.; Koehler, S.; Kratz, J. V.; Naehler, A.; Passler, G.; Trautmann, N.

    1997-01-15

    Resonance ionization mass spectroscopy (RIMS) is used for the precise determination of the first ionization potential (IP) of transuranium elements. Small amounts of material ({approx_equal}0.4 ng) are sufficient for these measurements due to the high sensitivity of RIMS enabling the investigation of the actinides beyond plutonium, which are accessible only in limited amounts and difficult to handle due to their high radioactivity. The method presented takes advantage of the dependence of the ionization threshold on an external static electric field. With samples of 10{sup 12} atoms of {sup 249}Bk and {sup 249}Cf experimental values for the first ionization potentials of IP{sub Bk}=49989(2) cm{sup -1} and IP{sub Cf}=50665(2) cm{sup -1} were obtained.

  2. Determination of the first ionization potential of berkelium and californium by resonance ionization mass spectroscopy

    SciTech Connect

    Nunnemann, M.; Eberhardt, K.; Erdmann, N.; Herrmann, G.; Huber, G.; Koehler, S.; Kratz, J.V.; Naehler, A.; Passler, G.; Trautmann, N.

    1997-01-01

    Resonance ionization mass spectroscopy (RIMS) is used for the precise determination of the first ionization potential ({ital IP}) of transuranium elements. Small amounts of material ({approx}0.4ng) are sufficient for these measurements due to the high sensitivity of RIMS enabling the investigation of the actinides beyond plutonium, which are accessible only in limited amounts and difficult to handle due to their high radioactivity. The method presented takes advantage of the dependence of the ionization threshold on an external static electric field. With samples of 10{sup 12} atoms of {sup 249}Bk and {sup 249}Cf experimental values for the first ionization potentials of IP{sub Bk}=49989(2)cm{sup {minus}1} and IP{sub Cf}=50665(2)cm{sup {minus}1} were obtained. {copyright} {ital 1997 American Institute of Physics.}

  3. Sensitive determination of RDX, nitroso-RDX metabolites, and other munitions in ground water by solid-phase extraction and isotope dilution liquid chromatography-atmospheric pressure electro-spray [correction of chemical] ionization mass spectrometry.

    PubMed

    Cassada, D A; Monson, S J; Snow, D D; Spalding, R F

    1999-06-04

    Recent improvements in the LC-MS interface have increased the sensitivity and selectivity of this instrument in the analysis of polar and thermally-labile aqueous constituents. Determination of RDX, nitroso-RDX metabolites, and other munitions was enhanced using LC-MS with solid-phase extraction, 15N3-RDX internal standard, and electrospray ionization (ESI) in negative ion mode. ESI produced a five-fold increase in detector response over atmospheric pressure chemical ionization (APCI) for the nitramine compounds, while the more energetic APCI produced more than twenty times the ESI response for nitroaromatics. Method detection limits in ESI for nitramines varied from 0.03 microgram l-1 for MNX to 0.05 microgram l-1 for RDX.

  4. Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

    SciTech Connect

    Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

    2008-10-15

    A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

  5. Characterization of a distributed plasma ionization source (DPIS) for ion mobility spectrometry and mass spectrometry.

    PubMed

    Waltman, Melanie J; Dwivedi, Prabha; Hill, Herbert H; Blanchard, William C; Ewing, Robert G

    2008-10-19

    A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry (MS) and ion mobility spectrometry (IMS). The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H(2)O)(n)H(+) with (H(2)O)(2)H(+) as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO(3)(-), NO(3)(-), NO(2)(-), O(3)(-) and O(2)(-) of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and amines were selected to evaluate the new ionization source. The source was operated continuously for 3 months and although surface deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions.

  6. Atmospheric pressure laser desorption/ionization of plant metabolites and plant tissue using colloidal graphite.

    PubMed

    Perdian, D C; Schieffer, G M; Houk, R S

    2010-02-01

    Colloidal graphite is a promising matrix for atmospheric pressure laser desorption/ionization mass spectrometry. Intact [M+H](+) and [M-H](-) ions are readily produced from a wide range of small molecule plant metabolites, particularly anthocyanins, fatty acids, lipids, glycerides, and ceramides. Compared with a more traditional organic acid matrix, colloidal graphite provides more efficient ionization for small hydrophobic molecules and has a much cleaner background spectrum, especially in negative ion mode. Some important metabolites, e.g., fatty acids and glycosylated flavonoids, can be observed from Arabidopsis thaliana leaf and flower petal tissues in situ. Copyright (c) 2010 John Wiley & Sons, Ltd.

  7. Mass analyzed threshold ionization spectroscopy of p-fluorostyrene

    NASA Astrophysics Data System (ADS)

    Georgiev, S.; Neusser, H. J.; Chakraborty, Tapas

    2004-05-01

    Adiabatic ionization energy (AIE) and two-color threshold ion vibrational spectra of p-fluorostyrene have been measured by mass analyzed threshold ionization (MATI) method via three different intermediate levels in the first excited state, vibrationless S1 origin, 421411, and 231 vibronic levels. Features of the ion vibrational spectra indicates that the geometry of the molecular ion including the conformation of the vinyl chain in the ionic ground state (D0) is almost identical to that of its neutral ground state (S0), and ionization has very little effect on the vibrational potentials of the aromatic ring modes. Comparison of the AIE with the reported value of styrene shows that fluorination at the para position of the aromatic ring has little effect on energy of the electron ejected in ionization process from the styrene chromophore.

  8. Electrochemical processes in electrospray ionization mass spectrometry

    PubMed

    Mora; Van Berkel GJ; Enke; Cole; Martinez-Sanchez; Fenn

    2000-08-01

    Editorial Comment Last month we presented, as a Special Feature, a set of five articles that constituted a Commentary on the fundamentals and mechanism of electrospray ionization (ESI). These articles produced some lively discussion among the authors on the role of electrochemistry in ESI. Six authors participated in a detailed exchange of views on this topic, the final results of which constitute this month's Special Feature. We particularly hope that younger scientists will find value in this month's Special Feature, not only for the science that it teaches but also what it reveals about the processes by which scientific conclusions are drawn. To a degree, the contributions part the curtains on these processes and show science in action. We sincerely thank the contributors to this discussion. The give and take of intellectual debate is not always easy, and to a remarkable extent this set of authors has maintained good humor and friendships, even when disagreeing strongly on substance. Graham Cooks and Richard Caprioli Copyright 2000 John Wiley & Sons, Ltd.

  9. Resonance ionization of rubidium in an ion trap mass spectrometer

    SciTech Connect

    Whitten, W.B.; Ramsey, J.M.; Goeringer, D.E.; Buckley, B.T.

    1990-01-01

    We have recently initiated a study of resonance ionization processes in a quadrupole ion storage trap. The trap is a commercially available Ion Trap Detector that uses the voltage dependence of ion mass instability to obtain a mass spectrum of the trapped ions. We have modified the trap to permit laser excitation of atomic and molecular species within the quadrupole electrodes. Mass resolved resonance ionization spectra have been obtained for NO and Rb, described below. Rb was selected for this study for a number of reasons. We want to explore the potential of the ion trap for high resolution (Doppler free) resonance ionization spectroscopy with CW laser excitation. Rb can be excited to upper Rydberg levels with a series of transitions that can be induced with commercially available semiconductor diode lasers. In addition, levels in the same energy range can be reached through two-photon processes with visible wavelength tunable dye lasers or with single-photon processes after the laser is frequency doubled. The upper Rydberg levels can be ionized by photons, electric field, or collisions. Collisional ionization of a reservoir of Rydberg atoms may be a sensitive scheme for detecting electronegative species. RB has two stable isotopes with nonzero nuclear spin so that isotopic and hyperfine splittings can be used to assess the spectral resolution that is attained.

  10. High-Pressure Photon Ionization Source for TOFMS and Its Application for Online Breath Analysis.

    PubMed

    Wang, Yan; Jiang, Jichun; Hua, Lei; Hou, Keyong; Xie, Yuanyuan; Chen, Ping; Liu, Wei; Li, Qingyun; Wang, Shuang; Li, Haiyang

    2016-09-20

    Photon ionization mass spectrometry (PI-MS) is a widely used technique for the online detection of trace substances in complex matrices. In this work, a new high-pressure photon ionization (HPPI) ion source based on a vacuum ultraviolet (VUV) Kr lamp was developed for time-of-flight mass spectrometry (TOFMS). The detection sensitivity was improved by elevating the ion source pressure to about 700 Pa. A radio frequency (RF)-only quadrupole was employed as the ion guide system following the HPPI source to achieve high ion transmission efficiency. In-source collision induced dissociation (CID) was conducted for accurate chemical identification by varying the voltage between the ion source and the ion guide. The high humidity of the breath air can promote the detection of some compounds with higher ionization potentials (IPs) that could not be well detected by single photon ionization (SPI) at low pressure. Under 100% relative humidity (37 °C), the limits of detection down to 0.015 ppbv (parts per billion by volume) for aliphatic and aromatic hydrocarbons were obtained. This HPPI-TOFMS system was preliminarily applied for online investigations of the exhaled breath from both healthy nonsmoker and smoker subjects, demonstrating its analytical capacity for complicated gases analysis. Subsequently, several frequently reported VOCs in the breath of healthy volunteers, i.e., acetone, isoprene, 2-butanone, ethanol, acetic acid, and isopropanol, were successfully identified and quantified.

  11. High-Compression-Ratio; Atkinson-Cycle Engine Using Low-Pressure Direct Injection and Pneumatic-Electronic Valve Actuation Enabled by Ionization Current and Foward-Backward Mass Air Flow Sensor Feedback

    SciTech Connect

    Harold Schock; Farhad Jaberi; Ahmed Naguib; Guoming Zhu; David Hung

    2007-12-31

    This report describes the work completed over a two and one half year effort sponsored by the US Department of Energy. The goal was to demonstrate the technology needed to produce a highly efficient engine enabled by several technologies which were to be developed in the course of the work. The technologies included: (1) A low-pressure direct injection system; (2) A mass air flow sensor which would measure the net airflow into the engine on a per cycle basis; (3) A feedback control system enabled by measuring ionization current signals from the spark plug gap; and (4) An infinitely variable cam actuation system based on a pneumatic-hydraulic valve actuation These developments were supplemented by the use of advanced large eddy simulations as well as evaluations of fuel air mixing using the KIVA and WAVE models. The simulations were accompanied by experimental verification when possible. In this effort a solid base has been established for continued development of the advanced engine concepts originally proposed. Due to problems with the valve actuation system a complete demonstration of the engine concept originally proposed was not possible. Some of the highlights that were accomplished during this effort are: (1) A forward-backward mass air flow sensor has been developed and a patent application for the device has been submitted. We are optimistic that this technology will have a particular application in variable valve timing direct injection systems for IC engines. (2) The biggest effort on this project has involved the development of the pneumatic-hydraulic valve actuation system. This system was originally purchased from Cargine, a Swedish supplier and is in the development stage. To date we have not been able to use the actuators to control the exhaust valves, although the actuators have been successfully employed to control the intake valves. The reason for this is the additional complication associated with variable back pressure on the exhaust valves when

  12. Quantitative matrix-assisted laser desorption/ionization mass spectrometry

    PubMed Central

    Roder, Heinrich; Hunsucker, Stephen W.

    2008-01-01

    This review summarizes the essential characteristics of matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOF MS), especially as they relate to its applications in quantitative analysis. Approaches to quantification by MALDI-TOF MS are presented and published applications are critically reviewed. PMID:19106161

  13. Comparison of the structures of triacylglycerols from native and transgenic medium-chain fatty acid-enriched rape seed oil by liquid chromatography--atmospheric pressure chemical ionization ion-trap mass spectrometry (LC-APCI-ITMS).

    PubMed

    Beermann, Christopher; Winterling, Nadine; Green, Angelika; Möbius, Michael; Schmitt, Joachim J; Boehm, Günther

    2007-04-01

    The sn position of fatty acids in seed oil lipids affects physiological function in pharmaceutical and dietary applications. In this study the composition of acyl-chain substituents in the sn positions of glycerol backbones in triacylglycerols (TAG) have been compared. TAG from native and transgenic medium-chain fatty acid-enriched rape seed oil were analyzed by reversed-phase high performance liquid chromatography coupled with online atmospheric-pressure chemical ionization ion-trap mass spectrometry. The transformation of summer rape with thioesterase and 3-ketoacyl-[ACP]-synthase genes of Cuphea lanceolata led to increased expression of 1.5% (w/w) caprylic acid (8:0), 6.7% (w/w) capric acid (10:0), 0.9% (w/w) lauric acid (12:0), and 0.2% (w/w) myristic acid (14:0). In contrast, linoleic (18:2n6) and alpha-linolenic acid (18:3n3) levels decreased compared with the original seed oil. The TAG sn position distribution of fatty acids was also modified. The original oil included eleven unique TAG species whereas the transgenic oil contained sixty. Twenty species were common to both oils. The transgenic oil included trioctadecenoyl-glycerol (18:1/18:1/18:1) and trioctadecatrienoyl-glycerol (18:3/18:3/18:3) whereas the native oil included only the latter. The transgenic TAG were dominated by combinations of caprylic, capric, lauric, myrisitic, palmitic (16:0), stearic (18:0), oleic (18:1n9), linoleic, arachidic (20:0), behenic (22:0), and lignoceric acids (24:0), which accounted for 52% of the total fat. In the original TAG palmitic, stearic, oleic, and linoleic acids accounted for 50% of the total fat. Medium-chain triacylglycerols with capric and lauric acids combined with stearic, oleic, linoleic, alpha-linolenic, arachidic, and gondoic acids (20:1n9) accounted for 25% of the transgenic oil. The medium-chain fatty acids were mainly integrated into the sn-1/3 position combined with the essential linoleic and alpha-linolenic acids at the sn-2 position. Eight species

  14. Subcellular analysis by laser ablation electrospray ionization mass spectrometry

    DOEpatents

    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.

  15. Low pressure electrospray ionization system and process for effective transmission of ions

    DOEpatents

    Tang, Keqi [Richland, WA; Page, Jason S [Kennewick, WA; Kelly, Ryan T [Wet Richland, WA; Smith, Richard D [Richland, WA

    2010-03-02

    A system and method are disclosed that provide up to complete transmission of ions between coupled stages with low effective ion losses. A novel "interfaceless" electrospray ionization system is further described that operates the electrospray at a reduced pressure such that standard electrospray sample solutions can be directly sprayed into an electrodynamic ion funnel which provides ion focusing and transmission of ions into a mass analyzer.

  16. Intracellular protein mass spectroscopy using mid-infrared laser ionization

    NASA Astrophysics Data System (ADS)

    Awazu, K.; Suzuki, S.

    2007-07-01

    Large-scale analysis of proteins, which can be regarded as functional biomolecule, assumes an important role in the life science. A MALDI using an ultraviolet laser (UV-MALDI) is one of ionization methods without fragmentation and has achieved conformation analysis of proteins. Recently, protein analysis has shifted from conformation analysis to functional and direct one that reserves posttranslational modifications such as the sugar chain addition and phosphorylation. We have proposed a MALDI using a mid-infrared tunable laser (IR-MALDI) as a new ionization method. IR-MALDI is promising because most biomolecules have a specific absorption in mid-infrared range, and IR-MALDI is expected to offer; (1) use of various matrices, (2) use of biomolecules such as water and lipid as the matrix, and (3) super-soft ionization. First, we evaluated the wavelength dependence of ionization of different matrices using a difference frequency generation (DFG) laser, which can tune the wavelength within a range from 5.5 to 10.0 μm. As results, ionization was specifically occurred at 5.8 μm which the C=O vibration stretching bond in matrix material and mass spectrum was observed. Next, protein mass spectrum was observed in the culture cells, MIN6, which secrete insulin, without the conventional cell-preparation processes. We demonstrate that the IR-MALDI has an advantage over the conventional method (UV-MALDI) in direct analysis of intracellular proteins.

  17. Mass analyzed threshold ionization spectroscopy of indazole cation

    NASA Astrophysics Data System (ADS)

    Su, Huawei; Pradhan, Manik; Tzeng, Wen Bih

    2005-08-01

    We have recorded the two-color resonant two-photon mass analyzed threshold ionization (MATI) spectra of indazole via four intermediate states. The adiabatic ionization energy of this molecule is determined to be 67 534 ± 5 cm -1. The observed MATI bands include in-plane ring bending as well as out-of-plane ring twisting and bending vibrations of the indazole cation. Comparing the present data with those of indole and 7-azaindole leads to a better understanding about the influence of the nitrogen atom in the aza-aromatic bicyclic system.

  18. Resonant Laser Ionization Mass Spectrometry: An Alternative to AMS?

    SciTech Connect

    Wendt, Klaus; Trautmann, N.; Bushaw, Bruce A.

    2001-02-15

    Resonant laser ionization mass spectrometry (RIMS) has developed into a versatile experimental method particularly concerning applications for highly selective ultratrace analaysis. Apart from providing nearly complete isobaric suspression and high overall efficiency, the possibolility for combining optical isotpic selectivity with that of hte mass spectrometer leads to remarkable specifications. The widespread analytical potential and applicability of different techniques based on resonant laser ionization is demonstrated in investigations on stable and radioactive ultratrace isotopes with the focus on applications which require high selectivity, concerning, e.g., the noble gas isotopes, 81,85KR, PU isotopes, 89,90SR, 99Tc and 41Ca. Selective ultratrace determination of these radioisotopes proved access to a variety of fundamental research problems in environmental sciences, geo- and cosmochemistry, archaeology, and biomedicine, which previously were often an exclusive domain for accelerator mass spectrometry (AMS).

  19. Analysis of lipids: metal oxide laser ionization mass spectrometry.

    PubMed

    McAlpin, Casey R; Voorhees, Kent J; Corpuz, April R; Richards, Ryan M

    2012-09-18

    Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has been used for lipid analysis; however, one of the drawbacks of this technique is matrix interference peaks at low masses. Metal oxide surfaces are described here for direct, matrix-free analysis of small (MW < 1000 Da) lipid compounds, without interferences in the resulting spectra from traditional matrix background peaks. Spectra from lipid standards produced protonated and sodiated molecular ions. More complex mixtures including vegetable oil shortening and lipid extracts from bacterial and algal sources provided similar results. Mechanistic insight into the mode of ionization from surface spectroscopy, negative ion mass spectrometry, and stable isotope studies is also presented. The metal oxide system is compared to other reported matrix-free systems.

  20. Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

    SciTech Connect

    Siegfried, M.

    2015-10-14

    The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For this study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.

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

    PubMed

    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 (<5 ppm), which may be attributed to its multifunctional role as metal chelator, preconcentrator, absorber, and reservoir of energy. Together with the comparison on the ionization behaviors of various metals having different ionization 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.

  2. Calculating Relative Ionization Probabilities of Plutonium for Resonance Ionization Mass Spectrometry to Support Nuclear Forensic Investigations

    NASA Astrophysics Data System (ADS)

    Lensegrav, Craig; Smith, Craig; Isselhardt, Brett

    2015-03-01

    Ongoing work seeks to apply the technology of Resonance Ionization Mass Spectrometry (RIMS) to problems related to nuclear forensics and, in particular, to the analysis and quantification of debris from nuclear detonations. As part of this effort, modeling and simulation methods are being applied to analyze and predict the potential for ionization by laser excitation of isotopes of both uranium and plutonium. Early work focused on the ionization potential of isotopes of uranium, and the present effort has expanded and extended the previous work by identifying and integrating new data for plutonium isotopes. In addition to extending the effort to this important new element, we have implemented more accurate descriptions of the spatial distribution of the laser beams to improve the accuracy of model predictions compared with experiment results as well as an ability to readily incorporate new experimental data as they become available. The model is used to estimate ionization cross sections and to compare relative excitation on two isotopes as a function of wavelength. This allows the study of sensitivity of these measurements to fluctuations in laser wavelength, irradiance, and bandwidth. We also report on initial efforts to include predictions of americium ionization probabilities into our modeling package. I would like to thank my co-authors, Gamani Karunasiri and Fabio Alves. My success is a product of their support and guidance.

  3. Plasma ionization under simulated ambient Mars conditions for quantification of methane by mass spectrometry.

    PubMed

    Taghioskoui, Mazdak; Zaghloul, Mona

    2016-04-07

    Ambient ionization techniques enable ion production in the native sample environment for mass spectrometry, without a need for sample preparation or separation. These techniques provide superior advantages over conventional ionization methods and are well developed and investigated for various analytical applications. However, employing ambient ionization techniques for in situ extra-terrestrial chemical analysis requires these techniques to be designed and developed according to the ambient conditions of extra-terrestrial environments, which substantially differ from the ambient conditions of Earth. Here, we report a plasma ionization source produced under simulated ambient Mars conditions for mass spectrometry. The plasma ionization source was coupled to a quadrupole mass spectrometer, and quantitative and qualitative analyses of trace amounts of methane, as an analyte of interest in Mars discovery missions, were demonstrated. The miniature plasma source was operational at a net power as low as ∼1.7 W in the pressure range of 4-16 Torr. A detection limit as low as ∼0.15 ppm (v/v) at 16 Torr for methane was demonstrated.

  4. Tissue-spray ionization mass spectrometry for raw herb analysis.

    PubMed

    Chan, Sharon Lai-Fung; Wong, Melody Yee-Man; Tang, Ho-Wai; Che, Chi-Ming; Ng, Kwan-Ming

    2011-10-15

    Tissue-spray ionization mass spectrometry is developed for the in situ chemical analysis of raw herbs under ambient conditions. We demonstrated that analyte molecules could be directly sprayed and ionized from solvent-wetted ginseng tissues upon the application of high electrical voltage to the tissue sample. Abundant phytochemicals/ metabolites, including ginsenosides, amino acids and oligosaccharides, could be detected from ginseng tissues when the tissue-spray experiments were conducted in positive ion mode. Thermally labile and easily hydrolyzed malonyl-ginsenosides were also detected in negative ion mode. The tissue-spray ionization method enables the direct detection of analytes from raw herb samples and preserves the sample integrity for subsequent morphological and/ or microscopic examination. In addition, this method is simple and fast for chemical profiling of wild-type and cultivated-type American ginsengs with differentiation. Copyright © 2011 John Wiley & Sons, Ltd.

  5. Resonance ionization mass spectroscopy for trace analysis of neptunium

    NASA Astrophysics Data System (ADS)

    Riegel, J.; Deißenberger, R.; Herrmann, G.; Köhler, S.; Sattelberger, P.; Trautmann, N.; Wendeler, H.; Ames, F.; Kluge, H.-J.; Scheerer, F.; Urban, F.-J.

    1993-05-01

    Resonance ionization mass spectroscopic (RIMS) measurements for trace analysis and spectroscopy of 237Np, the ecologically most important isotope of neptunium, are described. The chemical procedure for the separation of neptunium from aqueous samples as well as the preparation of filaments for RIMS are outlined. Several two- and three-step excitation schemes have been investigated in order to find suitable conditions for the sensitive detection of 237Np. Using a three-step, three-color excitation and ionization scheme an overall detection efficiency of 3×10-8 was obtained, resulting in a detection limit of 4×108 atoms (160 fg) of 237Np. The hyperfine structure splittings of the levels under investigation, which influence the detection limit, were measured. A new method to determine the first ionization potential (IP) was applied to neptunium yielding a value of IP=6.2655(2) eV.

  6. Mass analyzed threshold ionization spectroscopy of 7-azaindole cation

    NASA Astrophysics Data System (ADS)

    Lee Lin, Jung; Tzeng, Wen Bih

    2003-10-01

    The vibrationally resolved mass analyzed threshold ionization (MATI) spectra of jet-cooled 7-azaindole have been recorded by ionizing via four different intermediate levels. The adiabatic ionization energy of this molecule is determined to be 65 462±5 cm -1, which is greater than that of indole by 2871 cm -1. The vibrational spectra of 7-azaindole in the S 1 and D 0 states have been successfully assigned by comparing the measured frequencies with those of indole as well as the predicted values from the ab initio calculations. Detailed analysis on the MATI spectra shows that the structure of the cation is somewhat different from that of this species in the neutral S 1 state.

  7. Mass-Analyzed Threshold Ionization of LaO2

    NASA Astrophysics Data System (ADS)

    Wu, Lu; Zhang, Changhua; Krasnokutski, Sergiy; Yang, Dong-Sheng

    2010-06-01

    Lanthanum oxide, LaO2, is produced in a pulsed laser-vaporization metal-cluster source and studied by mass-analyzed threshold ionization (MATI) spectroscopy. From the MATI spectrum, the adiabatic ionization energy of LaO2 is determined to be 40134 (5) Cm-1 or 4.976 (6) eV, and La+-O stretching and O-La+-O bending frequencies are measured as 656 and 120 Cm-1. The measured ionization energy is about 3.0 eV lower than the value predicted by recent high-level ab initio calculations. In this talk, we will discuss the discrepancy between the experiment and theory and the electronic transition observed in our experiment. T. K. Todorova, I. Infante, L. Gagliardi, and J. M. Dyke, J. Phys. Chem. A 112, 7825 (2008).

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

    PubMed Central

    Huang, Yunguang; Li, Jinxu; Tang, Bin; Zhu, Liping; Hou, Keyong; Li, Haiyang

    2015-01-01

    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. PMID:26587023

  9. Electrospray ionizer for mass spectrometry of aerosol particles

    DOEpatents

    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.

  10. Evaluation of ionization techniques for mass spectrometric detection of contact allergenic hydroperoxides formed by autoxidation of fragrance terpenes.

    PubMed

    Nilsson, J; Carlberg, J; Abrahamsson, P; Hulthe, G; Persson, B-A; Karlberg, A-T

    2008-11-01

    Hydroperoxides formed by autoxidation of common fragrance terpenes are strong allergens and known to cause allergic contact dermatitis (ACD), a common skin disease caused by low molecular weight chemicals. Until now, no suitable methods for chemical analyses of monoterpene hydroperoxides have been available. Their thermolability prohibits the use of gas chromatography and their low UV-absorption properties do not promote sensitive analytical methods by liquid chromatography based on UV detection. In our study, we have investigated different liquid chromatography/mass spectrometry (LC/MS) ionization techniques, electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI), for detection of hydroperoxides from linalool and limonene.Flow injection analysis was used to evaluate the three different techniques to ionize the monoterpene hydroperoxides, linalool hydroperoxide and limonene hydroperoxide, by estimating the signal efficacy under experimental conditions for positive and negative ionization modes. The intensities for the species [M+H]+ and [M+H-H2O]+ in positive ionization mode and [M-H]- and [M-H-H2O]- in negative ionization mode were monitored. It was demonstrated that the mobile phase composition and instrumental parameters have major influences on the ionization efficiency of these compounds. ESI and APCI were both found to be appropriate as ionization techniques for detection of the two hydroperoxides. However, APPI was less suitable as ionization technique for the investigated hydroperoxides.

  11. Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.

    ERIC Educational Resources Information Center

    Cooks, R. G.; Busch, K. L.

    1982-01-01

    Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

  12. Products of the reaction between alpha- or gamma-tocopherol and nitrogen oxides analyzed by high-performance liquid chromatography with UV-visible and atmospheric pressure chemical ionization mass spectrometric detection.

    PubMed

    Nagata, Yoshiko; Matsumoto, Yohta; Kanazawa, Hideko

    2004-05-21

    The reaction products of alpha- or gamma-tocopherol with nitric oxide in the presence of molecular oxygen were isolated and characterized. The consumption of tocopherols and the formation of the major products were monitored by high-performance liquid chromatography (HPLC) by a gradient elution method. The quantitative analysis of these compounds with UV-Vis detectors, however, was interfered by several minor products having similar UV spectra and retention times as those of the major ones. In order to establish a quantitative analytical method for the products, we investigated other detection methods, and found that atmospheric pressure chemical ionization (APCI), LC-MS was a more selective and better analytical method for these compounds.

  13. High Sensitivity Combined with Extended Structural Coverage of Labile Compounds via Nanoelectrospray Ionization at Subambient Pressures

    DOE PAGES

    Cox, Jonathan T.; Kronewitter, Scott R.; Shukla, Anil K.; ...

    2014-09-15

    Subambient pressure ionization with nanoelectrospray (SPIN) has proven to be effective in producing ions with high efficiency and transmitting them to low pressures for high sensitivity mass spectrometry (MS) analysis. Here we present evidence that not only does the SPIN source improve MS sensitivity but also allows for gentler ionization conditions. The gentleness of a conventional heated capillary electrospray ionization (ESI) source and the SPIN source was compared by the liquid chromatography mass spectrometry (LC-MS) analysis of colominic acid. Colominic acid is a mixture of sialic acid polymers of different lengths containing labile glycosidic linkages between monomer units necessitating amore » gentle ion source. By coupling the SPIN source with high resolution mass spectrometry and using advanced data processing tools, we demonstrate much extended coverage of sialic acid polymer chains as compared to using the conventional ESI source. Additionally we show that SPIN-LC-MS is effective in elucidating polymer features with high efficiency and high sensitivity previously unattainable by the conventional ESI-LC-MS methods.« less

  14. Absolute pressure dependence of the second ionization level of EL2 in GaAs

    SciTech Connect

    Bliss, D.E.; Nolte, D.D.; Walukiewicz, W.; Haller, E.E. Department of Materials Science and Mineral Engineering, University of California at Berkeley, Berkeley, California 94720 ); Lagowski, J. )

    1990-03-19

    We report the results of deep level transient spectroscopy experiments with the second ionization level of the double donor defect (EL2) under uniaxial stress in {ital p}-type GaAs. We measure the shift in the hole emission rate as a function of stress applied in the (100) and (110) directions. By modeling the valence band with two independently displacing bands and appropriately derived effective masses, we determine the absolute hydrostatic pressure derivative of the defect to be 39{plus minus}15 meV GPa{sup {minus}1}. The shear contribution is negligible. These results are very different from those obtained for the first ionization level, which has a much higher absolute pressure derivative of 90 meV GPa{sup {minus}1}.

  15. Laser ionization and radiofrequency sustainment of high- pressure seeded plasmas

    NASA Astrophysics Data System (ADS)

    Kelly, Kurtis Lester

    2001-10-01

    The feasibility of using a low-ionization potential organic gas to initiate a high-pressure plasma discharge is examined. Laser photoionization of the organic gas creates a high-density initial condition that eliminates the need for capacitive breakdown to form the plasma. The seed gas, tetrakis(dimethylamino)ethylene, has an ionization potential of 6.1 eV and is ionized by an ultraviolet laser through 6.4 eV photon absorption forming a plasma column inside a vacuum chamber. The plasma absorbs power through collisional damping of the induced 13.56 MHz radiofrequency wave fields. The laser initiation of 2-6 mTorr of the seed gas in 1-150 Torr of argon is accomplished producing steady-state plasma densities of ne >= 1012 cm-3 in a volume of 300-500 cm3 with radiofrequency power densities of 3-10 Watts/cm3. Electron density measurements are taken using a millimeter wave interferometer. The dependence of the antenna radiation resistance and reactance on the plasma density and neutral gas pressure is measured, examined and compared to a transformer coupled equivalent circuit and to a computer model. The coupling can be described by propagation and absorption of the fields into a lossy plasma medium. Antenna design is aided by understanding the radial absorption profile of the inductive radiofrequency fields, and how these fields are excited by various antenna designs. It is found that the azimuthally symmetric helical coil excites the wave fields most conducive to sustaining the plasma at high pressure. The two-body recombination coefficient of the organic seed gas and its optimum partial pressure when mixed with argon at 50-150 Torr are experimentally determined. Particle losses and power requirements for maintaining the discharge are estimated by examining diffusion, two-body and three-body recombination processes. It is found that recombination losses play a dominant role at these high pressures which places an upper bound on the density that is achievable with the 2

  16. Application of multiphoton ionization mass spectrometry: protected dideoxyribonucleotides

    NASA Astrophysics Data System (ADS)

    Lindner, J.; Grotemeyer, J.

    1991-08-01

    This work demonstrates how IR-laser desorption of neutral molecules followed by resonantly enhanced multiphoton ionization can be employed to determine the molecular weight, base sequence of synthetic protected dinucleotides. All sixteen possible combinations of isomeric deoxyribodinucleotides which contain the phosphotriester linkage used in oligonucleotide synthesis have been investigated. The positively charged molecular ion was detected for each dinucleotide at low laser powers at an ionizing wavelength of 242.5 nm. In addition, fragment ions reflecting the primary structure were observed in the soft ionization mode. In the hard ionization mode intensive low mass fragment ions are formed by multiphoton absorption of the molecular ion. In this way the nucleic base composition of the dideoxyribonucleotide can be determined. Fragments containing the 5' end are preferentially detected indicating the high UV absorptivity of the aromatic protective function located at the 5' end. Beside absorption cross-sections, the stability of the N-glycosidic bond between the ribose, the nucleic base affects the intensity of both parent and daughter ions. By assigning the fragment ions generated by multiphoton absorption it is possible to distinguish isomeric sequences of these deoxyribodinucleotides. The influence of the type of the nucleobase and the position of the nucleoside with respect to the phosphate linkage on the relative intensities of the fragment ions are discussed.

  17. Ultra performance liquid chromatography coupled with electrospray and atmospheric pressure chemical ionization (ESCi)-quadrupole time-of-flight mass spectrometry with novel mass spectrometry(Elevated Energy) (MS(E)) data collection technique: determination and pharmacokinetics, tissue distribution and biliary excretion study of ergone in rat.

    PubMed

    Zhao, Ying-Yong; Cheng, Xian-Long; Wei, Feng; Bai, Xu; Lin, Rui-Chao

    2012-07-01

    Ergosta-4,6,8(14),22-tetraen-3-one (ergone) has been proved to have novel antitumor effects on HepG2 cells. The aim of this study was to investigate the pharmacokinetics, tissue distribution, and biliary excretion of ergone in rats following a single oral administration (5, 10, and 20 mg/kg). The levels of ergone in plasma, tissues, and bile were measured by ultra performance liquid chromatography coupled with electrospray and atmospheric pressure chemical ionization (ESCi)-quadrupole time-of-flight mass spectrometry with novel mass spectrometry(Elevated Energy) (MS(E)) data collection technique method. The results show ergone was distributed and eliminated from rat plasma and in non-linear pharmacokinetics from a dose range of 5-20 mg/kg. The ergone was found to distribute widely in the internal organs, with tissue concentrations in order of lungs, spleen, liver, intestine, kidneys, heart, stomach, parorchis, teasticles, and brain. At 12 h after dosing, the tissue concentrations in the organs were markedly decreased. The lungs, spleen, and liver were the dominant organs with high tissue concentrations that might be the primary sites for metabolism and elimination of ergone. Total recoveries of ergone within 24 h in bile were 34.14%.

  18. Mass-Analyzed Threshold Ionization Spectroscopy of 2-Phenylethanol: Probing of Conformational Changes Caused by Ionization

    NASA Astrophysics Data System (ADS)

    Georgiev, S.; Karaminkov, R.; Chervenkov, S.; Delchev, V.; Neusser, H. J.

    2009-10-01

    The vibrational structure of the ionic ground state of different conformers of the biologically relevant molecule 2-phenylethanol has been investigated by combination of two-photon two-color mass-analyzed threshold ionization spectroscopy (MATI) and quantum chemical calculations at M05, MP2, and coupled cluster (CC) levels of theory with extended basis sets. MATI spectra recorded via gauche vibronic bands are with poor structure and increasing background, whereas the ones measured via vibronic bands of the anti conformers feature well-resolved vibronic structure in the cation. Ab initio computations predict three stable conformers for the 2-phenylethanol cation out of five initial neutral structures. None of the theoretical structures in the cation features a nonclassical OH···π hydrogen bond in conjunction with the analysis of the MATI spectra. This provides clear evidence that the OH···π hydrogen bond stabilizing the lowest-energy gauche conformer in the neutral breaks upon ionization.

  19. Data-Independent Microbial Metabolomics with Ambient Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rath, Christopher M.; Yang, Jane Y.; Alexandrov, Theodore; Dorrestein, Pieter C.

    2013-08-01

    Atmospheric ionization methods are ideally suited for prolonged MS/MS analysis. Data-independent MS/MS is a complementary technique for analysis of biological samples as compared to data-dependent analysis. Here, we pair data-independent MS/MS with the ambient ionization method nanospray desorption electrospray ionization (nanoDESI) for untargeted analysis of bacterial metabolites. Proof-of-principle data and analysis are illustrated by sampling Bacillus subtilis and Pseudomonas aeruginosa directly from Petri dishes. We found that this technique enables facile comparisons between strains via MS and MS/MS plots which can be translated to chemically informative molecular maps through MS/MS networking. The development of novel techniques to characterize microbial metabolites allows rapid and efficient analysis of metabolic exchange factors. This is motivated by our desire to develop novel techniques to explore the role of interspecies interactions in the environment, health, and disease. This is a contribution to honor Professor Catherine C. Fenselau in receiving the prestigious ASMS Award for a Distinguished Contribution in Mass Spectrometry for her pioneering work on microbial mass spectrometry.

  20. Unexpected Analyte Oxidation during Desorption Electrospray Ionization - Mass Spectrometry

    SciTech Connect

    Pasilis, Sofie P; Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    During the analysis of surface spotted analytes using desorption electrospray ionization mass spectrometry (DESI-MS), abundant ions are sometimes observed that appear to be the result of oxygen addition reactions. In this investigation, the effect of sample aging, the ambient lab environment, spray voltage, analyte surface concentration, and surface type on this oxidative modification of spotted analytes, exemplified by tamoxifen and reserpine, during analysis by desorption electrospray ionization mass spectrometry was studied. Simple exposure of the samples to air and to ambient lighting increased the extent of oxidation. Increased spray voltage lead also to increased analyte oxidation, possibly as a result of oxidative species formed electrochemically at the emitter electrode or in the gas - phase by discharge processes. These oxidative species are carried by the spray and impinge on and react with the sampled analyte during desorption/ionization. The relative abundance of oxidized species was more significant for analysis of deposited analyte having a relatively low surface concentration. Increasing spray solvent flow rate and addition of hydroquinone as a redox buffer to the spray solvent were found to decrease, but not entirely eliminate, analyte oxidation during analysis. The major parameters that both minimize and maximize analyte oxidation were identified and DESI-MS operational recommendations to avoid these unwanted reactions are suggested.

  1. Clustering, methodology, and mechanistic insights into acetate chemical ionization using high-resolution time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Brophy, Patrick; Farmer, Delphine K.

    2016-08-01

    We present a comprehensive characterization of cluster control and transmission through the Tofwerk atmospheric pressure interface installed on various chemical ionization time-of-flight mass spectrometers using authentic standards. This characterization of the atmospheric pressure interface allows for a detailed investigation of the acetate chemical ionization mechanisms and the impact of controlling these mechanisms on sensitivity, selectivity, and mass spectral ambiguity with the aim of non-targeted analysis. Chemical ionization with acetate reagent ions is controlled by a distribution of reagent ion-neutral clusters that vary with relative humidity and the concentration of the acetic anhydride precursor. Deprotonated carboxylic acids are primarily detected only if sufficient declustering is employed inside the atmospheric pressure interface. The configuration of a high-resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) using an acetate chemical ionization source for non-targeted analysis is discussed. Recent approaches and studies characterizing acetate chemical ionization as it applies to the HR-TOF-CIMS are evaluated in light of the work presented herein.

  2. In situ mass analysis of particles by surface ionization mass spectrometry

    NASA Technical Reports Server (NTRS)

    Lassiter, W. S.; Moen, A. L.

    1974-01-01

    A qualitative study of the application of surface ionization and mass spectrometry to the in situ detection and constituent analysis of atmospheric particles was conducted. The technique consists of mass analysis of ions formed as a result of impingement of a stream of particles on a hot filament where, it is presumed, surface ionization takes place. Laboratory air particles containing K, Ca, and possibly hydrocarbons were detected. Other known particles such as Al2O3, Pb(NO3)2, and Cr2O3 were analyzed by detecting the respective metal atoms making up the particles. In some cases, mass numbers indicative of compounds making up the particles were detected showing surface ionization of particles sometimes leads to chemical analysis as well as to elemental analysis. Individual particles were detected, and it was shown that the technique is sensitive to Al2O3 particles with a mass of a few nanograms.

  3. Improved Imaging Resolution in Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kertesz, Vilmos; Van Berkel, Gary J

    2008-01-01

    Imaging resolution of desorption electrospray ionization mass spectrometry (DESI-MS) was investigated using printed patterns on paper and thin-layer chromatography (TLC) plate surfaces. Resolution approaching 40 m was achieved with a typical DESI-MS setup, which is approximately 5 times better than the best resolution reported previously. This improvement was accomplished with careful control of operational parameters (particularly spray tip-to-surface distance, solvent flow rate, and spacing of lane scans). Also, an appropriately strong analyte/surface interaction and uniform surface texture on the size scale no larger that the desired imaging resolution were required to achieve this resolution. Overall, conditions providing the smallest possible effective desorption/ionization area in the DESI impact plume region and minimizing the analyte redistribution on the surface during analysis led to the improved DESI-MS imaging resolution.

  4. Mass analyzed threshold ionization (MATI) spectroscopy of p-cresol

    NASA Astrophysics Data System (ADS)

    Shirhatti, P. R.; Wategaonkar, S.

    2012-03-01

    Experimental setup was developed for carrying out the mass analyzed threshold ionization (MATI) spectroscopy. Primary objective has been to carry out the vibronic spectroscopy of the novel hydrogen bonded complexes in the cationic state. To this end MATI spectroscopy is best suited for the purpose. This work presents the successful implementation of the same using p-cresol as a test case. This happens to be the prime substrate in most of our studies on weakly hydrogen bonded complexes that are dominated by the dispersion interaction contrary to the electrostatic nature of the conventional hydrogen bonds. The adiabatic ionization potential of p-cresol was determined as 65,904 ± 10 cm-1 which is in good agreement with the previously reported value. The MATI spectrum also shows a few vibronic bands of p-cresol cation.

  5. Surface Ionization and Soft Landing Techniques in Mass Spectrometry

    SciTech Connect

    Futrell, Jean H.; Laskin, Julia

    2010-04-01

    The advent of soft ionization techniques, notably electrospray and laser desorption ionization methods, has extended mass spectrometric methods to large molecules and molecular complexes. This both greatly expands appli¬cations of mass spectrometry and makes the activation and dissociation of complex ions an integral part of large molecule mass spectrometry. A corollary of the much greater number of internal degrees of freedom and high density of states associated with molecular complexity is that internal energies much higher than the dissociation energies for competing fragmentation processes are required for observable fragmentation in time scales sampled by mass spectrometers. This article describes the kinetics of surface-induced dissociation (SID), a particularly efficient activation method for complex ions. Two very important characteristics of SID are very rapid, sub-picosecond activation and precise control of ion internal energy by varying ion collision energy. The nature of the surface plays an important role in SID, determining both efficiency and mechanism of ion activation. Surface composition and morphology strongly influence the relative importance of competing reactions of SID, ion capture (soft-landing), surface reaction and neutralization. The important features of SID and ion soft-landing are described briefly in this review and more fully in the recommended reading list.

  6. Simultaneous extraction of acetylsalicylic acid and salicylic acid from human plasma and simultaneous estimation by liquid chromatography and atmospheric pressure chemical ionization/tandem mass spectrometry detection. Application to a pharmacokinetic study.

    PubMed

    Nirogi, Ramakrishna; Kandikere, Vishwottam; Mudigonda, Koteshwara; Ajjala, Devender; Suraneni, Ramakrishna; Thoddi, Parthasarathi

    2011-01-01

    A simple analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in atmospheric chemical ionization mode (APCI) for the simultaneous estimation of acetylsalicylic acid (ASA, CAS 50-78-2) and its active metabolite salicylic acid (SA, CAS 69-72-7) in human plasma has been developed and validated. ASA and SA were analyzed simultaneously despite differences in plasma concentration ranges of ASA and SA after oral administration of ASA. In spite of having different chemical, ionization and chromatographic properties, ASA and SA were extracted simultaneously from the plasma sample using acetonitrile protein precipitation followed by liquid-liquid extraction. The analytes were separated on a reversed phase column with rapid gradient program using mobile phase consisting of ammonium acetate buffer and methanol. The structural analogue diclofenac was used as an internal standard. The multiple reaction monitoring (MRM) transitions m/z 179 --> 137 for ASA, m/z 137 --> 65 for SA and m/z 294 --> 250 for IS were used. The assay exhibited a linear dynamic range of 0.02-10 microg/mL for ASA and 0.1-50 microg/mL for SA. The between-batch precision (%CV) ranged from 2.1 to 7.9% for ASA and from 0.2 to 5.2% for SA. The between-batch accuracy ranged from 95.4 to 96.7% for ASA and from 94.6 to 111.3% for SA. The validated method was successfully applied for the evaluation of pharmacokinetics of ASA after single oral administration of 650 mg test formulation versus two 325 mg reference formulations of ASA in human subjects.

  7. Ionization and transmission efficiency in an electrospray ionization-mass spectrometry interface

    SciTech Connect

    Page, Jason S.; Kelly, Ryan T.; Tang, Keqi; Smith, Richard D.

    2007-09-01

    The efficiency of sample ionization by electrospray ionization (ESI) and the transmission of the charged droplets and gas-phase ions through an ESI interface were investigated in order to advance the understanding of how these factors affect mass spectrometry (MS) sensitivity. In addition, the effects of the ES emitter distance to the inlet, solution flow rate, and inlet temperature to the ionization and transmission efficiency were characterized. Quantitative measurements of ES current loss throughout the ESI interface were accomplished by electrically isolating the front surface of the interface from the inner wall of the heated inlet capillary, enabling losses on the two surfaces to be distinguished. The ES current lost to the front surface of the ESI interface was also spatially profiled with a linear array of 340-µm-dia. electrodes placed adjacent to the inlet capillary entrance. Current transmitted as gas-phase ions was differentiated from charged droplets and solvent clusters by directly measuring sensitivity with a single quadrupole mass spectrometer. The study has revealed a large sampling efficiency into the inlet capillary (>90% at an emitter distance of 1 mm), a global rather than a local gas dynamic effect on the shape of the ES plume due to the gas flow conductance limit of the inlet capillary, a large (>80%) loss of analyte after transmission through the inlet due to incomplete desolvation at a solution flow rate of 1.0 µL/min, and a decrease in analyte peak intensity at lower temperatures, despite a large increase in ES current transmission efficiency. These studies provide a clearer understanding of the parameters affecting ion transmission into the mass spectrometer, and will serve to guide the design of more efficient instrument interfaces.

  8. Femtosecond laser ablation particle introduction to a liquid sampling-atmospheric pressure glow discharge ionization source

    SciTech Connect

    Carado, Anthony J.; Quarles, C. Derrick; Duffin, Andrew M.; Barinaga, Charles J.; Russo, Richard E.; Marcus, R. Kenneth; Eiden, Gregory C.; Koppenaal, David W.

    2012-01-01

    This work describes the use of a compact, liquid sampling – atmospheric pressure glow discharge (LS-APGD) ionization source to ionize metal particles within a laser ablation aerosol. Mass analysis was performed with a Thermo Scientific Exactive Mass Spectrometer which utilizes an orbitrap mass analyzer capable of producing mass resolution exceeding M/ΔM > 160,000. The LS-APGD source generates a low-power plasma between the surface of an electrolytic solution flowing at several µl min-1 through a fused silica capillary and a counter electrode consisting of a stainless steel capillary employed to deliver the laser ablation particles into the plasma. Sample particles of approximately 100 nm were generated with an Applied Spectra femtosecond laser located remotely and transported through 25 meters of polyurethane tubing by means of argon carrier gas. Samples consisted of an oxygen free copper shard, a disk of solder, and a one-cent U.S. coin. Analyte signal onset was readily detectable relative to the background signal produced by the carrier gas alone. The high mass resolution capability of the orbitrap mass spectrometer was demonstrated on the solder sample with resolution exceeding 90,000 for Pb and 160,000 for Cu. In addition, results from a laser ablation depth-profiling experiment of a one cent coin revealed retention of the relative locations of the ~10 µm copper cladding and zinc rich bulk layers.

  9. Evaluation of pulsed fast-atom bombardment ionization for increased sensitivity of tandem mass spectrometry

    SciTech Connect

    Tecklenburg, R.E. Jr.; Castro, M.E.; Russell, D.H.

    1989-01-15

    The use of pulsed valves for performing fast-atom bombardment (FAB) ionization on a sector ion-beam mass spectrometer is described. The objective of this work is to establish new methods for improving the sensitivity of tandem mass spectrometry. This paper deals with the use of pulsed FAB for improving total ion yields as well as signal-to-noise ratios for collision-induced dissociation and laser-ion beam photodissociation. Pulsing the neutral gas pressure used for FAB ionization results in neutral primary beam densities much greater (by a factor of 10) than those obtainable for continuous FAB. This approach yields enhancements for total ion yields and collision-induced dissociation signals by a factor of 15, while larger gains (> 28) are measured for the comparable photodissociation experiment.

  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

    SciTech Connect

    Perdian, David C.

    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. The Effects of Partial Ionization on Prominence Mass Formation

    NASA Astrophysics Data System (ADS)

    Karpen, J. T.; Olson, K.; DeVore, C. R.; Martinez Gomez, D.; Sokolov, I.

    2015-12-01

    The origin of the prominence mass has been an open question since this cool plasma suspended in the hot corona was first discovered. We have known for a long time that the mass must come from the chromosphere, but it is unclear whether this mass is lifted bodily through magnetic levitation, injected by reconnection-driven upflows, or driven from the chromosphere by evaporation and then condensed. One evaporation-condensation scenario, the thermal nonequilibrium (TNE) model, is the most fully developed, quantitative model for the prominence plasma to date. In the TNE scenario, localized heating concentrated at the coronal loop footpoints produces chromospheric evaporation, filling the flux tube with hot, dense plasma that subsequently collapses radiatively to form cool condensations. Thus far this model has been successful in explaining the key properties of the long, persistent threads and small, highly dynamic, transient blobs in prominences, the damping of large-amplitude field-aligned prominence oscillations, the appearance of horn-shaped features above the cool prominence in EUV images of coronal cavities, and coronal rain in the ambient corona. To date, all studies of TNE have assumed that the plasma is fully ionized, which is appropriate for the hot coronal gas but unrealistic for the cool plasma below ~30,000 K. The energetics, dynamics, and evolutionary time scales of the TNE process are expected to be altered when the effects of ionization and recombination are considered. We have modified ARGOS, our 1D hydrodynamic code with adaptive mesh refinement, to include an equation of state that accounts for the effects of partial ionization of the plasma over a wide range of temperatures and densities. We will discuss the results of these simulations and their comparison with our previous studies of TNE in typical filament-supporting flux tubes. This work was partially supported by NASA's LWS Strategic Capability program.

  12. Breaking the pumping speed barrier in mass spectrometry: discontinuous atmospheric pressure interface.

    PubMed

    Gao, Liang; Cooks, R Graham; Ouyang, Zheng

    2008-06-01

    The performance of mass spectrometers with limited pumping capacity is shown to be improved through use of a discontinuous atmospheric pressure interface (DAPI). A proof-of-concept DAPI interface was designed and characterized using a miniature rectilinear ion trap mass spectrometer. The interface consists of a simple capillary directly connecting the atmospheric pressure ion source to the vacuum mass analyzer region; it has no ion optical elements and no differential pumping stages. Gases carrying ionized analytes were pulsed into the mass analyzer for short periods at high flow rates rather than being continuously introduced at lower flow rates; this procedure maximized ion transfer. The use of DAPI provides a simple solution to the problem of coupling an atmospheric pressure ionization source to a miniature instrument with limited pumping capacity. Data were recorded using various atmospheric pressure ionization sources, including electrospray ionization (ESI), nano-ESI, atmospheric pressure chemical ionization (APCI), and desorption electrospray ionization (DESI) sources. The interface was opened briefly for ion introduction during each scan. With the use of the 18 W pumping system of the Mini 10, limits of detection in the low part-per-billion levels were achieved and unit resolution mass spectra were recorded.

  13. Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

    2010-01-01

    Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

  14. Identification of Fatty Acids, Phospholipids, and Their Oxidation Products Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry and Electrospray Ionization Mass Spectrometry

    ERIC Educational Resources Information Center

    Harmon, Christopher W.; Mang, Stephen A.; Greaves, John; Finlayson-Pitts, Barbara J.

    2010-01-01

    Electrospray ionization mass spectrometry (ESI-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) have found increasing application in the analysis of biological samples. Using these techniques to solve problems in analytical chemistry should be an essential component of the training of undergraduate chemists. We…

  15. Evaluation of volcano-style field ionization source and field emitting cathodes for mass spectrometry and applications

    NASA Technical Reports Server (NTRS)

    Buttrill, S. E., Jr.; Spindt, C. A.

    1978-01-01

    A volcano-style field ionization source was tested with eight different gases: hydrogen, helium, ammonia, methane, argon, neon, water vapor, and hydrogen sulfide. For ammonia, hydrogen sulfide, and water, the ionization efficiency of the field ionization source was determined as a function of the electrical potential difference between the ionizer and its counterelectrode. The ionization efficiencies for the other gases were too low to be measured in the present apparatus. The operating characteristics of a field emission cathode, were studied, in the presence of the same eight gases at pressures up to 0.00001 torr. The presence of the gases caused little or no significant change in the electron emission from the cathodes. Results indicate that the field emission cathode has advantages over electrically heated cathodes as a source of an electron beam in spacecraft mass spectrometers.

  16. INSTRUMENTS AND METHODS OF INVESTIGATION: Surface-ionization field mass-spectrometry studies of nonequilibrium surface ionization

    NASA Astrophysics Data System (ADS)

    Blashenkov, Nikolai M.; Lavrent'ev, Gennadii Ya

    2007-01-01

    The ionization of polyatomic molecules on tungsten and tungsten oxide surfaces is considered for quasiequilibrium or essentially nonequilibrium conditions (in the latter case, the term nonequilibrium surface ionization is used for adsorbate ionization). Heterogeneous reactions are supposed to proceed through monomolecular decay of polyatomic molecules or fragments of multimolecular complexes. The nonequilibrium nature of these reactions is established. The dependences of the current density of disordered ions on the surface temperature, electric field strength, and ionized particle energy distribution are obtained in analytical form. Heterogeneous dissociation energies, the ionization potentials of radicals, and the magnitude of reaction departure from equilibrium are determined from experimental data, as are energy exchange times between reaction products and surfaces, the number of molecules in molecular complexes, and the number of effective degrees of freedom in molecules and complexes. In collecting the data a new technique relying on surface-ionization field mass-spectrometry was applied.

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

    USGS Publications Warehouse

    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).

  18. Plasma-based ambient ionization mass spectrometry in bioanalytical sciences.

    PubMed

    Smoluch, Marek; Mielczarek, Przemyslaw; Silberring, Jerzy

    2016-01-01

    Plasma-based ambient ionization mass spectrometry techniques are gaining growing interest due to their specific features, such as the need for little or no sample preparation, its high analysis speed, and the ambient experimental conditions. Samples can be analyzed in gas, liquid, or solid forms. These techniques allow for a wide range of applications, like warfare agent detection, chemical reaction control, mass spectrometry imaging, polymer identification, and food safety monitoring, as well as applications in biomedical science, e.g., drug and pharmaceutical analysis, medical diagnostics, biochemical analysis, etc. Until now, the main drawback of plasma-based techniques is their quantitative aspect, but a lot of efforts have been done to improve this obstacle.

  19. Absolute pressure dependence of the second ionization level of EL2 in GaAs

    SciTech Connect

    Bliss, D.E.; Walukiewicz, W.; Nolte, D.D.; Haller, E.E.

    1989-11-01

    We report the results of DLTS experiments under uniaxial stress on the second ionization level of EL2(++/+) in p-type GaAs. We measured the shift in the hole emission rate as a function of stress applied in the (100) and (110) directions. By modeling the valence band with two independently displacing bands and appropriately derived effective masses, we obtain a small absolute hydrostatic pressure derivative for the defect, 39 {plus minus} 15 MeV GPa{sup {minus}1}. The shear contribution is negligible. This result is very different than for the first ionization level, EL2(+/o) with a emission energy pressure derivative of 90 {plus minus} 15 MeV GPa{sup {minus}1}. The difference can be accounted for by the pressure dependence of the electron capture barrier of EL2(+/o), 49 {plus minus} 15 MeV GPa{sup {minus}1}. The absolute pressure derivatives of the two levels are then comparable and in good agreement with simple theory for Ga site point defects. 20 refs., 2 figs.

  20. Constraining Anthropogenic and Biogenic Emissions Using Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Spencer, Kathleen M.

    Numerous gas-phase anthropogenic and biogenic compounds are emitted into the atmosphere. These gases undergo oxidation to form other gas-phase species and particulate matter. Whether directly or indirectly, primary pollutants, secondary gas-phase products, and particulate matter all pose health and environmental risks. In this work, ambient measurements conducted using chemical ionization mass spectrometry are used as a tool for investigating regional air quality. Ambient measurements of peroxynitric acid (HO2NO2) were conducted in Mexico City. A method of inferring the rate of ozone production, PO3, is developed based on observations of HO2NO 2, NO, and NO2. Comparison of this observationally based PO3 to a highly constrained photochemical box model indicates that regulations aimed at reducing ozone levels in Mexico City by reducing NOx concentrations may be effective at higher NO x levels than predicted using accepted photochemistry. Measurements of SO2 and particulate sulfate were conducted over the Los Angeles basin in 2008 and are compared to measurements made in 2002. A large decrease in SO2 concentration and a change in spatial distribution are observed. Nevertheless, only a modest reduction in sulfate concentration is observed at ground sites within the basin. Possible explanations for these trends are investigated. Two techniques, single and triple quadrupole chemical ionization mass spectrometry, were used to quantify ambient concentrations of biogenic oxidation products, hydroxyacetone and glycolaldehyde. The use of these techniques demonstrates the advantage of triple quadrupole mass spectrometry for separation of mass analogues, provided the collision-induced daughter ions are sufficiently distinct. Enhancement ratios of hydroxyacetone and glycolaldehyde in Californian biomass burning plumes are presented as are concentrations of these compounds at a rural ground site downwind of Sacramento.

  1. Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

    PubMed

    Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

    2011-05-01

    Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers.

  2. Electrospray Ionization Tandem Mass Spectrometry of Ammonium Cationized Polyethers

    NASA Astrophysics Data System (ADS)

    Nasioudis, Andreas; Heeren, Ron M. A.; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F.

    2011-05-01

    Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers.

  3. Electrospray ionization mass spectrometric characterization of acrylamide adducts to hemoglobin

    SciTech Connect

    Springer, D.L.; Goheen, S.C.; Edmonds, C.G. ); Bull, R.J.; Sylvester, D.M. )

    1993-01-01

    The most common procedure to identify hemoglobin adducts has been to cleave the adducts from the protein and characterize the adducting species, by, for example, derivatization and gas chromatography/mass spectrometry. To extend these approaches we used electrospray ionization mass spectrometry (ESI-MS) to characterize adducted hemoglobin. For this we incubated [[sup 14]C]acrylamide with the purified human hemoglobin (type A[sub 0]) under conditions that yielded high adduct levels. When the hemoglobin was separated by reversed-phase high-performance liquid chromatography (HPLC), 65% of the radioactivity copurified with the [beta]-subunit. Three adducted species were prominent in the ESI mass spectrum of the intact [beta]-subunit, indicating acrylamide adduction (i.e., mass increase of 71 Da) and two addition unidentified moieties with mass increments of 102 and 135 Da. Endoproteinase Glu-C digestion of the adducted [beta]-subunit resulted in a peptide mixture that, upon reversed-phase HPLC separation, provided several radiolabeled peptides. Using ESI-MS we identified these as the V[sub 91-101] and V[sub 102-122] peptides that represent the cysteine-containing peptides of the [beta]-subunit. These results provide definitive information on acrylamide-modified human hemoglobin and demonstrate that ESI-MS provides valuable structure information on chemically adducted proteins. 30 refs., 9 figs., 3 tabs.

  4. An approach based on ultrahigh performance liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry allowing the quantification of both individual phytosteryl and phytostanyl fatty acid esters in complex mixtures.

    PubMed

    Scholz, Birgit; Menzel, Nicole; Lander, Vera; Engel, Karl-Heinz

    2016-01-15

    A method for the analysis of both individual phytosteryl and phytostanyl fatty acid esters in complex mixtures was established. The approach was based on a previously not described combination of three elements: (i) the formation of [M-FA+H](+) fragment ions via APCI (atmospheric pressure chemical ionization), (ii) a highly efficient UHPLC-based separation on a 1.7 μ C8 column, previously established for phytostanyl fatty acid esters, allowing the distinction of individual fatty acid esters sharing the same sterol/stanol nucleus and of isotope peaks of phytosteryl fatty acid esters and corresponding phytostanyl fatty acid esters based on these [M-FA+H](+) fragment ions, and (iii) the adjustment of the APCI conditions allowing the differential APCI-MS-SIM (single ion monitoring) detection of phytostanyl esters of linoleic and linolenic acid based on their distinct formation of a [M+H](+) ion. The usefulness of the methodology was demonstrated by the analysis of a commercially available enriched margarine. Two runs per sample allowed the quantification of 35 target analytes; the total amounts of esters were between 124.7 and 125.3g/kg, being in good agreement with the labelled 125 g/kg. Validation data were elaborated for 35 individual fatty acid esters of sitosterol, campesterol, brassicasterol, stigmasterol, sitostanol and campestanol. Recovery rates ranged from 95 to 106%; the coefficients of variation were consistently <5%, except for stigmasteryl-18:1. The approach describes for the first time a quantification of both individual phytosteryl and phytostanyl fatty acid esters and thus closes an analytical gap related to this class of health-relevant food constituents. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed

    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. Switched ferroelectric plasma ionizer (SwiFerr) for ambient mass spectrometry.

    PubMed

    Neidholdt, Evan L; Beauchamp, J L

    2011-01-01

    We present the implementation of a switched ferroelectric plasma ionizer (SwiFerr) for ambient analysis of trace substances by mass spectrometry. The device utilizes the ferroelectric properties of barium titanate (BaTiO(3)) to take advantage of the high electric field resulting from polarization switching in the material. The source comprises a [001]-oriented barium titanate crystal (5 × 5 × 1 mm) with a metallic rear electrode and a metallic grid front electrode. When a high voltage AC waveform is applied to the rear electrode to switch polarization, the resulting electric field on the face of the crystal promotes electron emission and results in plasma formation between the crystal face and the grounded grid at ambient pressure. Interaction with this plasma and the resulting reagent ions effects ionization of trace neutrals. The source requires less than 1 W of power to operate under most circumstances, ionizes molecules with acidic and basic functional groups easily, and has proven quite versatile for ambient analysis of both vapor phase and aspirated powdered solid samples. Ionization of vapor phase samples of the organics triethylamine, tripropylamine, tributylamine, and pyridine results in observation of the singly protonated species in the positive ion mass spectrum with sensitivity extending into the high ppb range. With acetic acid, deprotonated clusters dominate the negative ion mass spectrum. Aerodynamic sampling of powdered samples is used to record mass spectra of the pharmaceuticals loperamide and ibuprofen. Chemical signatures, including protonated loperamide and deprotonated ibuprofen, are observed for each drug. The robust, low power source lends itself easily to miniaturization and incorporation in field-portable devices used for the rapid detection and characterization of trace substances and hazardous materials in a range of different environments.

  7. Plasma metabolome analysis by integrated ionization rapid-resolution liquid chromatography/tandem mass spectrometry.

    PubMed

    Tian, He; Bai, Jinfa; An, Zhuoling; Chen, Yanhua; Zhang, Ruiping; He, Jiuming; Bi, Xiaofeng; Song, Yongmei; Abliz, Zeper

    2013-09-30

    Acquiring global information on plasma-endogenous metabolites challenges metabolomics. This study has been designed to investigate the suitability of integrated ionization rapid-resolution liquid chromatography/tandem mass spectrometry (RRLC/MS/MS) for different kinds of metabolites in complex plasma, and provides an approach for plasma metabolomics in acquiring more comprehensive data of metabolites. Integrated ionization of electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) combined with RRLC/MS/MS has been carried out to perform analysis on the global plasma metabolome of healthy volunteers. The contributions to the total numbers of ion features by RRLC/MS with ESI, APCI, and APPI in positive and negative ion modes were calculated. Representative unique and identical ions were identified. The intensities of identical ions were compared. Each of ESI, APCI, and APPI coupled with RRLC/MS has its own advantage over the other two techniques for certain types of metabolites in plasma. LC/ESI-MS is very sensitive for detecting glycerophosphocholines, glycerophosphoethanolamines, acyl carnitines, bile acids, sulfate, etc. LC/APCI-MS is suitable for analyzing cyclic alcohols, fatty acids, and linoleic acids. LC/APPI-MS proves to be appropriate in detecting steroids, sphingolipids, some amino acids, nucleosides, and purines in plasma. It is suggested that the integrated ionization LC/MS approach should be applied for global plasma metabolomics. Moreover, the results obtained demonstrate that it is preferable to choose certain techniques from LC/ESI-MS, LC/APCI-MS, and LC/APPI-MS for metabolite target analysis. Copyright © 2013 John Wiley & Sons, Ltd.

  8. Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    St. Clair, J. M.; Spencer, K. M.; Beaver, M. R.; Crounse, J. D.; Paulot, F.; Wennberg, P. O.

    2014-04-01

    Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

  9. When API Mass Spectrometry Meets Super Atmospheric Pressure Ion Sources

    PubMed Central

    Chen, Lee Chuin

    2015-01-01

    In a tutorial paper on the application of free-jet technique for API-MS, John Fenn mentioned that “…for a number of years and a number of reasons, it has been found advantageous in many situations to carry out the ionization process in gas at pressures up to 1000 Torr or more” (Int. J. Mass Spectrom. 200: 459–478, 2000). In fact, the first ESI mass spectrometer constructed by Yamashita and Fenn had a counter-flow curtain gas source at 1050 Torr (ca. 1.4 atm) to sweep away the neutral (J. Phys. Chem. 88: 4451–4459, 1984). For gaseous ionization using electrospray plume, theoretical analysis also shows that “super-atmospheric operation would be more preferable in space-charge-limited situations.”(Int. J. Mass Spectrom. 300: 182–193, 2011). However, electrospray and the corona-based chemical ion source (APCI) in most commercial instrument are basically operated under an atmospheric pressure ambient, perhaps out of the concern of safety, convenience and simplicity in maintenance. Running the ion source at pressure much higher than 1 atm is not so common, but had been done by a number of groups as well as in our laboratory. A brief review on these ion sources will be given in this paper. PMID:26819912

  10. When API Mass Spectrometry Meets Super Atmospheric Pressure Ion Sources.

    PubMed

    Chen, Lee Chuin

    2015-01-01

    In a tutorial paper on the application of free-jet technique for API-MS, John Fenn mentioned that "…for a number of years and a number of reasons, it has been found advantageous in many situations to carry out the ionization process in gas at pressures up to 1000 Torr or more" (Int. J. Mass Spectrom. 200: 459-478, 2000). In fact, the first ESI mass spectrometer constructed by Yamashita and Fenn had a counter-flow curtain gas source at 1050 Torr (ca. 1.4 atm) to sweep away the neutral (J. Phys. Chem. 88: 4451-4459, 1984). For gaseous ionization using electrospray plume, theoretical analysis also shows that "super-atmospheric operation would be more preferable in space-charge-limited situations."(Int. J. Mass Spectrom. 300: 182-193, 2011). However, electrospray and the corona-based chemical ion source (APCI) in most commercial instrument are basically operated under an atmospheric pressure ambient, perhaps out of the concern of safety, convenience and simplicity in maintenance. Running the ion source at pressure much higher than 1 atm is not so common, but had been done by a number of groups as well as in our laboratory. A brief review on these ion sources will be given in this paper.

  11. Super-Atmospheric Pressure Ion Sources: Application and Coupling to API Mass Spectrometer.

    PubMed

    Chen, Lee Chuin; Rahman, Md Matiur; Hiraoka, Kenzo

    2014-01-01

    Pressurizing the ionization source to gas pressure greater than atmospheric pressure is a new tactic aimed at further improving the performance of atmospheric pressure ionization (API) sources. In principle, all API sources, such as ESI, APCI and AP-MALDI, can be operated at pressure higher than 1 atm if suitable vacuum interface is available. The gas pressure in the ion source can have different role for different ionization. For example, in the case of ESI, stable electrospray could be sustained for high surface tension liquid (e.g., pure water) under super-atmospheric pressure, owing to the absence of electric discharge. Even for nanoESI, which is known to work well with aqueous solution, its stability and sensitivity were found to be enhanced, particularly in the negative mode when the ion source was pressurized. For the gas phase ionization like APCI, measurement of gaseous compound also showed an increase in ion intensity with the ion source pressure until an optimum pressure at around 4-5 atm. The enhancement was due to the increased collision frequency among reactant ion and analyte that promoted the ion/molecule reaction and a higher intake rate of gas to the mass spectrometer. Because the design of vacuum interface for API instrument is based on the upstream pressure of 1 atm, some coupling aspects need to be considered when connecting the high pressure ion source to the mass spectrometer. Several coupling strategies are discussed in this paper.

  12. Super-Atmospheric Pressure Ion Sources: Application and Coupling to API Mass Spectrometer

    PubMed Central

    Chen, Lee Chuin; Rahman, Md. Matiur; Hiraoka, Kenzo

    2014-01-01

    Pressurizing the ionization source to gas pressure greater than atmospheric pressure is a new tactic aimed at further improving the performance of atmospheric pressure ionization (API) sources. In principle, all API sources, such as ESI, APCI and AP-MALDI, can be operated at pressure higher than 1 atm if suitable vacuum interface is available. The gas pressure in the ion source can have different role for different ionization. For example, in the case of ESI, stable electrospray could be sustained for high surface tension liquid (e.g., pure water) under super-atmospheric pressure, owing to the absence of electric discharge. Even for nanoESI, which is known to work well with aqueous solution, its stability and sensitivity were found to be enhanced, particularly in the negative mode when the ion source was pressurized. For the gas phase ionization like APCI, measurement of gaseous compound also showed an increase in ion intensity with the ion source pressure until an optimum pressure at around 4–5 atm. The enhancement was due to the increased collision frequency among reactant ion and analyte that promoted the ion/molecule reaction and a higher intake rate of gas to the mass spectrometer. Because the design of vacuum interface for API instrument is based on the upstream pressure of 1 atm, some coupling aspects need to be considered when connecting the high pressure ion source to the mass spectrometer. Several coupling strategies are discussed in this paper. PMID:26819896

  13. Understanding the atmospheric pressure ionization of petroleum components: The effects of size, structure, and presence of heteroatoms.

    PubMed

    Huba, Anna Katarina; Huba, Kristina; Gardinali, Piero R

    2016-10-15

    Understanding the composition of crude oil and its changes with weathering is essential when assessing its provenience, fate, and toxicity. High-resolution mass spectrometry (HRMS) has provided the opportunity to address the complexity of crude oil by assigning molecular formulae, and sorting compounds into "classes" based on heteroatom content. However, factors such as suppression effects and discrimination towards certain components severely limit a truly comprehensive mass spectrometric characterization, and, despite the availability of increasingly better mass spectrometers, a complete characterization of oil still represents a major challenge. In order to fully comprehend the significance of class abundances, as well as the nature and identity of compounds detected, a good understanding of the ionization efficiency of the various compound classes is indispensable. The current study, therefore, analyzed model compounds typically found in crude oils by high-resolution mass spectrometry with atmospheric pressure photoionization (APPI), atmospheric pressure chemical ionization (APCI), and electrospray ionization (ESI), in order to provide a better understanding of benefits and drawbacks of each source. The findings indicate that, overall, APPI provides the best results, being able to ionize the broadest range of compounds, providing the best results with respect to ionization efficiencies, and exhibiting the least suppression effects. However, just like in the other two sources, in APPI several factors have shown to affect the ionization efficiency of petroleum model compounds. The main such factor is the presence or absence of functional groups that can be easily protonated/deprotonated, in addition to other factors such as size, methylation level, presence of heteroatoms, and ring structure. Overall, this study evidences the intrinsic limitations and benefits of each of the three sources, and should provide the fundamental knowledge required to expand the power

  14. Non-Equilibrium Ionization Modeling of Coronal Mass Ejections

    NASA Astrophysics Data System (ADS)

    Rimple, Remington; Murphy, Nicholas Arnold; Shen, Chengcai

    2017-01-01

    Coronal Mass Ejections, or CMEs, are solar events that eject plasma and magnetic flux into interplanetary space. Contemporary sources have noted that the onset of CMEs are caused by some instability of the coronal magnetic field, and further allows heating of plasma upon expansion. Additionally, plasma that leaves the lower solar corona does not remain in ionization equilibrium due to the rapid expansion of plasma. We investigate the evolution of charge states of CME plasma using non-equilibrium ionization (NEI) modeling. These NEI models include radiative cooling and serve as baseline studies for special cases where no heat is being added to the plasma. Each of the simulated CMEs have initial conditions characteristic of active regions. Various function inputs, such as initial temperature, density and final velocity, allow us to examine the influence of certain parameters on the charge state evolution. The results of our project show that plasma originating from active regions display charge state evolutions substantially dependent on initial density and temperature. The CMEs starting with higher plasma density often show an abundance of lower charge states above the freeze-in height. Simulations starting from higher temperatures often show abundance peaks at charge states with closed electron shells.

  15. Reaction of arylium ions with the collision gas N2 in electrospray ionization mass spectrometry.

    PubMed

    Liang, Yuxue; Neta, Pedatsur; Simón-Manso, Yamil; Stein, Stephen E

    2015-04-15

    The tandem mass spectra of many compounds contained peaks which could not have arisen from the precursor ion. Such peaks were found to be due to reaction of arylium ions with N2 in the collision cell. Therefore, this reaction was studied in detail with representative compounds. Various classes of compounds were dissolved in acetonitrile/water/formic acid and studied by electrospray ionization mass spectrometry to record their MS(2) and pseudo-MS(3) spectra in a QqQ mass spectrometer and their accurate m/z values in an Orbitrap Elite instrument. Arylium ions were found to react with N2 in the collision cell. The reaction was confirmed by pseudo-MS(3) studies, by comparison with authentic diazonium ions, and by the pressure dependence of the product ion survival yield. Reactions of arylium ions with N2 were observed with p-toluenesulfonic acid, o-toluenesulfonamide, phenylphosphonic acid, phenol, aniline, aminonaphthalenes, benzoic acid, benzophenone, and other compounds. By using a QqQ mass spectrometer, we observed that the protonated compounds produce arylium ions, which then react with N2 to form diazonium ions. The diazonium ion was produced with N2 but not with Ar in the collision cell, and its abundance increased with increasing N2 pressure. Arylium ions generated from a wide variety of compounds in electrospray ionization tandem mass spectrometry may react with N2 to form diazonium ions. The abundance of the diazonium ions is affected by collision energy and N2 pressure. This reaction should be considered when annotating peaks in MS/MS libraries. Published in 2015. This article is a U.S. Government work and is in the public domain in the USA. Published in 2015. This article is a U.S. Government work and is in the public domain in the USA.

  16. Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry.

    PubMed

    Cai, Yi; Liu, Pengyuan; Held, Michael A; Dewald, Howard D; Chen, Hao

    2016-04-18

    A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room-temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI-MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI-MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI-MS, which could have an impact in electrochemistry and bioanalysis fields.

  17. Characterization of leucine zipper complexes by electrospray ionization mass spectrometry.

    PubMed Central

    Wendt, H.; Dürr, E.; Thomas, R. M.; Przybylski, M.; Bosshard, H. R.

    1995-01-01

    The development of "soft" ionization methods has enabled the mass spectrometric analysis of higher-order structural features of proteins. We have applied electrospray ionization mass spectrometry (ESI-MS) to the analysis of the number and composition of polypeptide chains in homomeric and heteromeric leucine zippers. In comparison with other methods that have been used to analyze leucine zippers, such as analytical ultracentrifugation, gel chromatography, or electrophoretic band shift assays, ESI-MS is very fast and highly sensitive and provides a straightforward way to distinguish between homomeric and heteromeric coiled-coil structures. ESI-MS analyses were carried out on the parallel dimeric leucine zipper domain GCN4-p1 of the yeast transcription factor GCN4 and on three synthetic peptides with the sequences Ac-EYEALEKKLAAX1EAKX2QALEKKLEALEHG-amide: peptide LZ (X1, X2 = Leu), peptide LZ(12A) (X1 = Ala, X2 = Leu), and peptide LZ(16N) (X1 = Leu, X2 = Asn). Equilibrium ultracentrifugation analysis showed that LZ forms a trimeric coiled coil and this could be confirmed unequivocally by ESI-MS as could the dimeric nature of GCN4-p1. The formation of heteromeric two- and three-stranded leucine zippers composed of chains from LZ and LZ(12A), or from GCN4-p1 and LZ, was demonstrated by ESI-MS and confirmed by fluorescence quenching experiments on fluorescein-labeled peptides. The results illustrate the adaptability and flexibility of the leucine zipper motif, properties that could be useful to the design of specific protein assemblies by way of coiled-coil domains. PMID:8520482

  18. Flame ionization mass spectrometry--Isotope ratio determinations for potassium

    USGS Publications Warehouse

    Taylor, Howard E.; Garbarino, John R.; Koirtyohann, S.R.

    1991-01-01

    The air/acetylene flame provides a convenient ion source for the determination of potassium isotopic ratios by mass spectrometry. Unlike the argon inductively coupled plasma (ICP), the flame provides low background in the mass region of interest. Ion production is quite satisfactory for isotope ratio measurements at the micrograms per milliliter (μg/mL) level and slightly below, with 1 μg/mL potassium giving about 105counts/second at a nominal mass-to-charge ratio of 39. The detection limit for potassium was 2-3 nanograms per milliliter (ng/mL). The ratio of 41K/39K was measured with 0.5-1% relative standard deviation, and a 41K spike representing 0.2% of the total potassium was readily detected. Both signal levels and signal stability were improved by adding a second easily ionized element such as cesium to samples and standards. Alternatively, a cesium solution could be aspirated for about 1 minute between sample measurements to ensure signal stability.

  19. Intraoperative tissue identification using rapid evaporative ionization mass spectrometry.

    PubMed

    Balog, Júlia; Sasi-Szabó, László; Kinross, James; Lewis, Matthew R; Muirhead, Laura J; Veselkov, Kirill; Mirnezami, Reza; Dezső, Balázs; Damjanovich, László; Darzi, Ara; Nicholson, Jeremy K; Takáts, Zoltán

    2013-07-17

    Rapid evaporative ionization mass spectrometry (REIMS) is an emerging technique that allows near-real-time characterization of human tissue in vivo by analysis of the aerosol ("smoke") released during electrosurgical dissection. The coupling of REIMS technology with electrosurgery for tissue diagnostics is known as the intelligent knife (iKnife). This study aimed to validate the technique by applying it to the analysis of fresh human tissue samples ex vivo and to demonstrate the translation to real-time use in vivo in a surgical environment. A variety of tissue samples from 302 patients were analyzed in the laboratory, resulting in 1624 cancerous and 1309 noncancerous database entries. The technology was then transferred to the operating theater, where the device was coupled to existing electrosurgical equipment to collect data during a total of 81 resections. Mass spectrometric data were analyzed using multivariate statistical methods, including principal components analysis (PCA) and linear discriminant analysis (LDA), and a spectral identification algorithm using a similar approach was implemented. The REIMS approach differentiated accurately between distinct histological and histopathological tissue types, with malignant tissues yielding chemical characteristics specific to their histopathological subtypes. Tissue identification via intraoperative REIMS matched the postoperative histological diagnosis in 100% (all 81) of the cases studied. The mass spectra reflected lipidomic profiles that varied between distinct histological tumor types and also between primary and metastatic tumors. Thus, in addition to real-time diagnostic information, the spectra provided additional information on divergent tumor biochemistry that may have mechanistic importance in cancer.

  20. New Types of Ionization Sources for Mass Spectrometry

    SciTech Connect

    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.

  1. Atomic force microscope controlled topographical imaging and proximal probe thermal desorption/ionization mass spectrometry imaging.

    PubMed

    Ovchinnikova, Olga S; Kjoller, Kevin; Hurst, Gregory B; Pelletier, Dale A; Van Berkel, Gary J

    2014-01-21

    This paper reports on the development of a hybrid atmospheric pressure atomic force microscopy/mass spectrometry imaging system utilizing nanothermal analysis probes for thermal desorption surface sampling with subsequent atmospheric pressure chemical ionization and mass analysis. The basic instrumental setup and the general operation of the system were discussed, and optimized performance metrics were presented. The ability to correlate topographic images of a surface with atomic force microscopy and a mass spectral chemical image of the same surface, utilizing the same probe without moving the sample from the system, was demonstrated. Co-registered mass spectral chemical images and atomic force microscopy topographical images were obtained from inked patterns on paper as well as from a living bacterial colony on an agar gel. Spatial resolution of the topography images based on pixel size (0.2 μm × 0.8 μm) was better than the resolution of the mass spectral images (2.5 μm × 2.0 μm), which were limited by current mass spectral data acquisition rate and system detection levels.

  2. Atomic Force Microscope Controlled Topographical Imaging and Proximal Probe Thermal Desorption/Ionization Mass Spectrometry Imaging

    SciTech Connect

    Ovchinnikova, Olga S; Kjoller, Kevin; Hurst, Gregory {Greg} B; Pelletier, Dale A; Van Berkel, Gary J

    2014-01-01

    This paper reports on the development of a hybrid atmospheric pressure atomic force microscopy/mass spectrometry imaging system utilizing nano-thermal analysis probes for thermal desorption surface sampling with subsequent atmospheric pressure chemical ionization and mass analysis. The basic instrumental setup and the general operation of the system were discussed and optimized performance metrics were presented. The ability to correlate topographic images of a surface with atomic force microscopy and a mass spectral chemical image of the same surface, utilizing the same probe without moving the sample from the system, was demonstrated. Co-registered mass spectral chemical images and atomic force microscopy topographical images were obtained from inked patterns on paper as well as from a living bacterial colony on an agar gel. Spatial resolution of the topography images based on pixel size (0.2 m x 0.8 m) was better than the resolution of the mass spectral images (2.5 m x 2.0 m), which were limited by current mass spectral data acquisition rate and system detection levels.

  3. Surface-activated chemical ionization ion trap mass spectrometry in the analysis of amphetamines in diluted urine samples.

    PubMed

    Cristoni, Simone; Bernardi, Luigi Rossi; Gerthoux, Piermario; Gonella, Elisabetta; Mocarelli, Paolo

    2004-01-01

    A new ionization method, named surface-activated chemical ionization (SACI), was employed for the analysis of five amphetamines (3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDE), amphetamine and methamphetamine) by ion trap mass spectrometry. The results so obtained have been compared with those achieved by using atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) using the same instrument, clearly showing that SACI is the most sensitive of the three. The limit of detection and linearity range for SACI were compared with those obtained using APCI and ESI, showing that the new SACI approach provides the best results for both criteria. SACI was used to analyze MDA, MDMA MDE, amphetamine and methamphetamine in four urine samples, and the quantitation results are compared with those achieved using ESI.

  4. Effect of instrument tuning on the detectabilityof biopolymers in electrospray ionization mass spectrometry.

    PubMed

    Oberacher, Herbert; Walcher, Wolfgang; Huber, Christian G

    2003-01-01

    Electrospray ionization mass spectrometry of multiply charged biopolymer ions of different molecular size revealed a strong influence of tuning parameters on their detectability in quadrupole ion trap and triple quadrupole mass spectrometers. Hence, after optimizing the ion optical parameters with the signal of the 4- charge state of (dT)(24) (low charge state tuning), a tenfold increase in the signal-to-noise ratio for a mixture of oligodeoxythymidylic acids (n = 12-18) was obtained compared with the results achieved with tune parameters optimized with a synthetic 80-mer oligodeoxynucleotide. By contrast, a detection limit in the upper femtomole region could only be reached for a 104-mer oligodeoxynucleotide utilizing the 24- charge state of the 80-mer (high charge state tuning). The same effect was observed for proteins investigated in the positive ion mode using low and high charge states of cytochrome c and carbonic anhydrase, respectively, for instrument tuning. By comparing the settings for low and high charge state tuning, it became obvious that the most significant difference was observed in the potential applied to the heated metal capillary used to transfer ions from the atmospheric pressure to the vacuum region of the ion source. Taking advantage of the optimized tuning procedure, the molecular mass of a 61 base pair product of polymerase chain reaction was accurately determined by electrospray ionization mass spectrometry on-line interfaced to ion-pair reversed-phase high-performance liquid chromatography. Copyright 2003 John Wiley & Sons, Ltd.

  5. Analysis of omnoponum by surface-ionization mass spectrometry and liquid chromatography tandem mass spectrometry methods.

    PubMed

    Usmanov, Dilshadbek; Khasanov, Usman; Pantsirev, Aleksey; Van Bocxlaer, Jan

    2010-12-01

    This paper provides the development of analytical capabilities of surface-ionization mass spectrometry (SI/MS) and high performance liquid chromatography with tandem mass spectrometry (HPLC/MS/MS) for narcotic analgesic omnoponum, which perfectly exemplifies a mixture of opium alkaloids. It has been revealed that the investigated opiates solution, omnoponum, is ionized by the surface ionization (SI) method with high sensitivity. In the SI mass spectrum, M+, (M-H)+, (M-H-2nH)+, (M-R)+ and (M-R-2nH)+ ion lines, where M is a molecule, H is the hydrogen atom and R is a radical, were observed. These ion lines consist of combined omnoponum mixture SI mass spectra, i.e. morphine, codeine, thebaine, papaverine, and narcotine. Moreover, while the study of omnoponum by HPLC/MS/MS methods has attested that the mixture really consists of 5 components, it has been demonstrated that the SI/MS method can be utilized for the analysis of this mixture without the necessity of its chromatographic separation. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  6. Ionization mechanism of the ambient pressure pyroelectric ion source (APPIS) and its applications to chemical nerve agent detection.

    PubMed

    Neidholdt, Evan L; Beauchamp, J L

    2009-11-01

    We present studies of the ionization mechanism operative in the ambient pressure pyroelectric ionization source (APPIS), along with applications that include detection of simulants for chemical nerve agents. It is found that ionization by APPIS occurs in the gas-phase. As the crystal is thermally cycled over a narrow temperature range, electrical discharges near the surface of the crystal produce energetic species which, through reactions with atmospheric molecules, result in reactant ions such as protonated water clusters or clusters of hydroxide and water. Reactant ions can be observed directly in the mass spectrometer. These go on to react with trace neutrals via proton transfer reactions to produce the ions observed in mass spectra, which are usually singly protonated or deprotonated species. Further implicating gas-phase ionization, observed product distributions are highly dependent on the composition of ambient gases, especially the concentration of water vapor and oxygen surrounding the source. For example, basic species such as triethylamine are observed as singly protonated cations at a water partial pressure of 10 torr. At a water pressure of 4 torr, reactive oxygen species are formed and lead to observation of protonated amine oxides. The ability of the APPIS source to detect basic molecules with high proton affinities makes it highly suited for the detection of chemical nerve agents. We demonstrate this application using simulants corresponding to VX and GA (Tabun). With the present source configuration pyridine is detected readily at a concentration of 4 ppm, indicating ultimate sensitivity in the high ppb range.

  7. Producing highly charged ions without solvent using laserspray ionization: a total solvent-free analysis approach at atmospheric pressure.

    PubMed

    Wang, Beixi; Lietz, Christopher B; Inutan, Ellen D; Leach, Samantha M; Trimpin, Sarah

    2011-06-01

    First examples of highly charged ions in mass spectrometry (MS) produced from the solid state without using solvent during either sample preparation or mass measurement are reported. Matrix material, matrix/analyte homogenization time and frequency, atmospheric pressure (AP) to vacuum inlet temperature, and mass analyzer ion trap conditions are factors that influence the abundance of the highly charged ions created by laserspray ionization (LSI). LSI, like matrix-assisted laser desorption/ionization (MALDI), uses laser ablation of a matrix/analyte mixture from a surface to produce ions. Preparing the matrix/analyte sample without the use of solvent provides the ability to perform total solvent-free analysis (TSA) consisting of solvent-free ionization and solvent-free gas-phase separation using ion mobility spectrometry (IMS) MS. Peptides and small proteins such as non-β-amyloid components of Alzheimer's disease and bovine insulin are examples in which LSI and TSA were combined to produce multiply charged ions, similar to electrospray ionization, but without the use of solvent. Advantages using solvent-free LSI and IMS-MS include simplicity, rapid data acquisition, reduction of sample complexity, and the potential for an enhanced effective dynamic range. This is achieved by more inclusive ionization and improved separation of mixture components as a result of multiple charging.

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

    PubMed

    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.

  9. Enhancement of ionization efficiency of mass spectrometric analysis from non-electrospray ionization friendly solvents with conventional and novel ionization techniques.

    PubMed

    Jiang, Ping; Lucy, Charles A

    2015-10-15

    Electrospray ionization mass spectrometry (ESI-MS) has significantly impacted the analysis of complex biological and petroleum samples. However ESI-MS has limited ionization efficiency for samples in low dielectric and low polarity solvents. Addition of a make-up solvent through a T union or electrospray solvent through continuous flow extractive desorption electrospray ionization (CF-EDESI) enable ionization of analytes in non-ESI friendly solvents. A conventional make-up solvent addition setup was used and a CF-EDESI source was built for ionization of nitrogen-containing standards in hexane or hexane/isopropanol. Factors affecting the performance of both sources have been investigated and optimized. Both the make-up solvent addition and CF-EDESI improve the ionization efficiency for heteroatom compounds in non-ESI friendly solvents. Make-up solvent addition provides higher ionization efficiency than CF-EDESI. Neither the make-up solvent addition nor the CF-EDESI eliminates ionization suppression of nitrogen-containing compounds caused by compounds of the same chemical class. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Multistage Reactive Transmission-Mode Desorption Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Peters, Kevin C.; Comi, Troy J.; Perry, Richard H.

    2015-09-01

    Elucidating reaction mechanisms is important for advancing many areas of science such as catalyst development. It is often difficult to probe fast reactions at ambient conditions with high temporal resolution. In addition, systems involving reagents that cross-react require analytical methods that can minimize interaction time and specify their order of introduction into the reacting system. Here, we explore the utility of transmission mode desorption electrospray ionization (TM-DESI) for reaction monitoring by directing a microdroplet spray towards a series of meshes with micrometer-sized openings coated with reagents, an approach we call multistage reactive TM-DESI (TM n -DESI, where n refers to the number of meshes; n = 2 in this report). Various stages of the reaction are initiated at each mesh surface, generating intermediates and products in microdroplet reaction vessels traveling towards the mass spectrometer. Using this method, we investigated the reactivity of iron porphyrin catalytic hydroxylation of propranolol and other substrates. Our experimental results indicate that TM n -DESI provides the ability to spatially separate reagents and control their order of introduction into the reacting system, thereby minimizing unwanted reactions that lead to catalyst deactivation and degradation products. In addition, comparison with DESI-MS analyses (the Zare and Latour laboratories published results suggesting accessible reaction times <1 ms) of the reduction of dichlorophenolindophenol by L-ascorbic acid suggest that TM 1 -DESI can access reaction times less than 1 ms. Multiple meshes allow sequential stages of desorption/ionization per MS scan, increasing the number of analytes and reactions that can be characterized in a single experiment.

  11. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry.

    PubMed

    Newsome, G Asher; Steinkamp, F Lucus; Giordano, Braden C

    2016-11-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane (i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance. Graphical Abstract ᅟ.

  12. Isobutane Made Practical as a Reagent Gas for Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Newsome, G. Asher; Steinkamp, F. Lucus; Giordano, Braden C.

    2016-11-01

    As a reagent gas for positive- and negative-mode chemical ionization mass spectrometry (CI-MS), isobutane ( i-C4H10) produces superior analyte signal abundance to methane. Isobutane has never been widely adopted for CI-MS because it fouls the ion source more rapidly and produces positive CI spectra that are more strongly dependent on reagent gas pressure compared with methane. Isobutane was diluted to various concentrations in argon for use as a reagent gas with an unmodified commercial gas chromatograph-mass spectrometer. Analyte spectra were directly compared using methane, isobutane, and isobutane/argon mixtures. A mixture of 10% i-C4H10 in argon produced twice the positive-mode analyte signal of methane, equal to pure isobutane, and reduced spectral dependence on reagent gas pressure. Electron capture negative chemical ionization using 1% i-C4H10 in argon tripled analyte signal compared with methane and was reproducible, unlike pure isobutane. The operative lifetime of the ion source using isobutane/argon mixtures was extended exponentially compared with pure isobutane, producing stable and reproducible CI signal throughout. By diluting the reagent gas in an inert buffer gas, isobutane CI-MS experiments were made as practical to use as methane CI-MS experiments but with superior analytical performance.

  13. Electrospray ionization mass spectrometry and its environmental applications

    SciTech Connect

    Long, J.M.

    1993-01-01

    An electrospray ionization (ESI) source was designed, fabricated and then installed on a VG TRIO-2 quadrupole mass spectrometer. A gold coated 50-[mu]m fused silica capillary was used instead of the conventional stainless steel needle. Analytes are desorbed into the gas phase via a heated metal transport capillary and are focused through a set of five electrostatic lenses into the analyzer region of the mass spectrometer. Environmentally significant compounds such as pesticides and herbicides that are polar, nonvolatile and thermally labile are not readily analyzed by conventional gas chromatography/mass spectrometry (GC/MS). Thirty pesticides from the 13 classes of carbamate, organophosphorus, organochlorine, bipyridyl, phthalimide, urea, carboxyllic acid, hydroxycoumarin, triazine, indandione, dinitroaniline, pyrethrin, and thiocarbamate were analyzed using this method. Analysis of these samples showed that addition of acid to the neat sample did not appreciably increase the protonated analyte signal nor the total ion current for any of the samples analyzed. This observation together with the extremely low pKa values of these pesticides, calculated by SPARC, indicates that the protonated analytes are formed in the gas rather than in the condensed phase. Sodium and ammonium ions were added to these pesticides but in no case was the total ion current increased over that from the neat sample. Solvent studies showed that 50/50 mixtures of methanol/water and acetonitrile/water are both suitable solvent systems but that a methanol fraction of 30% appears to be ideal for some of the pesticides studied. Evidence of radical cation formation was observed when pure acetonitrile was used. It was demonstrated, by spiking 5 carbamate pesticides into Yellowstone River water, that ESI/MS by the direct injection method is a potential candidate as a rapid screening method for pesticides in natural waters.

  14. CHARACTERIZATION OF CRYPTOSPORIDIUM PARVUM BY MATRIX-ASSISTED LASER DESORPTION -- IONIZATION TIME OF FLIGHT MASS SPECTROMETRY

    EPA Science Inventory

    Matrix assisted laser desorption/ionization (MALDI) mass spectrometry was used to investigate whole and freeze thawed Cryptosporidium parvum oocysts. Whole oocysts revealed some mass spectral features. Reproducible patterns of spectral markers and increased sensitivity were obtai...

  15. Ambient Ionization Mass Spectrometry for Cancer Diagnosis and Surgical Margin Evaluation

    PubMed Central

    Ifa, Demian R.; Eberlin, Livia S.

    2017-01-01

    Background There is a clinical need for new technologies that would enable rapid disease diagnosis based on diagnostic molecular signatures. Ambient ionization mass spectrometry has revolutionized the means by which molecular information can be obtained from tissue samples in real time and with minimal sample pretreatment. New developments in ambient ionization techniques applied to clinical research suggest that ambient ionization mass spectrometry will soon become a routine medical tool for tissue diagnosis. Content This review summarizes the main developments in ambient ionization techniques applied to tissue analysis, with focus on desorption electrospray ionization mass spectrometry, probe electrospray ionization, touch spray, and rapid evaporative ionization mass spectrometry. We describe their applications to human cancer research and surgical margin evaluation, highlighting integrated approaches tested for ex vivo and in vivo human cancer tissue analysis. We also discuss the challenges for clinical implementation of these tools and offer perspectives on the future of the field. Summary A variety of studies have showcased the value of ambient ionization mass spectrometry for rapid and accurate cancer diagnosis. Small molecules have been identified as potential diagnostic biomarkers, including metabolites, fatty acids, and glycerophospholipids. Statistical analysis allows tissue discrimination with high accuracy rates (>95%) being common. This young field has challenges to overcome before it is ready to be broadly accepted as a medical tool for cancer diagnosis. Growing research in new, integrated ambient ionization mass spectrometry technologies and the ongoing improvements in the existing tools make this field very promising for future translation into the clinic. PMID:26555455

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-11-28

    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. Graphical Abstract ᅟ.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    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.

  19. The effects of added hydrogen on a helium atmospheric-pressure plasma jet ambient desorption/ionization source.

    PubMed

    Wright, Jonathan P; Heywood, Matthew S; Thurston, Glen K; Farnsworth, Paul B

    2013-03-01

    We present mass spectrometric data demonstrating the effect that hydrogen has on a helium-based dielectric-barrier discharge (DBD) atmospheric-pressure plasma jet used as an ambient desorption/ionization (ADI) source. The addition of 0.9 % hydrogen to the helium support gas in a 35-W plasma jet increased signals for a range of test analytes, with enhancement factors of up to 68, without proportional increases in background levels. The changes in signal levels result from a combination of changes in the desorption kinetics from the surface and increased ion production in the gas phase. The enhancement in ADI-MS performance despite the quenching of key plasma species reported in earlier studies suggests that ionization with a H2/He plasma jet is the result of an alternate mechanism involving the direct generation of ionized hydrogen.

  20. Radiation pressure confinement - III. The origin of the broad ionization distribution in AGN outflows

    NASA Astrophysics Data System (ADS)

    Stern, Jonathan; Behar, Ehud; Laor, Ari; Baskin, Alexei; Holczer, Tomer

    2014-12-01

    The winds of ionized gas driven by active galactic nuclei (AGN) can be studied through absorption lines in their X-ray spectra. A recurring feature of these outflows is their broad ionization distribution, including essentially all ionization levels (e.g., Fe0+ to Fe25+). This characteristic feature can be quantified with the absorption measure distribution (AMD), defined as the distribution of column density with ionization parameter |dN/d log ξ|. Observed AMDs extend over 0.1 ≲ ξ ≲ 104 (cgs), and are remarkably similar in different objects. Power-law fits (|dN/d log ξ| ≈ N1ξa) yield N1 = 3 × 1021 cm- 2 ± 0.4 dex and a = 0-0.4. What is the source of this broad ionization distribution, and what sets the small range of observed N1 and a? A common interpretation is a multiphase outflow, with a wide range of gas densities in a uniform gas pressure medium. However, the incident radiation pressure leads to a gas pressure gradient in the photoionized gas, and therefore to a broad range of ionization states within a single slab. We show that this compression of the gas by the radiation pressure leads to an AMD with |dN/d log ξ| = 8 × 1021 ξ0.03 cm-2, remarkably similar to that observed. The calculated values of N1 and a depend weakly on the gas metallicity, the ionizing spectral slope, the distance from the nucleus, the ambient density, and the total absorber column. Thus, radiation pressure compression (RPC) of the photoionized gas provides a natural explanation for the observed AMD. RPC predicts that the gas pressure increases with decreasing ionization, which can be used to test the validity of RPC in ionized AGN outflows.

  1. Low pressure microplasmas enabled by field ionization: Kinetic modeling

    SciTech Connect

    Macheret, Sergey O. Tholeti, Siva Sashank; Alexeenko, Alina A.

    2016-05-09

    A principle of microplasma generation that utilizes field emission of electrons at the cathode and field ionization producing ions at the anode, both processes relying on nanorods or nanotubes, is explored theoretically. In this plasma generation concept, collisional ionization of atoms and molecules by electron impact would play a negligible role. Analytical estimates as well as plasma kinetic modeling by particle-in-cell method with Monte Carlo collisions in argon confirm that this principle can enable substantial plasma densities at near-collisionless microgaps, while requiring relatively low voltages, less than 100 V. An order of magnitude increase in electron number density can be achieved due to enhancement of field emission at the cathode by positive space charge at high field ionization ion current densities.

  2. Alternately Pulsed Nano-electrospray Ionization/Atmospheric Pressure Chemical Ionization for Ion/Ion Reactions in an Electrodynamic Ion Trap

    PubMed Central

    Liang, Xiaorong; Xia, Yu; McLuckey, Scott A.

    2008-01-01

    The alternate operation of nano-electrospray ionization (nano-ESI) and atmospheric pressure chemical ionization (APCI), using a common atmosphere/vacuum interface and ion path, has been implemented to facilitate ion/ion reaction experiments in a linear ion trap-based tandem mass spectrometer. The ion sources are operated in opposite polarity modes whereby one of the ion sources is used to form analyte ions while the other is used to form reagent ions of opposite polarity. This combination of ion sources is well-suited to implementation of experiments involving multiply charged ions in reaction with singly charged ions of opposite polarity. Three analytically useful ion/ion reactions types are illustrated: the partial deprotonation of a multiply protonated protein, the partial protonation of a multiply deprotonated oligonucleotide, and electron transfer to a multiply protonated peptide. The approach described herein is attractive in that it enables both single proton transfer and single electron transfer ion/ion reaction experiments to be implemented without requiring major modifications to the tandem mass spectrometer hardware. Furthermore, a wide range of reactant ions can be formed with these ionization methods and the pulsed nature of operation appears to lead to no significant compromise in the performance of either ion source. PMID:16643016

  3. A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

    2011-01-01

    A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

  4. Probing combustion chemistry in a miniature shock tube with synchrotron VUV photo ionization mass spectrometry.

    PubMed

    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 < 100 bar) behind reflected 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 < T5 < 1700 K, 3 < P5 < 16 bar) with ionization energies between 10 and 13 eV. Individual experiments have extremely low signal levels. However, product species and radical intermediates are well-resolved when averaging over hundreds of shots, which is ordinarily impractical in conventional 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.

  5. Matrix-assisted laser desorption/ionization mass spectrometry method for selectively producing either singly or multiply charged molecular ions.

    PubMed

    Trimpin, Sarah; Inutan, Ellen D; Herath, Thushani N; McEwen, Charles N

    2010-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is noted for its ability to produce primarily singly charged ions. This is an attribute when using direct ionization for complex mixtures such as protein digests or synthetic polymers. However, the ability to produce multiply charged ions, as with electrospray ionization (ESI), has advantages such as extending the mass range on mass spectrometers with limited mass-to-charge (m/z) range and enhancing fragmentation for structural characterization. We designed and fabricated a novel field free transmission geometry atmopsheric pressure (AP) MALDI source mounted to a high-mass resolution Orbitrap Exactive mass spectrometer. We report the ability to produce at will either singly charged ions or highly charged ions using a MALDI process by simply changing the matrix or the matrix preparation conditions. Mass spectra with multiply charged ions very similar to those obtained with ESI of proteins such as cytochrome c and ubiquitin are obtained with low femtomole amounts applied to the MALDI target plate and for peptides such as angiotensin I and II with application of attomole amounts. Single scan acquisitions produce sufficient ion current even from proteins.

  6. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

    NASA Astrophysics Data System (ADS)

    Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  7. Real Time Monitoring of Containerless Microreactions in Acoustically Levitated Droplets via Ambient Ionization Mass Spectrometry.

    PubMed

    Crawford, Elizabeth A; Esen, Cemal; Volmer, Dietrich A

    2016-09-06

    Direct in-droplet (in stillo) microreaction monitoring using acoustically levitated micro droplets has been achieved by combining acoustic (ultrasonic) levitation for the first time with real time ambient tandem mass spectrometry (MS/MS). The acoustic levitation and inherent mixing of microliter volumes of reactants (3 μL droplets), yielding total reaction volumes of 6 μL, supported monitoring the acid-catalyzed degradation reaction of erythromycin A. This reaction was chosen to demonstrate the proof-of-principle of directly monitoring in stillo microreactions via hyphenated acoustic levitation and ambient ionization mass spectrometry. The microreactions took place completely in stillo over 30, 60, and 120 s within the containerless stable central pressure node of an acoustic levitator, thus readily promoting reaction miniaturization. For the evaluation of the miniaturized in stillo reactions, the degradation reactions were also carried out in vials (in vitro) with a total reaction volume of 400 μL. The reacted in vitro mixtures (6 μL total) were similarly introduced into the acoustic levitator prior to ambient ionization MS/MS analysis. The in stillo miniaturized reactions provided immediate real-time snap-shots of the degradation process for more accurate reaction monitoring and used a fraction of the reactants, while the larger scale in vitro reactions only yielded general reaction information.

  8. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

    PubMed

    Winter, Gregory T; Wilhide, Joshua A; LaCourse, William R

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  9. A microfluidic reactor for rapid, low-pressure proteolysis with on-chip electrospray ionization.

    PubMed

    Liuni, Peter; Rob, Tamanna; Wilson, Derek J

    2010-02-01

    A microfluidic reactor that enables rapid digestion of proteins prior to on-line analysis by electrospray ionization mass spectrometry (ESI-MS) is introduced. The device incorporates a wide (1.5 cm), shallow (10 microm) reactor 'well' that is functionalized with pepsin-agarose, a design that facilitates low-pressure operation and high clogging resistance. Electrospray ionization is carried out directly from a short metal capillary integrated into the chip outlet. Fabrication, involving laser ablation of polymethyl methacrylate (PMMA), is exceedingly straightforward and inexpensive. High sequence coverage spectra of myoglobin (Mb), ubiquitin (Ub) and bovine serum albumin (BSA) digests were obtained after <4 s of residence time in the reactor. Stress testing showed little loss of performance over approximately 2 h continuous use at high flow rates (30 microL/min). The device provides a convenient platform for a range of applications in proteomics and structural biology, i.e. to enable high-throughput workflows or to limit back-exchange in spatially resolved hydrogen/deuterium exchange (HDX) experiments. Copyright 2010 John Wiley & Sons, Ltd.

  10. Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

    ERIC Educational Resources Information Center

    Stock, Naomi L.; March, Raymond E.

    2014-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

  11. Hands-on Electrospray Ionization-Mass Spectrometry for Upper-Level Undergraduate and Graduate Students

    ERIC Educational Resources Information Center

    Stock, Naomi L.; March, Raymond E.

    2014-01-01

    Electrospray ionization-mass spectrometry (ESI-MS) is a powerful technique for the detection, identification, and quantification of organic compounds. As mass spectrometers have become more user-friendly and affordable, many students--often with little experience in mass spectrometry--find themselves needing to incorporate mass spectrometry into…

  12. Ion/molecule reaction and ion evaporation in atmospheric pressure spray ionization

    NASA Astrophysics Data System (ADS)

    Hirabayashi, Atsumu; Takada, Yasuaki; Kambara, Hideki; Umemura, Yuta; Ohta, Hitoshi; Ito, Haruhiko; Kuchitsu, Kozo

    1992-12-01

    The positive ions produced in atmospheric pressure spray ionization of ammonia, alanine and sucrose in aqueous solution were detected with a double-focusing mass spectrometer. The relative intensities of the quasi-molecular ions of ammonia, NH+4 (H2O)n (n = 0-3), were found to be proportional to the concentration of the ammonia solution and to increase with increasing distance d between the nozzle tip and the sample aperture of the mass spectrometer; this observation shows that the ammonia molecule is produced by the spray and is protonated at atmospheric pressure by a proton transfer reaction with the hydronium ion and its hydrated clusters. The observed dependences of the relative intensities of the protonated alanine molecules from alanine solution and the cationized sucrose molecules from sucrose solution on d show that some part of these quasi-molecular ions are also produced by the ion/molecule reaction in the gas phase. However, their dependences on the concentration, which are steeper than that in the ammonia case, indicate that a significant proportion of these ions are produced by ion evaporation from a droplet or liquid.

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

    DTIC Science & Technology

    2015-06-01

    Light Emitting Diodes (LED) and Diode Lasers ...............................8  B.  THE LASER POWER AND MODES...RIMS selective ionization and mass analysis process, from [2] ........................1  Figure 2.  Current RIMS pump and ionization laser setup, from...element” [5]. The laser system that produces the photons for ionization is comprised of three tunable lasers (Ti:Sapph, Al2O3 crystal doped with Ti) pumped

  14. Resonance ionization mass spectrometric study of the promethium/samarium isobaric pair

    SciTech Connect

    Shaw, R.W.; Young, J.P.; Smith, D.H.

    1988-01-01

    Samarium daughters are problematic in isotope ratio measurements of promethium because they are isobaric. Resonance ionization mass spectrometry was utilized to circumvent this problem. An ionization selectivity factor of at least 1000:1 has been measured for promethium over samarium at 584.6 nm. Resonance ionization spectra have been recorded for both elements over the 528-560 and 580-614 nm wavelength ranges.

  15. Analysis of perchlorate in groundwater by electrospray ionization mass spectrometry/mass spectrometry

    SciTech Connect

    Koester, C.J.; Beller, H.R.; Halden, R.U.

    2000-05-01

    An electrospray ionization mass spectrometry/mass spectrometry (ESI/MS/MS) method was developed to measure part-per-billion ({micro}g/L) concentrations of perchlorate in groundwater. Selective and sensitive perchlorate detection was achieved by operating the mass spectrometer in the negative ionization mode and by using MS/MS to monitor the CIO{sub 4}{sup {minus}} to ClO{sub 3}{sup {minus}} transition. The method of standard additions was used to address the considerable signal suppression caused by anions that are typically present in groundwater, such as bicarbonate and sulfate. ESI-MS/MS analysis was rapid, accurate, reproducible, and provided a detection limit of 0.5 {micro}g/L perchlorate in groundwater. Accuracy and precision of the ESI/MS/MS method were assessed by analyzing performance evaluation samples in a groundwater matrix and by comparing ion chromatography (IC) and ESI/MS/MS results for local groundwater samples. Results for the performance evaluation samples differed from the certified values by 4--13%, and precision ranged from 3 to 10% (relative standard deviation). The IC and ESI/MS/MS results were statistically indistinguishable for perchlorate concentrations above the detection limits of both methods.

  16. Chemical Ionization Mass Spectrometry Using Carbon Nanotube Field Emission Electron Sources

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    DOEpatents

    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.

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

    DOEpatents

    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.

  20. A cautionary note on the effects of laboratory air contaminants on ambient ionization mass spectrometry measurements.

    PubMed

    Kumbhani, Sambhav R; Wingen, Lisa M; Perraud, Véronique; Finlayson-Pitts, Barbara J

    2017-10-15

    Ambient ionization mass spectrometry methods are convenient, sensitive and require little sample preparation. However, they are susceptible to species present in air surrounding the mass spectrometer. This study identifies some challenges associated with the potential impacts of indoor air contaminants on ionization and analysis involving open-air methods. Unexpected effects of volatile organic compounds (VOCs) from floor maintenance activities on ambient ionization mass spectrometry were studied using three different ambient ionization techniques. Extractive electrospray ionization (EESI), direct analysis in real time (DART) and ionization by piezoelectric direct discharge (PDD) plasma were demonstrated in this study to be affected by indoor air contaminants. Identification of contaminant vapors was verified by comparison with standards using EESI-MS/MS product ion scans. Emissions of diethylene glycol monoethyl ether and ethylene glycol monobutyl ether are identified from floor stripping and waxing solutions using three ambient ionization mass spectrometry techniques. These unexpected indoor air contaminants are capable of more than 75% ion suppression of target analytes due to their high volatility, proton affinity and solubility compared with the target analytes. The contaminant vapors are also shown to form adducts with one of the target analytes. The common practice in MS analysis of subtracting a background air spectrum may not be appropriate if the presence of ionizable air contaminants alters the spectrum in unexpected ways. For example, VOCs released into air from floor stripping and waxing are capable of causing ion suppression of target analytes. Copyright © 2017 John Wiley & Sons, Ltd.

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

    PubMed

    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

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

    SciTech Connect

    Isselhardt, Brett H.

    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.

  3. Evaluation of the performance of small diode pumped UV solid state (DPSS) Nd:YAG lasers as new radiation sources for atmospheric pressure laser ionization mass spectrometry (APLI-MS).

    PubMed

    Kersten, Hendrik; Lorenz, Matthias; Brockmann, Klaus J; Benter, Thorsten

    2011-06-01

    The performance of a KrF* bench top excimer laser and a compact diode pumped UV solid state (DPSS) Nd:YAG laser as photo-ionizing source in LC-APLI MS is compared. The commonly applied bench-top excimer laser, operating at 248 nm, provides power densities of the order of low MW/cm(2) on an illuminated area of 0.5 cm(2) (8 mJ/pulse, 5 ns pulse duration, beam waist area 0.5 cm(2), 3 MW/cm(2)). The DPSS laser, operating at 266 nm, provides higher power densities, however, on a two orders of magnitude smaller illuminated area (60 μJ/pulse, 1 ns pulse duration, beam waist area 2 × 10(-3) cm(2), 30 MW/cm(2)). In a common LC-APLI MS setup with direct infusion of a 10 nM pyrene solution, the DPSS laser yields a significantly smaller ion signal (0.9%) and signal to noise ratio (1.4%) compared with the excimer laser. With respect to the determined low detection limits (LODs) for PAHs of 0.1 fmol using an excimer laser, LODs in DPSS laser LC-APLI MS in the low pmol regime are expected. The advantages of the DPSS laser with respect to applicability (size, cost, simplicity) may render this light source the preferred one for APLI applications not focusing on ultimately high sensitivities. Furthermore, the impact of adjustable ion source parameters on the performance of both laser systems is discussed in terms of the spatial sensitivity distribution described by the distribution of ion acceptance (DIA) measurements. Perspectives concerning the impact on future APLI-MS applications are given.

  4. Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of methylcyclohexane in the supersonic jet

    NASA Astrophysics Data System (ADS)

    Han, Songhee; Yoo, Hyun Sik; Ahn, Doo-Sik; Choi, Young S.; Kim, Sang Kyu

    2011-12-01

    Vacuum ultraviolet (VUV) mass-analyzed threshold ionization (MATI) spectrum of supersonically cooled methylcyclohexane has been obtained to give the precise adiabatic ionization energy of 9.6958 ± 0.0025 eV for the chair equatorial conformer. Vibrationally resolved MATI spectrum has been analyzed with the aid of density functional theory and Franck-Condon calculations. The MATI spectrum reflects the structural change upon ionization and its origin is discussed by inspecting the shapes of the valence orbitals involved in the ionization process. The spectroscopic implication of the structural interconversion above the certain energy level is discussed with theoretical calculations of molecular structures and energetics.

  5. Toward a Fieldable Atomic Mass Spectrometer for Safeguards Applications: Sample Preparation and Ionization

    SciTech Connect

    Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth; Jones, Sarah MH; Manard, Benjamin T.

    2014-10-31

    The International Atomic Energy Agency’s (IAEA’s) long-term research and development plan calls for the development of new methods to detect misuse at nuclear fuel cycle facilities such as reprocessing and enrichment plants. At enrichment plants, for example, the IAEA’s contemporary safeguards approaches are based on a combination of routine and random inspections that include collection of UF6 samples from in-process material and selected cylinders for subsequent analyses. These analyses include destructive analysis (DA) in a laboratory (typically by mass spectrometry [MS]) for isotopic characterization, and environmental sampling (ES) for subsequent laboratory elemental and isotopic analysis (also both typically by MS). One area of new method development includes moving this kind of isotope ratio analytical capability for DA and ES activities into the field. Some of the reasons for these developments include timeliness of results, avoidance of hazardous material shipments, and guidance for additional sample collecting. However, this capability does not already exist for several reasons, such as that most lab-based chemical and instrumental methods rely on laboratory infrastructure (highly trained staff, power, space, hazardous material handling, etc.) and require significant amounts of consumables (power, compressed gases, etc.). In addition, there are no currently available, fieldable instruments for atomic or isotope ratio analysis. To address these issues, Pacific Northwest National Laboratory (PNNL) and collaborator, Clemson University, are studying key areas that limit the fieldability of isotope ratio mass spectrometry for atomic ions: sample preparation and ionization, and reducing the physical size of a fieldable mass spectrometer. PNNL is seeking simple and robust techniques that could be effectively used by inspectors who may have no expertise in analytical MS. In this report, we present and describe the preliminary findings for three candidate

  6. High-throughput solvent assisted ionization inlet for use in mass spectrometry.

    PubMed

    Wang, Beixi; Trimpin, Sarah

    2014-01-21

    In this work we developed a multiplexed analysis platform providing a simple high-throughput means to characterize solutions. Automated analyses, requiring less than 5 s per sample without carryover and 1 s per sample, accepting minor cross contamination, was achieved using multiplexed solvent assisted ionization inlet (SAII) mass spectrometry (MS). The method involves sequentially moving rows of pipet tips containing sample solutions in close proximity to the inlet aperture of a heated mass spectrometer inlet tube. The solution is pulled from the container into the mass spectrometer inlet by the pressure differential at the mass spectrometer inlet aperture. This sample introduction method for direct injection of solutions is fast, easily implemented, and widely applicable, as is shown by applications ranging from small molecules to proteins as large as carbonic anhydrase (molecular weight ca. 29,000). MS/MS fragmentation is applicable for sample characterization. An x,y-stage and common imaging software are incorporated to map the location of components in the sample wells of a microtiter plate. Location within an x,y-array of different sample solutions and the relative concentration of the sample are displayed using ion intensity maps.

  7. Multi-component analysis (sterols, tocopherols and triterpenic dialcohols) of the unsaponifiable fraction of vegetable oils by liquid chromatography-atmospheric pressure chemical ionization-ion trap mass spectrometry.

    PubMed

    Zarrouk, Wissem; Carrasco-Pancorbo, Alegría; Zarrouk, Mokhtar; Segura-Carretero, Antonio; Fernández-Gutiérrez, Alberto

    2009-12-15

    A simple and sensitive method for the analysis of sterols, tocopherols and triterpenic dialcohols from the unsaponifiable fraction from oil samples in a single analytical run using liquid chromatography coupled to mass spectrometry was developed. With this method, the compounds could be detected directly after dissolving the unsaponifiable fraction in acetonitrile without necessity of time-consuming sample pre-treatment or derivatization. Separation of the analytes was carried out at room temperature, by using a C18 column (5 microm i.d. 3.0 mm x 250 mm) with a linear gradient of acetonitrile/water (0.01% acetic acid) at a flow rate of 1.5 mL/min. The full scan mass spectra of the investigated compounds were measured by an ion trap mass spectrometer equipped with an APCI ion source. The optimized methodology was suitable for the identification of 23 compounds belonging to different families present in olive oil and other kinds of oils, as well as for the quantification of 15 analytes (vs. their commercial standards).

  8. Spatially resolved thermal desorption/ionization coupled with mass spectrometry

    DOEpatents

    Jesse, Stephen; Van Berkel, Gary J; Ovchinnikova, Olga S

    2013-02-26

    A system and method for sub-micron analysis of a chemical composition of a specimen are described. The method includes providing a specimen for evaluation and a thermal desorption probe, thermally desorbing an analyte from a target site of said specimen using the thermally active tip to form a gaseous analyte, ionizing the gaseous analyte to form an ionized analyte, and analyzing a chemical composition of the ionized analyte. The thermally desorbing step can include heating said thermally active tip to above 200.degree. C., and positioning the target site and the thermally active tip such that the heating step forms the gaseous analyte. The thermal desorption probe can include a thermally active tip extending from a cantilever body and an apex of the thermally active tip can have a radius of 250 nm or less.

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

    SciTech Connect

    Yang, Liyu; Lee, Cheng S.; Hofstadler, Steven A. ); Smith, Richard D. )

    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).

  10. Droplet dynamics and ionization mechanisms in desorption electrospray ionization mass spectrometry.

    PubMed

    Venter, Andre; Sojka, Paul E; Cooks, R Graham

    2006-12-15

    A droplet pickup and other mechanisms have been suggested for the ionization of biomolecules like peptides and proteins by desorption electrospray ionization. To verify this hypothesis phase Doppler particle analysis was used to study the sizes and velocities of droplets involved in DESI. It was found that impacting droplets typically have velocities of 120 m/s and average diameters of 2-4 microm. Small differences in sprayer construction influence the operating conditions at which droplets of these dimensions are produced. Under these conditions, the kinetic energy per impacting water molecule is less than 0.6 meV and sputtering through momentum transfer during collisions or ionization by other electronic processes is unlikely. Droplets arrive at the surface with velocities well below the speed of sound in common materials, thereby excluding the possibility of ionization by shockwave formation. Some droplets appear to roll along the surface, increasing contact time and presumably the amount of material that is taken up into droplets during conditions typical of the DESI experiment.

  11. Formation and reactions of negative ions relevant to chemical ionization mass spectrometry. I. Cl mass spectra of organic compounds produced by F− reactions

    PubMed Central

    Tiernan, T. O.; Chang, C.; Cheng, C. C.

    1980-01-01

    A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F− with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F− reagent ion was generated from CF3H or NF3, typically at an ion source pressure of 100 μm. In pure NF3, F− is the major ion formed and constitutes more than 90% of the total ion intensity. While F− is also the major primary ion formed in pure CF3H, it undergoes rapid ion-molecule