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Sample records for nano-secondary ion mass

  1. Speciation of Nitrogen-Bearing Species Using Negative and Positive Secondary Ion Spectra with Nano Secondary Ion Mass Spectrometry.

    PubMed

    Li, Kexue; Sinha, Baerbel; Hoppe, Peter

    2016-03-15

    In this study, we demonstrate that Nano Secondary Ion Mass Spectrometry (NanoSIMS) can be used to differentiate different nitrogen-containing species commonly observed in atmospheric aerosol particles with micrometer or submicrometer spatial resolution, on the basis of the relative intensity of secondary ion signals, both in negative and positive secondary ion mode, without the need to chemically or physically separate the samples. Compounds tested include nitrate, nitrite, ammonium salts, urea, amino acids, sugars, organic acids, amides, triazine, imidazole, protein, and biological tissue. We show that NO2(-) secondary ions are unique to the decomposition of nitrate and nitrite salts, whereas NH4(+) secondary ions are unique to samples containing ammonium ions, with low signal intensities observed from amino groups but none from biological tissue. CN(-) signals are obtained from all nitrogen-bearing compounds, but relative signal intensities are the highest for organic nitrogen-containing compounds. We demonstrate that quantitative determination of the elemental fractions of carbon, oxygen, and nitrate in nanometer-sized aerosol samples using normalized secondary ion intensities is possible. We further demonstrate that stable isotope ratios measured on in-house standards of unknown isotopic composition using the (12)C(15)N(-)/(12)C(14)N(-) ratio (all nitrogen-containing species), the (15)N(16)O2(-)/(14)N(16)O2(-) ratio (nitrate and nitrite species), and the (15)NH4(+)/(14)NH4(+) ratio (ammonium salts, amino acids, and urea) are stable and sufficiently precise for nitrogen isotope analysis. PMID:26854563

  2. Elemental mapping of Neuromelanin organelles of human Substantia Nigra: correlative ultrastructural and chemical analysis by analytical transmission electron microscopy and nano-secondary ion mass spectrometry.

    PubMed

    Biesemeier, Antje; Eibl, Oliver; Eswara, Santhana; Audinot, Jean-Nicolas; Wirtz, Tom; Pezzoli, Gianni; Zucca, Fabio A; Zecca, Luigi; Schraermeyer, Ulrich

    2016-07-01

    Neuromelanin (NM) is a compound which highly accumulates mainly in catecholamine neurons of the substantia nigra (SN), and is contained in organelles (NM-containing organelles) with lipid bodies and proteins. These neurons selectively degenerate in Parkinson's disease and NM can play either a protective or toxic role. NM-containing organelles of SN were investigated by Analytical Electron Microscopy (AEM) and Nano-Secondary Ion Mass Spectrometry (NanoSIMS) within human tissue sections with respect to ultrastructure and elemental composition. Within the NM-containing organelle, the single NM granules and lipid bodies had sizes of about 200-600 nm. Energy-Dispersive X-ray microanalysis spectra of the NM granules and lipid bodies were acquired with 100 nm beam diameter in AEM, NanoSIMS yielded elemental maps with a lateral resolution of about 150 nm. AEM yielded the quantitative elemental composition of NM granules and bound metals, e.g., iron with a mole fraction of about 0.15 atomic percent. Chemical analyses by AEM and NanoSIMS were consistent at the subcellular level so that nanoSIMS measurements have been quantitated. In NM granules of SN from healthy subjects, a significant amount of S, Fe, and Cu was found. In lipid bodies an amount of P consistent with the presence of phospholipids was measured. The improved detection limits of nanoSIMS offer new possibilities for chemical mapping, high-sensitivity trace element detection, and reduced acquisition times. Variations between individual NM granules can now be investigated effectively and quantitatively by NanoSIMS mapping Cu and Fe. This should yield new insight into the changes in chemical composition of NM pigments during healthy aging and disease. Neuromelanin-containing organelles of dopamine neurons in normal human substantia nigra were investigated by analytical electron mircoscopy and secondary ion mass spectroscopy (NanoSIMS) yielding the ultrastructure and elemental composition. In neuromelanin

  3. A New Radio Frequency Plasma Oxygen Primary Ion Source on Nano Secondary Ion Mass Spectrometry for Improved Lateral Resolution and Detection of Electropositive Elements at Single Cell Level.

    PubMed

    Malherbe, Julien; Penen, Florent; Isaure, Marie-Pierre; Frank, Julia; Hause, Gerd; Dobritzsch, Dirk; Gontier, Etienne; Horréard, François; Hillion, François; Schaumlöffel, Dirk

    2016-07-19

    An important application field of secondary ion mass spectrometry at the nanometer scale (NanoSIMS) is the detection of chemical elements and, in particular, metals at the subcellular level in biological samples. The detection of many trace metals requires an oxygen primary ion source to allow the generation of positive secondary ions with high yield in the NanoSIMS. The duoplasmatron oxygen source is commonly used in this ion microprobe but cannot achieve the same quality of images as the cesium primary ion source used to produce negative secondary ions (C(-), CN(-), S(-), P(-)) due to a larger primary ion beam size. In this paper, a new type of an oxygen ion source using a rf plasma is fitted and characterized on a NanoSIMS50L. The performances of this primary ion source in terms of current density and achievable lateral resolution have been characterized and compared to the conventional duoplasmatron and cesium sources. The new rf plasma oxygen source offered a net improvement in terms of primary beam current density compared to the commonly used duoplasmatron source, which resulted in higher ultimate lateral resolutions down to 37 nm and which provided a 5-45 times higher apparent sensitivity for electropositive elements. Other advantages include a better long-term stability and reduced maintenance. This new rf plasma oxygen primary ion source has been applied to the localization of essential macroelements and trace metals at basal levels in two biological models, cells of Chlamydomonas reinhardtii and Arabidopsis thaliana. PMID:27291826

  4. Ion Trap Mass Spectrometry

    SciTech Connect

    Eiden, Greg C.

    2005-09-01

    This chapter describes research conducted in a few research groups in the 1990s in which RF quadrupole ion trap mass spectrometers were coupled to a powerful atomic ion source, the inductively coupled plasma used in conventional ICP-MS instruments. Major section titles for this chapter are: RF Quadrupole Ion Traps Features of RF Quadrupole Ion Trap Mass Spectrometers Selective Ion Trapping methods Inductively Coupled Plasma Source Ion Trap Mass Spectrometers

  5. Ion mass spectrometer

    NASA Technical Reports Server (NTRS)

    Neugebauer, M. (Inventor); Clay, D. R.; Goldstein, B. E.; Goldstein, R.

    1984-01-01

    An ion mass spectrometer is described which detects and indicates the characteristics of ions received over a wide angle, and which indicates the mass to charge ratio, the energy, and the direction of each detected ion. The spectrometer includes a magnetic analyzer having a sector magnet that passes ions received over a wide angle, and an electrostatic analyzer positioned to receive ions passing through the magnetic analyzer. The electrostatic analyzer includes a two dimensional ion sensor at one wall of the analyzer chamber, that senses not only the lengthwise position of the detected ion to indicate its mass to charge ratio, but also detects the ion position along the width of the chamber to indicate the direction in which the ion was traveling.

  6. Highly charged ion secondary ion mass spectroscopy

    DOEpatents

    Hamza, Alex V.; Schenkel, Thomas; Barnes, Alan V.; Schneider, Dieter H.

    2001-01-01

    A secondary ion mass spectrometer using slow, highly charged ions produced in an electron beam ion trap permits ultra-sensitive surface analysis and high spatial resolution simultaneously. The spectrometer comprises an ion source producing a primary ion beam of highly charged ions that are directed at a target surface, a mass analyzer, and a microchannel plate detector of secondary ions that are sputtered from the target surface after interaction with the primary beam. The unusually high secondary ion yield permits the use of coincidence counting, in which the secondary ion stops are detected in coincidence with a particular secondary ion. The association of specific molecular species can be correlated. The unique multiple secondary nature of the highly charged ion interaction enables this new analytical technique.

  7. Mini ion trap mass spectrometer

    DOEpatents

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

    1995-09-19

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

  8. Mini ion trap mass spectrometer

    DOEpatents

    Dietrich, Daniel D.; Keville, Robert F.

    1995-01-01

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

  9. Ion mobility-mass spectrometry.

    PubMed

    Kanu, Abu B; Dwivedi, Prabha; Tam, Maggie; Matz, Laura; Hill, Herbert H

    2008-01-01

    This review article compares and contrasts various types of ion mobility-mass spectrometers available today and describes their advantages for application to a wide range of analytes. Ion mobility spectrometry (IMS), when coupled with mass spectrometry, offers value-added data not possible from mass spectra alone. Separation of isomers, isobars, and conformers; reduction of chemical noise; and measurement of ion size are possible with the addition of ion mobility cells to mass spectrometers. In addition, structurally similar ions and ions of the same charge state can be separated into families of ions which appear along a unique mass-mobility correlation line. This review describes the four methods of ion mobility separation currently used with mass spectrometry. They are (1) drift-time ion mobility spectrometry (DTIMS), (2) aspiration ion mobility spectrometry (AIMS), (3) differential-mobility spectrometry (DMS) which is also called field-asymmetric waveform ion mobility spectrometry (FAIMS) and (4) traveling-wave ion mobility spectrometry (TWIMS). DTIMS provides the highest IMS resolving power and is the only IMS method which can directly measure collision cross-sections. AIMS is a low resolution mobility separation method but can monitor ions in a continuous manner. DMS and FAIMS offer continuous-ion monitoring capability as well as orthogonal ion mobility separation in which high-separation selectivity can be achieved. TWIMS is a novel method of IMS with a low resolving power but has good sensitivity and is well intergrated into a commercial mass spectrometer. One hundred and sixty references on ion mobility-mass spectrometry (IMMS) are provided. PMID:18200615

  10. Halo ion trap mass spectrometer.

    PubMed

    Austin, Daniel E; Wang, Miao; Tolley, Samuel E; Maas, Jeffrey D; Hawkins, Aaron R; Rockwood, Alan L; Tolley, H Dennis; Lee, Edgar D; Lee, Milton L

    2007-04-01

    We describe a novel radio frequency ion trap mass analyzer based on toroidal trapping geometry and microfabrication technology. The device, called the halo ion trap, consists of two parallel ceramic plates, the facing surfaces of which are imprinted with sets of concentric ring electrodes. Radii of the imprinted rings range from 5 to 12 mm, and the spacing between the plates is 4 mm. Unlike conventional ion traps, in which hyperbolic metal electrodes establish equipotential boundary conditions, electric fields in the halo ion trap are established by applying different radio frequency potentials to each ring. The potential on each ring can be independently optimized to provide the best trapping field. The halo ion trap features an open structure, allowing easy access for in situ ionization. The toroidal geometry provides a large trapping and analyzing volume, increasing the number of ions that can be stored and reducing the effects of space-charge on mass analysis. Preliminary mass spectra show resolution (m/Deltam) of 60-75 when the trap is operated at 1.9 MHz and 500 Vp-p. PMID:17335180

  11. A cometary ion mass spectrometer

    NASA Technical Reports Server (NTRS)

    Shelley, E. G.; Simpson, D. A.

    1984-01-01

    The development of flight suitable analyzer units for that part of the GIOTTO Ion Mass Spectrometer (IMS) experiment designated the High Energy Range Spectrometer (HERS) is discussed. Topics covered include: design of the total ion-optical system for the HERS analyzer; the preparation of the design of analyzing magnet; the evaluation of microchannel plate detectors and associated two-dimensional anode arrays; and the fabrication and evaluation of two flight-suitable units of the complete ion-optical analyzer system including two-dimensional imaging detectors and associated image encoding electronics.

  12. Microscale ion trap mass spectrometer

    DOEpatents

    Ramsey, J. Michael; Witten, William B.; Kornienko, Oleg

    2002-01-01

    An ion trap for mass spectrometric chemical analysis of ions is delineated. The ion trap includes a central electrode having an aperture; a pair of insulators, each having an aperture; a pair of end cap electrodes, each having an aperture; a first electronic signal source coupled to the central electrode; a second electronic signal source coupled to the end cap electrodes. The central electrode, insulators, and end cap electrodes are united in a sandwich construction where their respective apertures are coaxially aligned and symmetric about an axis to form a partially enclosed cavity having an effective radius r.sub.0 and an effective length 2z.sub.0, wherein r.sub.0 and/or z.sub.0 are less than 1.0 mm, and a ratio z.sub.0 /r.sub.0 is greater than 0.83.

  13. The ion mass spectrometer on Giotto

    NASA Technical Reports Server (NTRS)

    Balsiger, H.; Altwegg, K.; Buehler, F.; Fischer, J.; Geiss, J.; Benson, J.; Hemmerich, P.; Goldstein, B. E.; Goldstein, R.; Neugebauer, M.

    1987-01-01

    The design of the Giotto ion mass spectrometer (IMS) system, its calibration, and the initial flight performance are discussed. The IMS system consists of two sensors: one optimized for the outer coma, the other for the inner coma, with each sensor obtaining complementary information in the region for which it was not optimized. Both sensors feature mass-imaging characteristics, permitting simultaneous measurements of several ion species by means of multi-detector arrays, with resultant mass per charge resolution of not less than 20. In addition to mass per charge, the energy per charge and the elevation and azimuth of the incident ions were measured during the Giotto flight.

  14. Mass spectrometry and inhomogeneous ion optics

    NASA Technical Reports Server (NTRS)

    White, F. A.

    1973-01-01

    Work done in several areas to advance the state of the art of magnetic mass spectrometers is described. The calculations and data necessary for the design of inhomogeneous field mass spectrometers, and the calculation of ion trajectories through such fields are presented. The development and testing of solid state ion detection devices providing the capability of counting single ions is discussed. New techniques in the preparation and operation of thermal-ionization ion sources are described. Data obtained on the concentrations of copper in rainfall and uranium in air samples using the improved thermal ionization techniques are presented. The design of a closed system static mass spectrometer for isotopic analyses is discussed. A summary of instrumental aspects of a four-stage mass spectrometer comprising two electrostatic and two 90 deg. magnetic lenses with a 122-cm radius used to study the interaction of ions with solids is presented.

  15. Ions in oceanic and continental air masses

    SciTech Connect

    Tanner, D.J.; Eisele, F.L. )

    1991-01-20

    Measurements of tropospheric ions and several trace atmospheric neutral species have been performed at Cheeka Peak Research Station and at Mauna Loa Observatory. Two new positive ion species at masses 114 and 102 have been identified as protonated caprolactam and a saturated 6-carbon primary amine, respectively. In the negative ion spectrum, methane sulfonic acid (MSA) has been identified as the parent species responsible for an ion commonly observed at mass 95 during these two studies. The diurnal variations of gas phase H{sub 2}SO{sub 4} and MSA were also measured at Cheeka Peak and have typically been found to be present in the sub-ppt range. Ion assisted measurements at Mauna Loa Observatory of pyridine and ammonia indicate concentrations of 2.5 and 70 ppt, respectively, with at least a factor of 2 uncertainty. Interesting variations and potential sources of several of the observed ions are also discussed.

  16. Secondary ion coincidence in highly charged ion based secondary ion mass spectroscopy for process characterization

    SciTech Connect

    Hamza, A.V.; Schenkel, T.; Barnes, A.V.; Schneider, D.H.

    1999-01-01

    Coincidence counting in highly charged ion based secondary ion mass spectroscopy has been applied to the characterization of selective tungsten deposition via disilane reduction of tungsten hexafluoride on a patterned SiO{sub 2}/Si wafer. The high secondary ion yield and the secondary ion emission from a small area produced by highly charged ions make the coincidence technique very powerful.

  17. An electrostatic autoresonant ion trap mass spectrometer

    SciTech Connect

    Ermakov, A. V.; Hinch, B. J.

    2010-01-15

    A new method for ion extraction from an anharmonic electrostatic trap is introduced. Anharmonicity is a common feature of electrostatic traps which can be used for small scale spatial confinement of ions, and this feature is also necessary for autoresonant ion extraction. With the aid of ion trajectory simulations, novel autoresonant trap mass spectrometers (ART-MSs) have been designed based on these very simple principles. A mass resolution {approx}60 is demonstrated for the prototypes discussed here. We report also on the pressure dependencies, and the (mV) rf field strength dependencies of the ART-MS sensitivity. Importantly the new MS designs do not require heavy magnets, tight manufacturing tolerances, introduction of buffer gases, high power rf sources, nor complicated electronics. The designs described here are very inexpensive to implement relative to other instruments, and can be easily miniaturized. Possible applications are discussed.

  18. Miniaturized Linear Wire Ion Trap Mass Analyzer.

    PubMed

    Wu, Qinghao; Li, Ailin; Tian, Yuan; Zare, Richard N; Austin, Daniel E

    2016-08-01

    We report a linear ion trap (LIT) in which the electric field is formed by fine wires held under tension and accurately positioned using holes drilled in two end plates made of plastic. The coordinates of the hole positions were optimized in simulation. The stability diagram and mass spectra using boundary ejection were compared between simulation and experiment and good agreement was found. The mass spectra from experiments show peak widths (fwhm) in units of mass-to-charge of around 0.38 Th using a scan rate of 3830 Th/s. The limits of detection are 137 ppbv and 401 ppbv for benzene and toluene, respectively. Different sizes of the wire ion trap can be easily fabricated by drilling holes in scaled positions. Other distinguishing features, such as high ion and photon transmission, low capacitance, high tolerance to mechanical and assembly error, and low weight, are discussed. PMID:27373557

  19. Accelerator mass spectrometry with heavy ions

    NASA Astrophysics Data System (ADS)

    Haberstock, Günther; Heinzl, Johann; Korschinek, Gunther; Morinaga, Haruhiko; Nolte, Eckehart; Ratzinger, Ulrich; Kato, Kazuo; Wolf, Manfred

    1986-11-01

    Accelerator mass spectrometry measurements with fully stripped 36Cl ions have been performed at the Munich accelerator laboratory in order to date groundwaters and palaeontological samples, to study anthropogenic 36Cl produced through nuclear tests and to determine the fast neutron flux of the Hiroshima A-bomb.

  20. Secondary ion mass spectrometry of MCsn+molecular ion complexes

    NASA Astrophysics Data System (ADS)

    Saha, Biswajit; Chakraborty, Purushottam

    2007-05-01

    Excellent detection sensitivity, high dynamic range and good depth resolution make the SIMS technique extremely powerful for the analysis of surfaces and interfaces. However, a serious problem in SIMS analysis is its "matrix effect" that hinders the quantification of a certain species in a sample and consequently, probing the composition of surfaces or interfaces by SIMS is greatly hindered. Appropriate corrective measures are therefore, needed to calibrate the secondary ion currents into respective concentrations for accurate compositional analysis. Working in the MCs+-SIMS mode (M - element to be analyzed, Cs+ - bombarding ions) can circumvent the matrix effect. The quantitative potential of the MCs+-SIMS method is understood by assuming that an MCs+ ion is generated by the combination of a secondary neutral M0 atom with a re-sputtered Cs+ ion in the near-surface region. The emission process for the species M0 is thus decoupled from the subsequent MCs+ ion formation process, in analogy with the ion formation in secondary neutral mass spectrometry (SNMS), resulting in a drastic decrease in matrix effect. Although this technique has found its applicability in direct quantification, it generally suffers from a low useful yield. In such cases, detection of MCsn+(n = 2, 3, …) molecular ions offers a better sensitivity as the yields of such molecular ion complexes have often been found higher than that of MCs+ ions. This is true in most of the cases where the elements are strongly electronegative with respect to cesium. Several works have been reported on the emission of MCsn+molecular ions in the SIMS process, but a complete understanding on the formation mechanism of these ion complexes is still lacking. The kinetic energy distributions of secondary MCsn+molecular ion complexes has been found to be an effective approach to estimate the local instantaneous surface work function changes under various surface exposure conditions, thereby enabling one to elucidate on

  1. New Cs sputter ion source with polyatomic ion beams for secondary ion mass spectrometry applications

    SciTech Connect

    Belykh, S. F.; Palitsin, V. V.; Veryovkin, I. V.; Kovarsky, A. P.; Chang, R. J. H.; Adriaens, A.; Dowsett, M. G.; Adams, F.

    2007-08-15

    A simple design for a cesium sputter ion source compatible with vacuum and ion-optical systems as well as with electronics of the commercially available Cameca IMS-4f instrument is reported. This ion source has been tested with the cluster primary ions of Si{sub n}{sup -} and Cu{sub n}{sup -}. Our experiments with surface characterization and depth profiling conducted to date demonstrate improvements of the analytical capabilities of the secondary ion mass spectrometry instrument due to the nonadditive enhancement of secondary ion emission and shorter ion ranges of polyatomic projectiles compared to atomic ones with the same impact energy.

  2. AFE ion mass spectrometer design study

    NASA Technical Reports Server (NTRS)

    Wright, Willie

    1989-01-01

    This final technical report covers the activities engaged in by the University of Texas at Dallas, Center for Space Sciences in conjunction with the NASA Langley Research Center, Systems Engineering Division in design studies directed towards defining a suitable ion mass spectrometer to determine the plasma parameter around the Aeroassisted Flight Experiment vehicle during passage through the earth's upper atmosphere. Additional studies relate to the use of a Langmuir probe to measure windward ion/electron concentrations and temperatures. Selected instrument inlet subsystems were tested in the NASA Ames Arc-Jet Facility.

  3. Ion Mobility Spectrometry (IMS) and Mass Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.

    2010-04-20

    In a media of finite viscosity, the Coulomb force of external electric field moves ions with some terminal speed. This dynamics is controlled by “mobility” - a property of the interaction potential between ions and media molecules. This fact has been used to separate and characterize gas-phase ions in various modes of ion mobility spectrometry (IMS) developed since 1970. Commercial IMS devices were introduced in 1980-s for field detection of volatile traces such as explosives and chemical warfare agents. Coupling to soft-ionization sources, mass spectrometry (MS), and chromatographic methods in 1990-s had allowed IMS to handle complex samples, enabling new applications in biological and environmental analyses, nanoscience, and other areas. Since 2003, the introduction of commercial systems by major instrument vendors started bringing the IMS/MS capability to broad user community. The other major development of last decade has been the differential IMS or “field asymmetric waveform IMS” (FAIMS) that employs asymmetric time-dependent electric field to sort ions not by mobility itself, but by the difference between its values in strong and weak electric fields. Coupling of FAIMS to conventional IMS and stacking of conventional IMS stages have enabled two-dimensional separations that dramatically expand the power of ion mobility methods.

  4. The ion mass loading rate at Io

    NASA Astrophysics Data System (ADS)

    Saur, Joachim; Strobel, Darrell F.; Neubauer, Fritz M.; Summers, Michael E.

    2003-06-01

    The Io plasma torus, composed of mostly heavy ions of oxygen and sulfur, is sustained by an Iogenic mass loading rate of ˜10 30 amu s -1 = 1.6 × 10 28 SO 2 s -1 or approximately 10 3 kg s -1(A.L. Broadfoot et al., 1979, Science 204, 979-982). We argue on the basis of available power sources, reanalysis of F. Bagenal (1997, Geophys. Res. Lett. 24, 2111-2114), HST UV remote sensing, and detailed model calculations that at most 20% of this mass leaves Io in the form of ions, i.e., ≤3 × 10 27 × ( ne,0 /3600 cm -3) ions s -1, where ne,0 is the average torus electron density. For the Galileo spacecraft Io pass in December 1995, the ion mass loading rate was ≤3 × 10 27 ions s -1, whereas for the Voyager epoch with lower ne,0 (=2000 cm -3), this rate would be ≤1.7 × 10 27 ions s -1, consistent with the D.E. Shemansky (1980, Astrophys. J. 242, 1266-1277) mass loading limit of ≤1 × 10 27 ions s -1. We investigate the processes that control Io's large scale electrodynamic interaction and find that the elastic collision rate exceeds the ionization/pickup rate by at least a factor of 5 for all atmospheric column densities considered (10 16-10 21 m -2) and by a factor of ˜100 for the most realistic column density. Consequently, elastic collisions are mostly responsible for Io's high conductances and thus generate Io's large scale electrodynamic interaction such as the generation of Io's electric current system and the slowing of the plasma flow. The electrodynamic part of Io's interaction is thus best described as an ionosphere-like interaction rather than a comet-like interaction. An analytic expression for total electron impact rates is derived for Io's atmosphere, which is independent of any particular model for the 3D interaction of torus electrons with its atmosphere.

  5. Noise reduction in negative-ion quadrupole mass spectrometry

    DOEpatents

    Chastagner, Philippe

    1993-01-01

    A quadrupole mass spectrometer (QMS) system having an ion source, quadrupole mass filter, and ion collector/recorder system. A weak, transverse magnetic field and an electron collector are disposed between the quadrupole and ion collector. When operated in negative ion mode, the ion source produces a beam of primarily negatively-charged particles from a sample, including electrons as well as ions. The beam passes through the quadrupole and enters the magnetic field, where the electrons are deflected away from the beam path to the electron collector. The negative ions pass undeflected to the ion collector where they are detected and recorded as a mass spectrum.

  6. Noise reduction in negative-ion quadrupole mass spectrometry

    DOEpatents

    Chastagner, P.

    1993-04-20

    A quadrupole mass spectrometer (QMS) system is described having an ion source, quadrupole mass filter, and ion collector/recorder system. A weak, transverse magnetic field and an electron collector are disposed between the quadrupole and ion collector. When operated in negative ion mode, the ion source produces a beam of primarily negatively-charged particles from a sample, including electrons as well as ions. The beam passes through the quadrupole and enters the magnetic field, where the electrons are deflected away from the beam path to the electron collector. The negative ions pass undeflected to the ion collector where they are detected and recorded as a mass spectrum.

  7. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom T.; Alexander, M. Lizabeth

    2003-06-11

    Proton transfer reaction mass spectrometry is a relatively new field that has attracted a great deal of interest in the last few years. This technique uses H₃Oþ as a chemical ionization (CI) reagent to measure volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) to parts per trillion by volume (pptv) range. Mass spectra acquired with a proton transfer reaction mass spectrometer (PTR-MS) are simple because proton transfer chemical ionization is ‘soft’ and results in little or no fragmentation. Unfortunately, peak identification can still be difficult due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). The use of an ITMS is appealing because of its ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates are possible that will allow for detection of multiple compounds. Here we present the first results from a proton transfer reaction ion trap mass spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype instrument in order to estimate possible detection limits of a second-generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated. Modifications are suggested that will enable further reduction in detection limits to the low-ppbv to high-pptv range. Furthermore, the applicability of MS/MS in differentiating between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making differentiation possible, even when a mixture of both species is present in the same sample. However, MS/MS spectra of acetone and propanal produce fragments with the same molecular masses but with different intensity ratios

  8. Precision mass measurements of highly charged ions

    NASA Astrophysics Data System (ADS)

    Kwiatkowski, A. A.; Bale, J. C.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Ettenauer, S.; Frekers, D.; Gallant, A. T.; Grossheim, A.; Lennarz, A.; Mane, E.; MacDonald, T. D.; Schultz, B. E.; Simon, M. C.; Simon, V. V.; Dilling, J.

    2012-10-01

    The reputation of Penning trap mass spectrometry for accuracy and precision was established with singly charged ions (SCI); however, the achievable precision and resolving power can be extended by using highly charged ions (HCI). The TITAN facility has demonstrated these enhancements for long-lived (T1/2>=50 ms) isobars and low-lying isomers, including ^71Ge^21+, ^74Rb^8+, ^78Rb^8+, and ^98Rb^15+. The Q-value of ^71Ge enters into the neutrino cross section, and the use of HCI reduced the resolving power required to distinguish the isobars from 3 x 10^5 to 20. The precision achieved in the measurement of ^74Rb^8+, a superallowed β-emitter and candidate to test the CVC hypothesis, rivaled earlier measurements with SCI in a fraction of the time. The 111.19(22) keV isomeric state in ^78Rb was resolved from the ground state. Mass measurements of neutron-rich Rb and Sr isotopes near A = 100 aid in determining the r-process pathway. Advanced ion manipulation techniques and recent results will be presented.

  9. In situ secondary ion mass spectrometry analysis

    SciTech Connect

    Groenewold, G.S.; Applehans, A.D.; Ingram, J.C.; Delmore, J.E.; Dahl, D.A.

    1993-01-01

    The direct detection of tributyl phosphate (TBP) on rocks using molecular beam surface analysis [MBSA or in situ secondary ion mass spectrometry (SIMS)] is demonstrated. Quantities as low as 250 ng were detected on basalt and sandstone with little or no sample preparation. Detection of TBP on soil has proven to be more problematic and requires further study. Ethylenediaminetetraacetic acid (EDTA) is more difficult to detect because it is very reactive with surfaces of interest. Nevertheless, it is possible to detect EDTA if the acidity of the surface is controlled. The detection of EDTA-metal complexes is currently an open question, but evidence is presented for the detection of ions arising from a EDTA-lead complex. Carboxylic acids (i.e., citric, ascorbic, malic, succinic, malonic, and oxalic) give characteristic SIM spectra, but their detection on sample surfaces awaits evaluation.

  10. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom; Alexander, M. Lizabeth

    2003-07-07

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a relatively new field that has attracted a great deal of interest in the last several years. This technique uses H3O+ as a chemical ionization (CI) agent for measuring volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) - parts per trillion by volume (pptv) range. PTR-MS mass spectra are simple because the ionization method of proton transfer is “soft”, resulting in little or no fragmentation. Unfortunately, the simplicity of the mass spectra can cause problems in peak identification due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). ITMS is appealing because of the ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates can be realized for detection of multiple compounds. We present here the first results from a Proton Transfer Reaction Ion Trap Mass Spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype interface in order to estimate possible detection limits of a second generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated for the PTR-ITMS. Modifications are suggested that will enable further reduction in detection limits to the low ppbv to pptv range. Furthermore the applicability of MS/MS to differentiate between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making a differentiation possible even when a mixture of both species is present in the same sample. MS/MS spectra of acetone and propanal produce fragments with the same molecular weight but different ratios, allowing quantitative distinction only if one species

  11. THOR Ion Mass Spectrometer instrument - IMS

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  12. Compact mass spectrometer for plasma discharge ion analysis

    DOEpatents

    Tuszewski, M.G.

    1997-07-22

    A mass spectrometer and methods are disclosed for mass spectrometry which are useful in characterizing a plasma. This mass spectrometer for determining type and quantity of ions present in a plasma is simple, compact, and inexpensive. It accomplishes mass analysis in a single step, rather than the usual two-step process comprised of ion extraction followed by mass filtering. Ions are captured by a measuring element placed in a plasma and accelerated by a known applied voltage. Captured ions are bent into near-circular orbits by a magnetic field such that they strike a collector, producing an electric current. Ion orbits vary with applied voltage and proton mass ratio of the ions, so that ion species may be identified. Current flow provides an indication of quantity of ions striking the collector. 7 figs.

  13. Compact mass spectrometer for plasma discharge ion analysis

    DOEpatents

    Tuszewski, Michel G.

    1997-01-01

    A mass spectrometer and methods for mass spectrometry which are useful in characterizing a plasma. This mass spectrometer for determining type and quantity of ions present in a plasma is simple, compact, and inexpensive. It accomplishes mass analysis in a single step, rather than the usual two-step process comprised of ion extraction followed by mass filtering. Ions are captured by a measuring element placed in a plasma and accelerated by a known applied voltage. Captured ions are bent into near-circular orbits by a magnetic field such that they strike a collector, producing an electric current. Ion orbits vary with applied voltage and proton mass ratio of the ions, so that ion species may be identified. Current flow provides an indication of quantity of ions striking the collector.

  14. Secondary Ion Mass Spectrometry of Environmental Aerosols

    SciTech Connect

    Gaspar, Daniel J.; Cliff, John B.

    2010-08-01

    Atmospheric particles influence many aspects of climate, air quality and human health. Understanding the composition, chemistry and behavior of atmospheric aerosols is a key remaining challenge in improving climate models. Furthermore, particles may be traced back to a particular source based on composition, stable isotope ratios, or the presence of particular surface chemistries. Finally, the characterization of atmospheric particles in the workplace plays an important role in understanding the potential for exposure and environmental and human health effects to engineered and natural nanoscale particles. Secondary ion mass spectrometry (SIMS) is a useful tool in determining any of several aspects of the structure, composition and chemistry of these particles. Often used in conjunction with other surface analysis and electron microscopy methods, SIMS has been used to determine or confirm reactions on and in particles, the presence of particular organic species on the surface of atmospheric aerosols and several other interesting and relevant findings. Various versions of SIMS instruments – dynamic SIMS, time of flight secondary ion mass spectrometry or TOF-SIMS, nanoSIMS – have been used to determine specific aspects of aerosol structure and chemistry. This article describes the strengths of each type of SIMS instrument in the characterization of aerosols, along with guidance on sample preparation, specific characterization specific to the particular information sought in the analysis. Examples and guidance are given for each type of SIMS analysis.

  15. Secondary Ion Mass Spectrometry SIMS XI

    NASA Astrophysics Data System (ADS)

    Gillen, G.; Lareau, R.; Bennett, J.; Stevie, F.

    2003-05-01

    This volume contains 252 contributions presented as plenary, invited and contributed poster and oral presentations at the 11th International Conference on Secondary Ion Mass Spectrometry (SIMS XI) held at the Hilton Hotel, Walt Disney World Village, Orlando, Florida, 7 12 September, 1997. The book covers a diverse range of research, reflecting the rapid growth in advanced semiconductor characterization, ultra shallow depth profiling, TOF-SIMS and the new areas in which SIMS techniques are being used, for example in biological sciences and organic surface characterization. Papers are presented under the following categories: Isotopic SIMS Biological SIMS Semiconductor Characterization Techniques and Applications Ultra Shallow Depth Profiling Depth Profiling Fundamental/Modelling and Diffusion Sputter-Induced Topography Fundamentals of Molecular Desorption Organic Materials Practical TOF-SIMS Polyatomic Primary Ions Materials/Surface Analysis Postionization Instrumentation Geological SIMS Imaging Fundamentals of Sputtering Ion Formation and Cluster Formation Quantitative Analysis Environmental/Particle Characterization Related Techniques These proceedings provide an invaluable source of reference for both newcomers to the field and experienced SIMS users.

  16. PULSED POSITIVE ION NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRIC APPLICATONS TO ENVIRONMENTAL AND HAZARDOUS WASTE ANALYSIS

    EPA Science Inventory

    The simultaneous acquisition of both positive ion and negative ion data under chemical ionization mass spectrometric conditions can aid in the confirmation of assignments made by electron impact gas chromatography mass spectrometry or electron capture gas chromatography. Pulsed p...

  17. Ion trajectories in an electrostatic ion guide for external ion source fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Marto, J A; Marshall, A G; May, M A; Limbach, P A

    1995-10-01

    An electrostatic ion guide (EIG) that consists of concentric cylinder and central wire electrodes can transport ions efficiently from an external ion source to an ion cyclotron resonance (ICR) ion trap for mass analysis, with several advantages over current injection methods. Because the electrostatic force of the EIG captures ions in a stable orbit about the wire electrode, ions with initially divergent trajectories may be redirected toward the ICR ion trap for improved ion transmission efficiency. SIMION trajectory calculations (ion kinetic energy, 1-200 eV; elevation angle, 0.30 °; azimuthal angle, 0.360°) predict that ions of m/z 1000 may be transmitted through a strong (0.01 → 3.0-T) magnetic field gradient. Judicious choice of ion source position and EIG potential minimizes the spread in ion axial kinetic energy at the ICR ion trap. Advantages of the EIG include large acceptance angle, even for ions that have large initial kinetic energy and large radial displacement with respect to the central z-axis, low ion extraction voltage (5-20 V), and efficient trapping because ions need not be accelerated to high velocity to pass through the magnetic field gradient. PMID:24214038

  18. Ion Neutral Mass Spectrometer Measurements from Titan

    NASA Technical Reports Server (NTRS)

    Waite, J. H., Jr.; Niemann, H.; Yelle, R. V.; Kasprzak, W.; Cravens, T.; Luhmann, J.; McNutt, R.; Ip, W.-H.; Gell, D.; Muller-Wordag, I. C. F.

    2005-01-01

    Introduction: The Ion Neutral Mass Spectrometer (INMS) aboard the Cassini orbiter has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, argon, and a host of stable carbon-nitrile compounds in its first flyby of Titan. The bulk composition and thermal structure of the moon s upper atmosphere do not appear to be changed since the Voyager flyby in 1979. However, the more sensitive techniques provided by modern in-situ mass spectrometry also give evidence for large-spatial-scale large-amplitude atmospheric waves in the upper atmosphere and for a plethora of stable carbon-nitrile compounds above 1174 km. Furthermore, they allow the first direct measurements of isotopes of nitrogen, carbon, and argon, which provide interesting clues about the evolution of the atmosphere. The atmosphere was first accreted as ammonia and ammonia ices from the Saturn sub-nebula. Subsequent photochemistry likely converted the atmosphere into molecular nitrogen. The early atmosphere was 1.5 to 5 times more substantial and was lost via escape over the intervening 4.5 billion years due to the reduced gravity associated with the relatively small mass of Titan. Carbon in the form of methane has continued to outgas over time from the interior with much of it being deposited in the form of complex hydrocarbons on the surface and some of it also being lost to space.

  19. Improved ion optics for introduction of ions into a 9.4-T Fourier transform ion cyclotron resonance mass spectrometer

    SciTech Connect

    Chen, Yu; Leach, Franklin E.; Kaiser, Nathan K.; Dang, Xibei; Ibrahim, Yehia M.; Norheim, Randolph V.; Anderson, Gordon A.; Smith, Richard D.; Marshall, Alan G.

    2015-01-19

    Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides unparalleled mass accuracy and resolving power.[1],[2] With electrospray ionization (ESI), ions are typically transferred into the mass spectrometer through a skimmer, which serves as a conductance-limiting orifice. However, the skimmer allows only a small fraction of incoming ions to enter the mass spectrometer. An ion funnel, originally developed by Smith and coworkers at Pacific Northwest National Laboratory (PNNL)[3-5] provides much more efficient ion focusing and transfer. The large entrance aperture of the ion funnel allows almost all ions emanating from a heated capillary to be efficiently captured and transferred, resulting in nearly lossless transmission.

  20. Mass spectrometer and methods of increasing dispersion between ion beams

    DOEpatents

    Appelhans, Anthony D.; Olson, John E.; Delmore, James E.

    2006-01-10

    A mass spectrometer includes a magnetic sector configured to separate a plurality of ion beams, and an electrostatic sector configured to receive the plurality of ion beams from the magnetic sector and increase separation between the ion beams, the electrostatic sector being used as a dispersive element following magnetic separation of the plurality of ion beams. Other apparatus and methods are provided.

  1. Ion trap array mass analyzer: structure and performance.

    PubMed

    Li, Xiaoxu; Jiang, Gongyu; Luo, Chan; Xu, Fuxing; Wang, Yuanyuan; Ding, Li; Ding, Chuan-Fan

    2009-06-15

    An ion trap array (ITA) mass analyzer--a novel ion trap mass analyzer with multiple ion trapping and analyzing channels--was designed and constructed. Its property and performance were investigated and reported in this paper. The ITA was built with several planar electrodes including two parallel printed circuit board (PCB) plates. Each PCB plate was fabricated to several identical rectangular electric strips based on normal PCB fabrication technology and was placed symmetrically to those on the opposite plate. There is no electrode between any two adjacent strips. Every strip was supplied with an rf voltage while the polarity of the voltage applied to the adjacent two strips was opposite. So the electric potential at the central plane between two adjacent strips is zero. Multiple identical electric field regions that contain the dominant quadrupole plus some other high-order fields were produced between the two PCB plates. The multiple identical electric field regions will have the property of ion trapping, ion storage, and mass analysis functions. So an ITA could work as multiple ion trap mass analyzers. It could perform multiple sample ion storage, mass-selected ion isolation, ion ejection, and mass analysis simultaneously. The ITA was operated at both "digital ion trap mode" and "conventional rf mode" experimentally. A preliminary mass spectrum has been carried out in one of the ion trap channels, and it shows a mass resolution of over 1000. Additional functions such as mass-selected ion isolation and mass-selected ion ejection have also been tested. Furthermore, the ITA has a small size and very low cost. An ITA with four channels is less than 30 cm(3) in total volume, and it shows a great promise for the miniaturization of the whole mass spectrometer instrument and high-throughput mass analysis. PMID:19441854

  2. Radiation Design of Ion Mass Spectrometers

    NASA Technical Reports Server (NTRS)

    Sittler, Ed; Cooper, John; Christian, Eric; Moore, Tom; Sturner, Steve; Paschalidis, Nick

    2011-01-01

    In the harsh radiation environment of Jupiter and with the JUpiter ICy moon Explorer (JUICE) mission including two Europa flybys where local intensities are approx. 150 krad/month behind 100 mils of Al shielding, so background from penetrating radiation can be a serious issue for detectors inside an Ion Mass Spectrometer (IMS). This can especially be important for minor ion detection designs. Detectors of choice for time-of-flight (TOF) designs are microchannel plates (MCP) and some designs may include solid state detectors (SSD). The standard approach is to use shielding designs so background event rates are low enough that the detector max rates and lifetimes are first not exceeded and then the more stringent requirement that the desired measurement can successfully be made (i.e., desired signal is sufficiently greater than background noise after background subtraction is made). GEANT codes are typically used along with various electronic techniques, but such designs need to know how the detectors will respond to the simulated primary and secondary radiations produced within the instrument. We will be presenting some preliminary measurements made on the response of MCPs to energetic electrons (20 ke V to 1400 ke V) using a Miniature TOF (MTOF) device and the High Energy Facility at Goddard Space Flight Center which has a Van de Graaff accelerator.

  3. Electron source for a mini ion trap mass spectrometer

    DOEpatents

    Dietrich, Daniel D.; Keville, Robert F.

    1995-01-01

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

  4. Electron source for a mini ion trap mass spectrometer

    DOEpatents

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

    1995-12-19

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

  5. Universal collisional activation ion trap mass spectrometry

    DOEpatents

    McLuckey, S.A.; Goeringer, D.E.; Glish, G.L.

    1993-04-27

    A universal collisional activation ion trap comprises an ion trapping means containing a bath gas and having connected thereto a noise signal generator. A method of operating a universal collisional activation ion trap comprises the steps of: providing an ion trapping means; introducing into the ion trapping means a bath gas; and, generating a noise signal within the ion trapping means; introducing into the ion trapping means a substance that, when acted upon by the noise signal, undergoes collisional activation to form product ions.

  6. Universal collisional activation ion trap mass spectrometry

    DOEpatents

    McLuckey, Scott A.; Goeringer, Douglas E.; Glish, Gary L.

    1993-01-01

    A universal collisional activation ion trap comprises an ion trapping means containing a bath gas and having connected thereto a noise signal generator. A method of operating a universal collisional activation ion trap comprises the steps of: providing an ion trapping means; introducing into the ion trapping means a bath gas; and, generating a noise signal within the ion trapping means; introducing into the ion trapping means a substance that, when acted upon by the noise signal, undergoes collisional activation to form product ions.

  7. C60 Secondary Ion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    SciTech Connect

    Smith, Donald F.; Robinson, Errol W.; Tolmachev, Aleksey V.; Heeren, Ronald M.; Pasa-Tolic, Ljiljana

    2011-12-15

    Secondary ion mass spectrometry (SIMS) has seen increased application for high spatial chemical imaging of complex biological surfaces. The advent and commercial availability of cluster and polyatomic primary ion sources (e.g. Au and Bi cluster and buckminsterfullerene (C60)) provide improved secondary ion yield and decreased fragmentation of surface species, thus accessibility to intact molecular ions. Despite developments in primary ion sources, development of mass spectrometers to fully exploit their advantages has been limited. Tandem mass spectrometry for identification of secondary ions is highly desirable, but implementation has proven to be difficult. Similarly, high mass resolution and high mass measurement accuracy would greatly improve the chemical specificity of SIMS. Here we combine, for the first time, the advantages of a C60 primary ion source with the ultra-high mass resolving power and high mass measurement accuracy of Fourier transform ion cyclotron resonance mass spectrometry. Mass resolving power in excess of 100,000 (m/Δm50%) is demonstrated, with mass measurement accuracies below 3 parts-per-million. Imaging of mouse brain tissue at 40 μm pixel size is shown. Tandem mass spectrometry of ions from biological tissue is demonstrated and molecular formulae can be assigned to fragment ions.

  8. An ion mobility mass spectrometer for investigating photoisomerization and photodissociation of molecular ions

    SciTech Connect

    Adamson, B. D.; Coughlan, N. J. A.; Markworth, P. B.; Bieske, E. J.; Continetti, R. E.

    2014-12-15

    An ion mobility mass spectrometry apparatus for investigating the photoisomerization and photodissociation of electrosprayed molecular ions in the gas phase is described. The device consists of a drift tube mobility spectrometer, with access for a laser beam that intercepts the drifting ion packet either coaxially or transversely, followed by a quadrupole mass filter. An ion gate halfway along the drift region allows the instrument to be used as a tandem ion mobility spectrometer, enabling mobility selection of ions prior to irradiation, with the photoisomer ions being separated over the second half of the drift tube. The utility of the device is illustrated with photoisomerization and photodissociation action spectra of carbocyanine molecular cations. The mobility resolution of the device for singly charged ions is typically 80 and it has a mass range of 100-440 Da, with the lower limit determined by the drive frequency for the ion funnels, and the upper limit by the quadrupole mass filter.

  9. STRUCTURAL CHARACTERIZATION OF SULFONATED AZO DYES USING LIQUID SECONDARY ION MASS SPECTROMETRY/TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    Eight monosulfonated and disulfonated azo dyes were analyzed using liquid secondary ion mass spectrometry/tandem mass spectrometry, in the negative ion mode, under low-energy conditions (110-150 eV). any structurally characteristic fragment ions were obtained, several of which ha...

  10. NEGATIVE-ION MASS SPECTROMETRY OF SULFONYLUREA HERBICIDES

    EPA Science Inventory

    Sulfonylurea herbicides have been studied using neg-ion desorption chem.-ionization (DCI) mass spectrometry (MS) and DCI-MS/MS techniques. Both {M-H]- and M.- ions were obsd. in the DCI mass spectra. The collisonally activated dissocn. (CAD) spectra were characteristic of the str...

  11. Ion-molecule adduct formation in tandem mass spectrometry.

    PubMed

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

    2016-02-01

    Nowadays most LC-MS methods rely on tandem mass spectrometry not only for quantitation and confirmation of compounds by multiple reaction monitoring (MRM), but also for the identification of unknowns from their product ion spectra. However, gas-phase reactions between charged and neutral species inside the mass analyzer can occur, yielding product ions at m/z values higher than that of the precursor ion, or at m/z values difficult to explain by logical losses, which complicate mass spectral interpretation. In this work, the formation of adduct ions in the mass analyzer was studied using several mass spectrometers with different mass analyzers (ion trap, triple quadrupole, and quadrupole-Orbitrap). Heterocyclic amines (AαC, MeAαC, Trp-P-1, and Trp-P-2), photo-initiators (BP and THBP), and pharmaceuticals (phenacetin and levamisole) were selected as model compounds and infused in LCQ Classic, TSQ Quantum Ultra AM, and Q-Exactive Orbitrap (ThermoFisher Scientific) mass spectrometers using electrospray as ionization method. The generation of ion-molecule adducts depended on the compound and also on the instrument employed. Adducts with neutral organic solvents (methanol and acetonitrile) were only observed in the ion trap instrument (LCQ Classic), because of the ionization source on-axis configuration and the lack of gas-phase barriers, which allowed inertial entrance of the neutrals into the analyzer. Adduct formation (only with water) in the triple quadrupole instruments was less abundant than in the ion trap and quadrupole-Orbitrap mass spectrometers, because of the lower residence time of the reactive product ions in the mass analyzer. The moisture level of the CID and/or damper gas had a great effect in beam-like mass analyzers such as triple quadrupole, but not in trap-like mass analyzers, probably because of the long residence time that allowed adduct formation even with very low concentrations of water inside the mass spectrometer. PMID:26700446

  12. DETERMINING ION COMPOSITIONS USING AN ACCURATE MASS, TRIPLE QUADRUPOLE MASS SPECTROMETER

    EPA Science Inventory

    For the past decade, we have used double focusing mass spectrometers to determine
    compositions of ions observed in mass spectra produced from compounds introduced by GC
    based on measured exact masses of the ions and their +1 and +2 isotopic profiles arising from atoms of ...

  13. Secondary Ion Mass Spectrometry Imaging of Dictyostelium discoideum Aggregation Streams

    SciTech Connect

    Debord, J. Daniel; Smith, Donald F.; Anderton, Christopher R.; Heeren, Ronald M.; Pasa-Tolic, Ljiljana; Gomer, Richard H.; Fernandez-Lima, Francisco A.

    2014-06-09

    High resolution imaging mass spectrometry could become a valuable tool for cell and developmental biology, but both, high spatial and mass spectral resolution are needed to enable this. In this report, we employed Bi3 bombardment time-of-flight (Bi3 ToF-SIMS) and C60 bombardment Fourier transform ion cyclotron resonance secondary ion mass spectrometry (C60 FTICR-SIMS) to image Dictyostelium discoideum aggregation streams. Nearly 300 lipid species were identified from the aggregation streams. High resolution mass spectrometry imaging (FTICR-SIMS) enabled the generation of multiple molecular ion maps at the nominal mass level and provided good coverage for fatty acyls, prenol lipids, and sterol lipids. The comparison of Bi3 ToF-SIMS and C60 FTICR-SIMS suggested that while the first provides fast, high spatial resolution molecular ion images, the chemical complexity of biological samples warrants the use of high resolution analyzers for accurate ion identification.

  14. Improved ion optics for introduction of ions into a 9.4-T Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Chen, Yu; Leach, Franklin E; Kaiser, Nathan K; Dang, Xibei; Ibrahim, Yehia M; Norheim, Randolph V; Anderson, Gordon A; Smith, Richard D; Marshall, Alan G

    2015-01-01

    Enhancements to the ion source and transfer optics of our 9.4 T Fourier transform ion cyclotron resonance (ICR) mass spectrometer have resulted in improved ion transmission efficiency for more sensitive mass measurement of complex mixtures at the MS and MS/MS levels. The tube lens/skimmer has been replaced by a dual ion funnel and the following octopole by a quadrupole for reduced ion cloud radial expansion before transmission into a mass-selective quadrupole. The number of ions that reach the ICR cell is increased by an order of magnitude for the funnel/quadrupole relative to the tube lens/skimmer/octopole. PMID:25601704

  15. Characterization of protonated phospholipids as fragile ions in quadrupole ion trap mass spectrometry

    PubMed Central

    Garrett, Timothy J.; Merves, Matthew; Yost, Richard A.

    2011-01-01

    Some ions exhibit “ion fragility” in quadrupole ion trap mass spectrometry (QIT-MS) during mass analysis with resonance ejection. In many cases, different ions generated from the same compound exhibit different degrees of ion fragility, with some ions (e.g., the [M+H]+ ion) stable and other ions (e.g., the [M+Na]+ ion) fragile. The ion fragility for quadrupole ion trap (QIT) mass spectrometry (MS) for protonated and sodiated ions of three phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, PC (16:0/16:0), 1,2-dipalmitoyl-sn-glycero-3-phophoethanolamine, PE (16:0/16:0), and N-palmitoyl-D-erythro-sphingosylphosphorylcholine, SM (d18:1/16:0), was determined using three previously developed experiments: 1) the peak width using a slow scan speed, 2) the width of the isolation window for efficient isolation, and 3) the energy required for collision-induced dissociation. In addition, ion fragility studies were designed and performed to explore a correlation between ion fragility in QIT mass analysis and ion fragility during transport between the ion source and the ion trap. These experiments were: 1) evaluating the amount of thermal-induced dissociation as a function of heated capillary temperature, and 2) determining the extent of fragmentation occurring with increasing tube lens voltage. All phospholipid species studied exhibited greater ion fragility as protonated species in ion trap mass analysis than as sodiated species. In addition, the protonated species of both SM (d18:0/16:0) and PC (16:0/16:0) exhibited greater tendencies to fragment at higher heated capillary temperatures and high tube lens voltages, whereas the PE (16:0/16:0) ions did not appear to exhibit fragility during ion transport. PMID:22247650

  16. Characterization of the Ion Beam Focusing in a Mass Spectrometer using an IonCCD™ Detector

    SciTech Connect

    Johnson, Grant E.; Hadjar, Omar; Laskin, Julia

    2011-07-26

    A position sensitive pixel-based detector array, referred to as the IonCCDTM, has been employed to characterize the ion optics and ion beam focusing in a custom built mass spectrometer designed for soft and reactive landing of mass-selected ions onto surfaces. The IonCCDTM was placed at several stages along the path of the ion beam to determine the focusing capabilities of the various ion optics which include an electrodynamic ion funnel, two radiofrequency (RF) only collision quadrupoles, a mass resolving quadrupole, a quadrupole bender, and two Einzel lens assemblies. The focusing capabilities of the RF-only collision quadrupoles and Einzel lenses are demonstrated by large decreases in the diameter of the ion beam. In contrast, the mass resolving quadrupole is shown to significantly defocus the mass-selected ion beam resulting in an expansion of the measured ion beam diameter. Combined with SIMION simulations we demonstrate that the IonCCDTM can identify minor errors in the alignment of charged-particle optics that result in erratic trajectories and significant deflections of the ion beam.. This information can be used to improve the design assembly and maintenance of custom-built mass spectrometry instrumentation.

  17. Characterization of the ion beam focusing in a mass spectrometer using an IonCCD™ detector.

    PubMed

    Johnson, Grant E; Hadjar, Omar; Laskin, Julia

    2011-08-01

    A position sensitive pixel-based detector array, referred to as the IonCCD, has been employed to characterize the ion optics and ion beam focusing in a custom built mass spectrometer designed for soft and reactive landing of mass-selected ions onto surfaces. The IonCCD was placed at several stages along the path of the ion beam to determine the focusing capabilities of the various ion optics, which include an electrodynamic ion funnel, two radiofrequency (rf)-only collision quadrupoles, a mass resolving quadrupole, a quadrupole bender, and two einzel lens assemblies. The focusing capabilities of the rf-only collision quadrupoles and einzel lenses are demonstrated by large decreases in the diameter of the ion beam. In contrast, the mass resolving quadrupole is shown to significantly defocus the mass-selected ion beam resulting in an expansion of the measured ion beam diameter. Combined with SIMION simulations, we demonstrate that the IonCCD can identify minor errors in the alignment of charged-particle optics that result in erratic trajectories and significant deflections of the ion beam. This information may be used to facilitate the design, assembly, and maintenance of custom-built mass spectrometry instrumentation. PMID:21953193

  18. 10 K Ring Electrode Trap—Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions

    NASA Astrophysics Data System (ADS)

    Goebbert, Daniel J.; Meijer, Gerard; Asmis, Knut R.

    2009-03-01

    A novel instrumental setup for measuring infrared photodissociation spectra of buffer gas cooled, mass-selected ions is described and tested. It combines a cryogenically cooled, linear radio frequency ion trap with a tandem mass spectrometer, optimally coupling continuous ion sources to pulsed laser experiments. The use of six independently adjustable DC potentials superimposed over the trapping radio frequency field provides control over the ion distribution within, as well as the kinetic energy distribution of the ions extracted from the ion trap. The scheme allows focusing the ions in space and time, such that they can be optimally irradiated by a pulsed, widely tunable infrared photodissociation laser. Ion intensities are monitored with a time-of-flight mass spectrometer mounted orthogonally to the ion trap axis.

  19. Comet Encke: Meteor metallic ion identification by mass spectrometer

    NASA Technical Reports Server (NTRS)

    Goldberg, R. A.; Aikin, A. C.

    1973-01-01

    Positive metallic ions have been measured in the earth's atmosphere between 85 and 120 km, during the period of the beta Taurids meteor shower, which is associated with Comet Encke. The ions originate during and following ablation of extraterrestrial debris by the earth's atmosphere. The enhancement of metal ion density during meteor showers is primary evidence for their extraterrestrial origin. The present results were obtained from a rocket-borne ion mass spectrometer.

  20. Ion source for high-precision mass spectrometry

    DOEpatents

    Todd, Peter J.; McKown, Henry S.; Smith, David H.

    1984-01-01

    The invention is directed to a method for increasing the precision of positive-ion relative abundance measurements conducted in a sector mass spectrometer having an ion source for directing a beam of positive ions onto a collimating slit. The method comprises incorporating in the source an electrostatic lens assembly for providing a positive-ion beam of circular cross section for collimation by the slit.

  1. Mass spectra of heavy ions near comet Halley

    NASA Technical Reports Server (NTRS)

    Korth, A.; Richter, A. K.; Loidl, A.; Anderson, K. A.; Carlson, C. W.

    1986-01-01

    The heavy-ion analyzer, RPA2-PICCA, aboard the Giotto spacecraft, detected the first cometary ions at a distance of about 1.05 million km from the nucleus of comet Halley. In the inner coma the major ions identified are associated with the H2O, CO and CO2 groups. Ions of larger atomic mass unit are also present, corresponding possibly to various hydrocarbons, heavy metals of the iron-group or to sulphur compounds.

  2. Ion source for high-precision mass spectrometry

    DOEpatents

    Todd, P.J.; McKown, H.S.; Smith, D.H.

    1982-04-26

    The invention is directed to a method for increasing the precision of positive-ion relative abundance measurements conducted in a sector mass spectrometer having an ion source for directing a beam of positive ions onto a collimating slit. The method comprises incorporating in the source an electrostatic lens assembly for providing a positive-ion beam of circular cross section for collimation by the slit. 2 figures, 3 tables.

  3. Mass Spectra and Ion Collision Cross Sections of Hemoglobin

    NASA Astrophysics Data System (ADS)

    Kang, Yang; Terrier, Peran; Douglas, D. J.

    2011-02-01

    Mass spectra of commercially obtained hemoglobin (Hb) show higher levels of monomer and dimer ions, heme-deficient dimer ions, and apo-monomer ions than hemoglobin freshly prepared from blood. This has previously been attributed to oxidation of commercial Hb. Further, it has been reported that that dimer ions from commercial bovine Hb have lower collision cross sections than low charge state monomer ions. To investigate these effects further, we have recorded mass spectra of fresh human Hb, commercial human and bovine Hb, fresh human Hb oxidized with H2O2, lyophilized fresh human Hb, fresh human Hb both lyophilized and chemically oxidized, and commercial human Hb oxidized with H2O2. Masses of α-monomer ions of all hemoglobins agree with the masses expected from the sequences within 3 Da or better. Mass spectra of the β chains of commercial Hb and oxidized fresh human Hb show a peak or shoulder on the high mass side, consistent with oxidation of the protein. Both commercial proteins and oxidized fresh human Hb produce heme-deficient dimers with masses 32 Da greater than expected and higher levels of monomer and dimer ions than fresh Hb. Lyophilization or oxidation of Hb both produce higher levels of monomer and dimer ions in mass spectra. Fresh human Hb, commercial human Hb, commercial bovine Hb, and oxidized commercial human Hb all give dimer ions with cross sections greater than monomer ions. Thus, neither oxidation of Hb or the difference in sequence between human and bovine Hb make substantial differences to cross sections of ions.

  4. Ion acoustic shock wave in collisional equal mass plasma

    NASA Astrophysics Data System (ADS)

    Adak, Ashish; Ghosh, Samiran; Chakrabarti, Nikhil

    2015-10-01

    The effect of ion-ion collision on the dynamics of nonlinear ion acoustic wave in an unmagnetized pair-ion plasma has been investigated. The two-fluid model has been used to describe the dynamics of both positive and negative ions with equal masses. It is well known that in the dynamics of the weakly nonlinear wave, the viscosity mediates wave dissipation in presence of weak nonlinearity and dispersion. This dissipation is responsible for the shock structures in pair-ion plasma. Here, it has been shown that the ion-ion collision in presence of collective phenomena mediated by the plasma current is the source of dissipation that causes the Burgers' term which is responsible for the shock structures in equal mass pair-ion plasma. The dynamics of the weakly nonlinear wave is governed by the Korteweg-de Vries Burgers equation. The analytical and numerical investigations revealed that the ion acoustic wave exhibits both oscillatory and monotonic shock structures depending on the frequency of ion-ion collision parameter. The results have been discussed in the context of the fullerene pair-ion plasma experiments.

  5. Ion acoustic shock wave in collisional equal mass plasma

    SciTech Connect

    Adak, Ashish; Ghosh, Samiran; Chakrabarti, Nikhil

    2015-10-15

    The effect of ion-ion collision on the dynamics of nonlinear ion acoustic wave in an unmagnetized pair-ion plasma has been investigated. The two-fluid model has been used to describe the dynamics of both positive and negative ions with equal masses. It is well known that in the dynamics of the weakly nonlinear wave, the viscosity mediates wave dissipation in presence of weak nonlinearity and dispersion. This dissipation is responsible for the shock structures in pair-ion plasma. Here, it has been shown that the ion-ion collision in presence of collective phenomena mediated by the plasma current is the source of dissipation that causes the Burgers' term which is responsible for the shock structures in equal mass pair-ion plasma. The dynamics of the weakly nonlinear wave is governed by the Korteweg-de Vries Burgers equation. The analytical and numerical investigations revealed that the ion acoustic wave exhibits both oscillatory and monotonic shock structures depending on the frequency of ion-ion collision parameter. The results have been discussed in the context of the fullerene pair-ion plasma experiments.

  6. Differentially pumped dual linear quadrupole ion trap mass spectrometer

    SciTech Connect

    Owen, Benjamin C.; Kenttamaa, Hilkka I.

    2015-10-20

    The present disclosure provides a new tandem mass spectrometer and methods of using the same for analyzing charged particles. The differentially pumped dual linear quadrupole ion trap mass spectrometer of the present disclose includes a combination of two linear quadrupole (LQIT) mass spectrometers with differentially pumped vacuum chambers.

  7. Ion microprobe mass spectrometry using sputtering atomization and resonance ionization

    SciTech Connect

    Donohue, D.L.; Christie, W.H.; Goeringer, D.E.

    1985-01-01

    Resonance ionization mass spectrometry (RIMS) has recently been developed into a useful technique for isotope ratio measurements. Studies performed in our laboratory (1-6) have been reported for a variety of elements using thermal vaporization sources to produce the atom reservoir for laser-induced resonance ionization. A commercial ion microprobe mass analyzer (IMMA) has been interfaced with a tunable pulsed dye laser for carrying out resonance ionization mass spectrometry of sputtered atoms. The IMMA instrument has many advantages for this work, including a micro-focused primary ion beam (2 ..mu..m in diameter) of selected mass, complete sample manipulation and viewing capability, and a double-focusing mass spectrometer for separation and detection of the secondary or laser-generated ions. Data were obtained demonstrating the number and type of ions formed along with optical spectral information showing the wavelengths at which resonance ionization occurs. 7 refs.

  8. Fast neutral beam ion source coupled to a Fourier transform ion cyclotron resonance mass spectrometer

    SciTech Connect

    Hill, N.C.; Limbach, P.A.; Shomo, R.E. II; Marshall, A.G. ); Appelhans, A.D.; Delmore, J.E. )

    1991-11-01

    The coupling of an autoneutralizing SF{sup {minus}}{sub 6} fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis (e.g., production of abundant pseudomolecular (M+H){sup +} ions) of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with {ital tetra}-butylammonium bromide and a Tylenol{sup ( )} sample. The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon{sup ( )}. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.

  9. Fast neutral beam ion source coupled to a Fourier transform ion cyclotron resonance mass spectrometer

    NASA Astrophysics Data System (ADS)

    Hill, Nicholas C.; Limbach, Patrick A.; Shomo, Ronald E., II; Marshall, Alan G.; Appelhans, Anthony D.; Delmore, James E.

    1991-11-01

    The coupling of an autoneutralizing SF-6 fast ion-beam gun to a Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometer is described. The fast neutral beam provides for secondary-ion-type FT/ICR mass analysis [e.g., production of abundant pseudomolecular (M+H)+ ions] of involatile samples without the need for external ion injection, since ions are formed at the entrance to the ICR ion trap. The design, construction, and testing of the hybrid instrument are described. The feasibility of the experiment (for both broadband and high-resolution FT/ICR positive-ion mass spectra) is demonstrated with tetra-butylammonium bromide and a Tylenol■ sample. The ability to analyze high molecular weight polymers with high mass resolution is demonstrated for Teflon■. All of the advantages of the fast neutral beam ion source previously demonstrated with quadrupole mass analysis are preserved, and the additional advantages of FT/ICR mass analysis (e.g., high mass resolving power, ion trapping) are retained.

  10. Ion implantation of solar cell junctions without mass analysis

    NASA Technical Reports Server (NTRS)

    Fitzgerald, D.; Tonn, D. G.

    1981-01-01

    This paper is a summary of an investigation to determine the feasibility of producing solar cells by means of ion implantation without the use of mass analysis. Ion implants were performed using molecular and atomic phosphorus produced by the vaporization of solid red phosphorus and ionized in an electron bombardment source. Solar cell junctions were ion implanted by mass analysis of individual molecular species and by direct unanalyzed implants from the ion source. The implant dose ranged from 10 to the 14th to 10 to the 16th atoms/sq cm and the energy per implanted atom ranged from 5 KeV to 40 KeV in this study.

  11. Improved Ion Optics for Introduction of Ions into a 9.4 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    PubMed Central

    Chen, Yu; Leach, Franklin E.; Kaiser, Nathan K.; Dang, Xibei; Ibrahim, Yehia M.; Norheim, Randolph V.; Anderson, Gordon A.; Smith, Richard D.; Marshall, Alan G.

    2014-01-01

    Enhancements to the ion source and transfer optics of our 9.4 T FT-ICR mass spectrometer have resulted in improved ion transmission efficiency for more sensitive mass measurement of complex mixtures at the MS and MS/MS levels. The tube lens/skimmer has been replaced by a dual ion funnel and the following octopole by a quadrupole for reduced ion cloud radial expansion before transmission into a mass-selective quadrupole. The number of ions that reach the ICR cell is increased by an order of magnitude for the funnel/quadrupole relative to the tube lens/skimmer/octopole. PMID:25601704

  12. AUTOMATED DETERMINATION OF PRECURSOR ION, PRODUCT ION, AND NEUTRAL LOSS COMPOSITIONS AND DECONVOLUTION OF COMPOSITE MASS SPECTRA USING ION CORRELATION BASED ON EXACT MASSES AND RELATIVE ISOTOPIC ABUNDANCES

    EPA Science Inventory

    After a dispersive event, rapid determination of elemental compositions of ions in mass spectra is essential for tentatively identifying compounds. A Direct Analysis in Real Time (DART)® ion source interfaced to a JEOL AccuTOF® mass spectrometer provided exact masses accurate to ...

  13. Formation of high-mass cluster ions from compound semiconductors using time-of-flight secondary ion mass spectrometry with cluster primary ions.

    PubMed

    Goacher, Robyn E; Luo, Hong; Gardella, Joseph A

    2008-05-01

    The detection of high-mass, nonstoichiometric, GaxAsy and InxPy secondary ion clusters using time-of-flight secondary ion mass spectrometry is reported for the first time. The GaxAsy and InxPy clusters are detected in both positive and negative ion spectra and extend to masses of at least 6000 dalton (Da). Consecutive clusters differ by the addition of one gallium (indium) atom. This leads to nonstoichiometric clusters at high mass (i.e., Ga15As3 at 1270 Da) which are metastable above a critical mass. The relative secondary ion yields of high-mass GaxAsy clusters detected using several primary ion sources (Cs+, Bi+, Bi3+, Bi32+, Bi52+, C60+, and C602+) are compared. The relative secondary ion yield of high-mass GaxAsy clusters is significantly enhanced by the use of cluster primary ions and the best relative secondary ion yield is obtained using Bi3+ primary ions. An application of the high-mass GaxAsy clusters is presented, in which these clusters are utilized to distinguish between contaminant levels of Ga and bulk GaAs structure in a depth profile of a MnAs/GaAs heterojunction. These results illustrate improved analysis of inorganic materials using cluster primary ions and break the paradigm of stoichiometric secondary cluster ion formation for SIMS of inorganic compounds. PMID:18358011

  14. Improved ion optics for introduction of ions into a 9.4-T Fourier transform ion cyclotron resonance mass spectrometer

    DOE PAGESBeta

    Chen, Yu; Leach, Franklin E.; Kaiser, Nathan K.; Dang, Xibei; Ibrahim, Yehia M.; Norheim, Randolph V.; Anderson, Gordon A.; Smith, Richard D.; Marshall, Alan G.

    2015-01-19

    Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides unparalleled mass accuracy and resolving power.[1],[2] With electrospray ionization (ESI), ions are typically transferred into the mass spectrometer through a skimmer, which serves as a conductance-limiting orifice. However, the skimmer allows only a small fraction of incoming ions to enter the mass spectrometer. An ion funnel, originally developed by Smith and coworkers at Pacific Northwest National Laboratory (PNNL)[3-5] provides much more efficient ion focusing and transfer. The large entrance aperture of the ion funnel allows almost all ions emanating from a heated capillary to be efficiently captured and transferred, resulting inmore » nearly lossless transmission.« less

  15. Linear electronic field time-of-flight ion mass spectrometers

    DOEpatents

    Funsten, Herbert O.

    2010-08-24

    Time-of-flight mass spectrometer comprising a first drift region and a second drift region enclosed within an evacuation chamber; a means of introducing an analyte of interest into the first drift region; a pulsed ionization source which produces molecular ions from said analyte of interest; a first foil positioned between the first drift region and the second drift region, which dissociates said molecular ions into constituent atomic ions and emits secondary electrons; an electrode which produces secondary electrons upon contact with a constituent atomic ion in second drift region; a stop detector comprising a first ion detection region and a second ion detection region; and a timing means connected to the pulsed ionization source, to the first ion detection region, and to the second ion detection region.

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

    PubMed

    Smith, Donald F; Kiss, Andras; Leach, Franklin E; Robinson, Errol W; Paša-Tolić, Ljiljana; Heeren, Ron M A

    2013-07-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the sub-micrometer scale. Such experiments are typically performed on time-of-flight mass spectrometers for high sensitivity and high repetition rate imaging. However, such mass analyzers lack the mass resolving power to ensure separation of isobaric ions and the mass accuracy for elemental formula assignment based on exact mass measurement. We have recently reported a secondary ion mass spectrometer with the combination of a C60 primary ion gun with a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) for high mass resolving power, high mass measurement accuracy, and tandem mass spectrometry capabilities. In this work, high specificity and high sensitivity secondary ion FT-ICR MS was applied to chemical imaging of biological tissue. An entire rat brain tissue was measured with 150 μm spatial resolution (75 μm primary ion spot size) with mass resolving power (m/Δm(50%)) of 67,500 (at m/z 750) and root-mean-square measurement accuracy less than two parts-per-million for intact phospholipids, small molecules and fragments. For the first time, ultra-high mass resolving power SIMS has been demonstrated, with m/Δm(50%) > 3,000,000. Higher spatial resolution capabilities of the platform were tested at a spatial resolution of 20 μm. The results represent order of magnitude improvements in mass resolving power and mass measurement accuracy for SIMS imaging and the promise of the platform for ultra-high mass resolving power and high spatial resolution imaging. PMID:23685962

  17. High Mass Accuracy and High Mass Resolving Power FT-ICR Secondary Ion Mass Spectrometry for Biological Tissue Imaging

    SciTech Connect

    Smith, Donald F.; Kiss, Andras; Leach, Franklin E.; Robinson, Errol W.; Pasa-Tolic, Ljiljana; Heeren, Ronald M.

    2013-07-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the micrometer scale. Such experiments are typically performed on time-of-flight mass spectrometers for high sensitivity and high repetition rate imaging. However, such mass analyzers lack the mass resolving power to ensure separation of isobaric ions and the mass accuracy for exact mass elemental formula assignment. We have recently reported a secondary ion mass spectrometer with the combination of a C60 primary ion gun with a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) for high mass resolving power, high mass measurement accuracy and tandem mass spectrometry capabilities. In this work, high specificity and high sensitivity secondary ion FT-ICR MS was applied to chemical imaging of biological tissue. An entire rat brain tissue was measured with 150 μm spatial resolution (75 μm primary ion spot size) with mass resolving power (m/Δm50%) of 67,500 (at m/z 750) and root-mean-square measurement accuracy less than two parts-per-million for intact phospholipids, small molecules and fragments. For the first time, ultra-high mass resolving power SIMS has been demonstrated, with m/Δm50% > 3,000,000. Higher spatial resolution capabilities of the platform were tested at a spatial resolution of 20 μm. The results represent order of magnitude improvements in mass resolving power and mass measurement accuracy for SIMS imaging and the promise of the platform for ultra-high mass resolving power and high spatial resolution imaging.

  18. Simulating data processing for an Advanced Ion Mobility Mass Spectrometer

    SciTech Connect

    Chavarría-Miranda, Daniel; Clowers, Brian H.; Anderson, Gordon A.; Belov, Mikhail E.

    2007-11-03

    We have designed and implemented a Cray XD-1-based sim- ulation of data capture and signal processing for an ad- vanced Ion Mobility mass spectrometer (Hadamard trans- form Ion Mobility). Our simulation is a hybrid application that uses both an FPGA component and a CPU-based soft- ware component to simulate Ion Mobility mass spectrome- try data processing. The FPGA component includes data capture and accumulation, as well as a more sophisticated deconvolution algorithm based on a PNNL-developed en- hancement to standard Hadamard transform Ion Mobility spectrometry. The software portion is in charge of stream- ing data to the FPGA and collecting results. We expect the computational and memory addressing logic of the FPGA component to be portable to an instrument-attached FPGA board that can be interfaced with a Hadamard transform Ion Mobility mass spectrometer.

  19. Laser desorption in an ion trap mass spectrometer

    SciTech Connect

    Eiden, G.C.; Cisper, M.E.; Alexander, M.L.; Hemberger, P.H.; Nogar, N.S.

    1993-02-01

    Laser desorption in a ion-trap mass spectrometer shows significant promise for both qualitative and trace analysis. Several aspects of this methodology are discussed in this work. We previously demonstrated the generation of both negative and positive ions by laser desorption directly within a quadrupole ion trap. In the present work, we explore various combinations of d.c., r.f., and time-varying fields in order to optimize laser generated signals. In addition, we report on the application of this method to analyze samples containing compounds such as amines, metal complexes, carbon clusters, and polynuclear aromatic hydrocarbons. In some cases the ability to rapidly switch between positive and negative ion modes provides sufficient specificity to distinguish different compounds of a mixture with a single stage of mass spectrometry. In other experiments, we combined intensity variation studies with tandem mass spectrometry experiments and positive and negative ion detection to further enhance specificity.

  20. Design and development of a fast ion mass spectrometer

    NASA Technical Reports Server (NTRS)

    Burch, J. L.

    1983-01-01

    Two Fast Ion Mass Spectrometers (FIMS A and FIMS B) were developed. The design, development, construction, calibration, integration, and flight of these instruments, along with early results from the data analysis efforts are summarized. A medium energy ion mass spectrometer that covers mass velocity space with significantly higher time resolution, improved mass resolution, (particularly for heavier ions), and wider energy range than existing instruments had achieved was completed. The initial design consisted of a dual channel cylindrical electrostatic analyzer followed by a dual channel cylindrical velocity filter. The gain versus count rate characteristics of the high current channel electron multipliers (CEM's), which were chosen for ion detection, revealed a systematic behavior that can be used as a criterion for selection of CEM's for long counting lifetimes.

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

    PubMed

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

    2011-11-01

    This study presents the first report on the development of a matrix-assisted laser desorption ionization (MALDI) linear ion trap mass spectrometer for large biomolecular ion detection by frequency scan. We designed, installed, and tested this radio frequency (RF) scan linear ion trap mass spectrometer and its associated electronics to dramatically extend the mass region to be detected. The RF circuit can be adjusted from 300 to 10 kHz with a set of operation amplifiers. To trap the ions produced by MALDI, a high pressure of helium buffer gas was employed to quench extra kinetic energy of the heavy ions produced by MALDI. The successful detection of the singly charged secretory immunoglobulin A ions indicates that the detectable mass-to-charge ratio (m/z) of this system can reach ~385 000 or beyond. PMID:21932813

  2. Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

    NASA Technical Reports Server (NTRS)

    Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

    1991-01-01

    This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

  3. Ion Mobility Mass Spectrometry Analysis of Isomeric Disaccharide Precursor, Product and Cluster Ions

    PubMed Central

    Li, Hongli; Bendiak, Brad; Siems, William F.; Gang, David R.; Hill, Herbert H.

    2015-01-01

    RATIONALE Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and general branching features. The separation of carbohydrate isomers poses a great challenge for current analytical techniques. METHODS The isomeric heterogeneity of disaccharide ions and monosaccharideglycolaldehyde product ions evaluated using electrospray traveling wave ion mobility mass spectrometry (Synapt G2 high definition mass spectrometer) in both positive and negative ion modes investigation. RESULTS The separation of isomeric disaccharide ions was observed but not fully achieved based on their mobility profiles. The mobilities of isomeric product ions, the monosaccharide-glycolaldehydes, derived from different disaccharide isomers were measured. Multiple mobility peaks were observed for both monosaccharide-glycolaldehyde cations and anions, indicating that there was more than one structural configuration in the gas phase as verified by NMR in solution. More importantly, the mobility patterns for isomeric monosaccharide-glycolaldehyde product ions were different, which enabled partial characterization of their respective disaccharide ions. Abundant disaccharide cluster ions were also observed. The Results showed that a majority of isomeric cluster ions had different drift times and, moreover, more than one mobility peak was detected for a number of specific cluster ions. CONCLUSIONS It is demonstrated that ion mobility mass spectrometry is an advantageous method to assess the isomeric heterogeneity of carbohydrate compounds. It is capable of differentiating different types of carbohydrate ions having identical m/z values as well as multiple structural configurations of single compounds. PMID:24591031

  4. Collisional activation with random noise in ion trap mass spectrometry

    SciTech Connect

    McLuckey, S.A.; Goeringer, D.E.; Glish, G.L.

    1992-07-01

    Random noise applied to the end caps of a quadrupole ion trap is shown to be an effective means for the collisional activation of trapped ions independent of mass/charge ratio and number of ions. This technique is compared and contrasted with conventional single-frequency collisional activation for the molecular ion of N,N-dimethylaniline, protonated cocaine, the molecular anion of 2,4,6-trinitrotoluene, and doubly protonated neuromedin U-8. Collisional activation with noise tends to produce more extensive fragmentation than the conventional approach due to the fact that product ions are also kinetically excited in the noise experiment. The efficiency of the noise experiment in producing detectable product ions relative to the conventional approach ranges from being equivalent to being a factor of 3 less efficient. Furthermore, discrimination against low mass/charge product ions is apparent in the data from multiply charged biomolecules. Nevertheless, collisional activation with random noise provides a very simple means for overcoming problems associated with the dependence of single-frequency collisional activation on mass/charge ratio and the number of ions in the ion trap. 45 refs., 7 figs.

  5. Ion deposition by inductively coupled plasma mass spectrometry

    SciTech Connect

    Hu, K.; Houk, R.S.

    1996-03-01

    An atmospheric pressure inductively coupled plasma (ICP) is used with a quadrupole mass spectrometer (MS) for ion deposition. The deposited element is introduced as a nebulized aqueous solution. Modifications to the ICP-MS device allow generation and deposition of a mass-resolved beam of {sup 165}Ho{sup +} at 5{times}10{sup 12} ions s{sup {minus}1}. The ICP is a universal, multielement ion source that can potentially be used for applications such as deposition of mixtures of widely varying stoichiometry or of alternating layers of different elements. {copyright} {ital 1996 American Vacuum Society}

  6. Fluorescence imaging for visualization of the ion cloud in a quadrupole ion trap mass spectrometer.

    PubMed

    Talbot, Francis O; Sciuto, Stephen V; Jockusch, Rebecca A

    2013-12-01

    Laser-induced fluorescence is used to visualize populations of gaseous ions stored in a quadrupole ion trap (QIT) mass spectrometer. Presented images include the first fluorescence image of molecular ions collected under conditions typically used in mass spectrometry experiments. Under these "normal" mass spectrometry conditions, the radial (r) and axial (z) full-width at half maxima (FWHM) of the detected ion cloud are 615 and 214 μm, respectively, corresponding to ~6% of r0 and ~3% of z0 for the QIT used. The effects on the shape and size of the ion cloud caused by varying the pressure of helium bath gas, the number of trapped ions, and the Mathieu parameter q z are visualized and discussed. When a "tickle voltage" is applied to the exit end-cap electrode, as is done in collisionally activated dissociation, a significant elongation in the axial, but not the radial, dimension of the ion cloud is apparent. Finally, using spectroscopically distinguishable fluorophores of two different m/z values, images are presented that illustrate stratification of the ion cloud; ions of lower m/z (higher qz) are located in the center of the trapping region, effectively excluding higher m/z (lower qz) ions, which form a surrounding layer. Fluorescence images such as those presented here provide a useful reference for better understanding the collective behavior of ions in radio frequency (rf) trapping devices and how phenomena such as collisions and space-charge affect ion distribution. PMID:24092629

  7. Fluorescence Imaging for Visualization of the Ion Cloud in a Quadrupole Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Talbot, Francis O.; Sciuto, Stephen V.; Jockusch, Rebecca A.

    2013-12-01

    Laser-induced fluorescence is used to visualize populations of gaseous ions stored in a quadrupole ion trap (QIT) mass spectrometer. Presented images include the first fluorescence image of molecular ions collected under conditions typically used in mass spectrometry experiments. Under these "normal" mass spectrometry conditions, the radial ( r) and axial ( z) full-width at half maxima (FWHM) of the detected ion cloud are 615 and 214 μm, respectively, corresponding to ~6 % of r 0 and ~3 % of z 0 for the QIT used. The effects on the shape and size of the ion cloud caused by varying the pressure of helium bath gas, the number of trapped ions, and the Mathieu parameter q z are visualized and discussed. When a "tickle voltage" is applied to the exit end-cap electrode, as is done in collisionally activated dissociation, a significant elongation in the axial, but not the radial, dimension of the ion cloud is apparent. Finally, using spectroscopically distinguishable fluorophores of two different m/ z values, images are presented that illustrate stratification of the ion cloud; ions of lower m/ z (higher q z ) are located in the center of the trapping region, effectively excluding higher m/ z (lower q z ) ions, which form a surrounding layer. Fluorescence images such as those presented here provide a useful reference for better understanding the collective behavior of ions in radio frequency (rf) trapping devices and how phenomena such as collisions and space-charge affect ion distribution.

  8. Restrained Ion Population Transfer: A Novel Ion Transfer Method for Mass Spectrometry.

    SciTech Connect

    Kaiser, Nathan K.; Skulason, Gunnar; Weisbrod, Chad R.; Wu, Si; Zhang, Kai; Prior, David C.; Buschbach, Michael A.; Anderson, Gordon A.; Bruce, James E.

    2008-06-30

    With modern Fourier transform ion cyclotron resonance (ICR) mass spectrometers, ions are created and accumulated exterior to the mass analyzer. The ion accumulation event takes place in a region of higher pressure which allows ions to be thermally cooled before being given kinetic energy and accelerated toward the ICR cell where they are to be decelerated and re-trapped. When gated trapping is used to collect ions in the ICR cell for analysis, mass discrimination can occur due to time-of-flight effects. Also, trapping ions with large axial kinetic energy can decrease the performance of the ICR instrument when compared to the analysis of thermally-cooled ions located at the trap center. Therefore, it is desirable to limit the energy imparted in the ions within the ICR cell as well as minimize time-of-flight effects. The approach presented here for ion transfer called restrained ion population transfer or RIPT provides complete axial control of an ion population throughout the entire transfer sequence from the accumulation region to the ICR cell. This is accomplished by utilization of a number of quadrupole segments arranged in series with independent control of the dc bias voltage applied to each segment of the quadrupole ion guide. This approach circumvents problems associated with time-of-flight effects and minimizes the energy imparted to the ions allowing transfer of the cooled ion packet from the ion accumulation region to the ICR cell. Initial data are presented to illustrate feasibility of restrained ion population transfer. RIPT was also modeled with SIMION 7.0 and simulation results that support our feasibility studies of the ions transfer process are presented.

  9. Ion trap simulation program, ITSIM: A powerful heuristic and predictive tool in ion trap mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bui, Huy Anh

    The multi-particle simulation program, ITSIM version 4.0, takes advantage of the enhanced performance of the Windows 95 and NT operating systems in areas such as memory management, user friendliness, flexibility of graphics and speed, to investigate the motion of ions in the quadrupole ion trap. The objective of this program is to use computer simulations based on mathematical models to improve the performance of the ion trap mass spectrometer. The simulation program can provide assistance in understanding fundamental aspects of ion trap mass spectrometry, precede and help to direct the course of experiments, as well as having didactic value in elucidating and allowing visualization of ion behavior under different experimental conditions. The program uses the improved Euler method to calculate ion trajectories as numerical solutions to the Mathieu differential equation. This Windows version can simultaneously simulate the trajectories of ions with a virtually unlimited number of different mass-to-charge ratios and hence allows realistic mass spectra, ion kinetic energy distributions and other experimentally measurable properties to be simulated. The large number of simulated ions allows examination of (i) the offsetting effects of mutual ion repulsion and collisional cooling in an ion trap and (ii) the effects of higher order fields. Field inhomogeneities arising from exit holes, electrode misalignment, imperfect electrode surfaces or new trap geometries can be simulated with the program. The simulated data are used to obtain mass spectra from mass-selective instability scans as well as by Fourier transformation of image currents induced by coherently moving ion clouds. Complete instruments, from an ion source through the ion trap mass analyzer to a detector, can now be simulated. Applications of the simulation program are presented and discussed. Comparisons are made between the simulations and experimental data. Fourier transformed experiments and a novel six

  10. Mass spectrometry. [in organic ion and biorganic chemistry and medicine

    NASA Technical Reports Server (NTRS)

    Burlingame, A. L.; Cox, R. E.; Derrick, P. J.

    1974-01-01

    Review of the present status of mass spectrometry in the light of pertinent recent publications spanning the period from December 1971 to January 1974. Following an initial survey of techniques, instruments, and computer applications, a sharp distinction is made between the chemistry of organic (radical-)ions and analytical applications in biorganic chemistry and medicine. The emphasis is on the chemistry of organic (radical-)ions at the expense of inorganic, organometallic, and surface ion chemistry. Biochemistry and medicine are chosen because of their contemporary importance and because of the stupendous contributions of mass spectroscopy to these fields in the past two years. In the review of gas-phase organic ion chemistry, special attention is given to studies making significant contributions to the understanding of ion chemistry.

  11. USING AN ACCURATE MASS, TRIPLE QUADRUPOLE MASS SPECTROMETER AND AN ION CORRELATION PROGRAM TO IDENTIFY COMPOUNDS

    EPA Science Inventory

    Most compounds are not found in mass spectral libraries and must be identified by other means. Often, compound identities can be deduced from the compositions of the ions in their mass spectra and review of the chemical literature. Confirmation is provided by mass spectra and r...

  12. Miniature Ion Optics Towards a Micro Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Chaudhary, Ashish

    This PhD dissertation reports the development of miniature ion optics components of a mass spectrometer (MS) with the ultimate goal to lay the foundation for a compact low-power micromachined MS (microMS) for broad-range chemical analysis. Miniaturization of two specific components a) RF ion traps and b) an ion funnel have been investigated and miniature low-power versions of these components have been developed and demonstrated successfully in lab experiments. Power savings, simpler electronics and packaging schemes required to operate the micro-scale RF cylindrical ion traps have been the key motivation driving this research. Microfabricated cylindrical ion traps (microCITs) and arrays in silicon, silicon-on-insulator and stainless steel substrates have been demonstrated and average power of as low as 55 mW for a low mass range (28 to 136 amu) and mass spectra with better than a unit-mass-resolution have been recorded. For the ion funnel miniaturization effort, simple assembly, small form factor and ease of integration have been emphasized. A simplification of the conventional 3D ion funnel design, called the planar ion funnel, has been developed in a single plate and has been tested to demonstrate ion funneling at medium vacuum levels (1E-5 Torr) using DC voltages and power less than 0.5 W. Miniaturization of these components also enables use of other novel ion optics components, packaging and integration, which will allow a new class of microMS architectures amenable for radical miniaturization.

  13. Ion optics system incorporating radio frequency mass separation

    NASA Technical Reports Server (NTRS)

    Anderson, John R.; Carruth, M. R., Jr.

    1990-01-01

    Results of an experimental study are presented. They show that an RF mass discriminator, based on a Bennett mass spectrometer concept, can be used to discriminate between two species of ions with about a 2-to-1 charge-to-mass ratio. Such a device would be useful for separating monatomic and diatomic oxygen ions in a system designed to simulate the environment that spacecraft encounter in low earth orbit. The influence of changing mass discriminator parameters - such as the spacing of its grids, the amplitude and frequency of RF voltage signals applied to it and the current density of ions incident upon it - on its species discrimination capabilities is discussed. Experimental results are also compared to the results of a simple theoretical model to gain insight into the processes occurring in the discriminator. These results are shown to be in good agreement.

  14. Quadrupole Ion Mass Spectrometer for Masses of 2 to 50 Da

    NASA Technical Reports Server (NTRS)

    Helms, William; Griffin, Timothy P.; Ottens, Andrew; Harrison, Willard

    2005-01-01

    A customized quadrupole ion-trap mass spectrometer (QITMS) has been built to satisfy a need for a compact, rugged instrument for measuring small concentrations of hydrogen, helium, oxygen, and argon in a nitrogen atmosphere. This QITMS can also be used to perform quantitative analyses of other gases within its molecular-mass range, which is 2 to 50 daltons (Da). (More precisely, it can be used to perform quantitative analysis of gases that, when ionized, are characterized by m/Z ratios between 2 and 50, where m is the mass of an ion in daltons and Z is the number of fundamental electric charges on the ion.

  15. Mass-dependent channel electron multiplier operation. [for ion detection

    NASA Technical Reports Server (NTRS)

    Fields, S. A.; Burch, J. L.; Oran, W. A.

    1977-01-01

    The absolute counting efficiency and pulse height distributions of a continuous-channel electron multiplier used in the detection of hydrogen, argon and xenon ions are assessed. The assessment technique, which involves the post-acceleration of 8-eV ion beams to energies from 100 to 4000 eV, provides information on counting efficiency versus post-acceleration voltage characteristics over a wide range of ion mass. The charge pulse height distributions for H2 (+), A (+) and Xe (+) were measured by operating the experimental apparatus in a marginally gain-saturated mode. It was found that gain saturation occurs at lower channel multiplier operating voltages for light ions such as H2 (+) than for the heavier ions A (+) and Xe (+), suggesting that the technique may be used to discriminate between these two classes of ions in electrostatic analyzers.

  16. Mass determination of megadalton-DNA Electrospray Ions usingCharge Detection Mass Spectrometry

    SciTech Connect

    Schultz, Jocelyn C.; Hack, Christopher; Benner, Henry W.

    1997-10-01

    Charge detection mass spectrometry (CD-MS) has been used to determine the mass of double-stranded, circular DNA and single-stranded, circular DNA in the range of 2500 to 8000 base pairs (1.5-5.0 MDa). Simultaneous measurement of the charge and velocity of an electrostatically accelerated ion allows a mass determination of the ion, with instrument calibration determined independently of samples. Positive ion mass spectra of electrosprayed commercial DNA samples supplied in tris(hydroxymethyl)ethylenediamine tetraacetic acid buffer, diluted in 50 vol. percent acetonitrile, were obtained without cleanup of the sample. ACD mass spectrum constructed from 3000 ion measurements takes 10 min to acquire and yields the DNA molecular mass directly (mass resolution = 6). The data collected represent progress toward a more automatable alternative to sizing of DNA by gel electrophoresis. In addition to the mass spectra, CD-MS generates charge versus mass plots, which provide another means to investigate the creation and fate of large electrospray ions.

  17. Laser-based studies with an ion-trap mass spectrometer: Ion tomography and analytical applications

    NASA Astrophysics Data System (ADS)

    Alexander, M. L.; Cisper, M. E.; Hemberger, P. H.; Nogar, N. S.; Williams, J. D.; Syka, J. E. P.

    The iron trap mass spectrometer (ITMS) is an ion storage device which consists of two hyperbolic endcaps and a hyperbolic ring electrode. This forms a trapping cavity having a volume of several cm(sup 3). An RF potential applied to the ring electrode produces a time-varying potential which can be used to trap and/or manipulate ions under controlled conditions. This device has been used in ion trapping studies for a number of years. More recently, a commercial version has been produced and sold which allows for mass-selective ejection of trapped ions, with subsequent detection by an electron multiplier. In this mode, it operates as a compact, high efficiency, high resolution mass spectrometer. The instrument has found applications in GC/MS, in tandem mass spectroscopy and in portable mass spectral analysis. In this manuscript, we present a survey of recent results incorporating laser desorption, ionization, or photodissociation with ITMS. In one instance, we describe the use of laser photodissociation to map the spatial distribution of trapped ions in the ITMS. In this tomographic study, we have parameterized the effects of trapping potential, buffer gas pressure, supplementary RF-potential, and laser intensity. In separate studies, laser desorption was used to generate gas phase ions in the ITMS from a solid probe, by irradiation of both neat and matrix-dissolved samples. The latter experiment produced both high molecular weight ions and significant numbers of negative ions.

  18. "Fast Excitation" CID in Quadrupole Ion Trap Mass Spectrometer

    SciTech Connect

    Murrell, J.; Despeyroux, D.; Lammert, Stephen {Steve} A; Stephenson Jr, James {Jim} L; Goeringer, Doug

    2003-01-01

    Collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer is usually performed by applying a small amplitude excitation voltage at the same secular frequency as the ion of interest. Here we disclose studies examining the use of large amplitude voltage excitations (applied for short periods of time) to cause fragmentation of the ions of interest. This process has been examined using leucine enkephalin as the model compound and the motion of the ions within the ion trap simulated using ITSIM. The resulting fragmentation information obtained is identical with that observed by conventional resonance excitation CID. ''Fast excitation'' CID deposits (as determined by the intensity ratio of the a{sub 4}/b{sub 4} ion of leucine enkephalin) approximately the same amount of internal energy into an ion as conventional resonance excitation CID where the excitation signal is applied for much longer periods of time. The major difference between the two excitation techniques is the higher rate of excitation (gain in kinetic energy) between successive collisions with helium atoms with ''fast excitation'' CID as opposed to the conventional resonance excitation CID. With conventional resonance excitation CID ions fragment while the excitation voltage is still being applied whereas for ''fast excitation'' CID a higher proportion of the ions fragment in the ion cooling time following the excitation pulse. The fragmentation of the (M + 17H){sup 17+} of horse heart myoglobin is also shown to illustrate the application of ''fast excitation'' CID to proteins.

  19. Conditioning of ion sources for mass spectrometry of plasmas

    SciTech Connect

    Dylla, H.F.; Blanchard, W.R.

    1983-02-01

    Mass spectrometry is a useful diagnostic technique for monitoring plasma species and plasma-surface interactions. In order to maximize the sensitivity of measurements of hydrogen-fueled fusion plasmas or hydrogen-based discharge cleaning and etching plasmas, the ion sources of mass spectrometers are operated at or near the high pressure limit of 10/sup -4/ Torr (10/sup -2/ Pa). Such high ambient pressures of hydrogen give rise to high background levels of residual gases such as H/sub 2/O, CO, and CH/sub 4/, due to surface reactions on the ion source electrodes. For a commonly used ion source configuration, the residual gas production is a linear function of the ambient H/sub 2/ pressure. Hydrogen conditioning can reduce the absolute residual gas levels. Steady-state residual gas production is observed in a conditioned ion source, which is related to a balance of diffusion and sorption on the electrode surfaces.

  20. Fundamental studies of ion injection and trapping of electrosprayed ions on a quadrupole ion trap mass spectrometer

    NASA Astrophysics Data System (ADS)

    Quarmby, Scott Thomas

    The quadrupole ion trap is a highly versatile and sensitive analytical mass spectrometer. Because of the advantages offered by the ion trap, there has been intense interest in coupling it to ionization techniques such as electrospray which form ions externally to the ion trap. In this work, experiments and computer simulations were employed to study the injection of electrosprayed ions into the ion trap of a Finnigan MAT LCQ LC/MS n mass spectrometer. The kinetic energy distribution of the ion beam was characterized and found to be relatively wide, a result of the high pressures from the atmospheric pressure source. One of the most important experimental parameters which affects ion injection efficiency is the RF voltage applied to the ring electrode. A theoretical model was fit to experimental data allowing the optimum RF voltage for trapping a given m/z ion to be predicted. Computer simulations of ion motion were performed to study the effect of various instrumental parameters on trapping efficiency. A commercially available ion optics program, SIMION v6.0, was chosen because it allowed the actual ion trap electrode geometry including endcap holes to be simulated. In contrast to previous computer simulations, SIMION provided the ability to start ions outside the ion trap and to simulate more accurately the injection of externally formed ions. The endcap holes were found to allow the RF field to penetrate out of the ion trap and affect ions as they approached the ion trap. From these simulations, a model for the process by which injected ions are trapped was developed. Using these computer simulations, techniques of improving trapping efficiency were investigated. Most previous techniques perturb ions which are already in the ion trap and therefore cannot be used to accumulate ions; the ability to accumulate ions is a necessity with ionization sources such as electrospray which form ions continuously. One such novel technique for improving trapping efficiency

  1. Ion mobility–mass spectrometry for structural proteomics

    PubMed Central

    Zhong, Yueyang; Hyung, Suk-Joon; Ruotolo, Brandon T

    2012-01-01

    Ion mobility coupled to mass spectrometry has been an important tool in the fields of chemical physics and analytical chemistry for decades, but its potential for interrogating the structure of proteins and multiprotein complexes has only recently begun to be realized. Today, ion mobility– mass spectrometry is often applied to the structural elucidation of protein assemblies that have failed high-throughput crystallization or NMR spectroscopy screens. Here, we highlight the technology, approaches and data that have led to this dramatic shift in use, including emerging trends such as the integration of ion mobility–mass spectrometry data with more classical (e.g., ‘bottom-up’) proteomics approaches for the rapid structural characterization of protein networks. PMID:22292823

  2. Laser ion acceleration from mass-limited targets with preplasma

    NASA Astrophysics Data System (ADS)

    Lezhnin, K. V.; Kamenets, F. F.; Esirkepov, T. Zh.; Bulanov, S. V.; Klimo, O.; Weber, S.; Korn, G.

    2016-05-01

    The interaction of high intensity laser radiation with mass-limited target exhibits significant enhancement of the ion acceleration when the target is surrounded by an underdense plasma corona, as seen in numerical simulations. The self-generated quasistatic magnetic field squeezes the corona causing the intensification of a subsequent Coulomb explosion of the target. The electric field intensification at the target edges and plasma resonance effects results in the generation of characteristic density holes and further contributes to the ion acceleration.

  3. Multiple Mass Analysis Using an Ion Trap Array (ITA) Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Xiao, Yu; Chu, Yanqiu; Ling, Xing; Ding, Zhengzhi; Xu, Chongsheng; Ding, Li; Ding, Chuan-Fan

    2013-09-01

    A novel ion trap array (ITA) mass analyzer with six ion trapping and analyzing channels was investigated. It is capable of analyzing multiple samples simultaneously. The ITA was built with several planar electrodes made of stainless steel and 12 identical parallel zirconia ceramic substrates plated with conductive metal layers. Each two of the opposing ceramic electrode plates formed a boundary of an ion trap channel and six identical ion trapping and analyzing channels were placed in parallel without physical electrode between any two adjacent channels. The electric field distribution inside each channel was studied with simulation. The new design took the advantage of high precision machining attributable to the rigidity of ceramic, and the convenience of surface patterning technique. The ITA system was tested by using a two-channel electrospray ionization source, a multichannel simultaneous quadruple ion guide, and two detectors. The simultaneous analysis of two different samples with two adjacent ITA channels was achieved and independent mass spectra were obtained. For each channel, the mass resolution was tested. Additional ion trap functions such as mass-selected ion isolation and collision-induced dissociation (CID) were also tested. The results show that one ITA is well suited for multiple simultaneous mass analyses.

  4. Multiple mass analysis using an ion trap array (ITA) mass analyzer.

    PubMed

    Yu, Xiao; Chu, Yanqiu; Ling, Xing; Ding, Zhengzhi; Xu, Chongsheng; Ding, Li; Ding, Chuan-Fan

    2013-09-01

    A novel ion trap array (ITA) mass analyzer with six ion trapping and analyzing channels was investigated. It is capable of analyzing multiple samples simultaneously. The ITA was built with several planar electrodes made of stainless steel and 12 identical parallel zirconia ceramic substrates plated with conductive metal layers. Each two of the opposing ceramic electrode plates formed a boundary of an ion trap channel and six identical ion trapping and analyzing channels were placed in parallel without physical electrode between any two adjacent channels. The electric field distribution inside each channel was studied with simulation. The new design took the advantage of high precision machining attributable to the rigidity of ceramic, and the convenience of surface patterning technique. The ITA system was tested by using a two-channel electrospray ionization source, a multichannel simultaneous quadruple ion guide, and two detectors. The simultaneous analysis of two different samples with two adjacent ITA channels was achieved and independent mass spectra were obtained. For each channel, the mass resolution was tested. Additional ion trap functions such as mass-selected ion isolation and collision-induced dissociation (CID) were also tested. The results show that one ITA is well suited for multiple simultaneous mass analyses. PMID:23797864

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

    NASA Astrophysics Data System (ADS)

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

    2004-05-01

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

  6. Developments in ion mobility spectrometry-mass spectrometry.

    PubMed

    Collins, D C; Lee, M L

    2002-01-01

    Ion mobility spectrometry (IMS) has been used for over 30 years as a sensitive detector of organic compounds. The following is a brief review of IMS and its principles with an emphasis on its usage when coupled to mass spectrometry. Since its inception, IMS has been interfaced with quadrupole, time-of-flight, and Fourier-transform ion cyclotron resonance mass spectrometry. These hybrid instruments have been employed for the analysis of a variety of target analytes, including biomolecules, explosives, chemical warfare degradation products, and illicit drugs. PMID:11939214

  7. A retarding ion mass spectrometer for the Dynamics Explorer-1

    NASA Technical Reports Server (NTRS)

    Wright, W.

    1985-01-01

    The Retarding Ion Mass Spectrometer (RIMS) for Dynamics Explorer-1 is an instrument designed to measure the details of the thermal plasma distribution. It combines the ion temperature determining capability of the retarding potential analyzer with the compositional capabilities of the mass spectrometer and adds multiple sensor heads to sample all directions relative to the spacecraft ram direction. This manual provides a functional description of the RIMS, the instrument calibration, and a description of the commands which can be stored in the instrument logic to control its operation.

  8. Ion mass spectrometer experiment for ISIS-2 spacecraft

    NASA Astrophysics Data System (ADS)

    Hoffman, John H.

    1987-07-01

    The International Satellite for Ionospheric Studies (ISIS) program of NASA was the longest duration program in NASA history. A number of satellites were flown under this program, the last being called ISIS-2, which was launched on April 1, 1971 and operated successfully for over 13 years. An experiment called the Ion Mass Spectrometer (IMS) was flown on the ISIS-2 spacecraft. It operated for 10 years providing a large data base of positive ion composition and ion flow velocities along the orbit of the satellite, the latter being circular at 1400 km with a 90 degree inclination. The data were processed and reside in the National Space Sciences Data Center.

  9. Ion mass spectrometer experiment for ISIS-2 spacecraft

    NASA Technical Reports Server (NTRS)

    Hoffman, John H.

    1987-01-01

    The International Satellite for Ionospheric Studies (ISIS) program of NASA was the longest duration program in NASA history. A number of satellites were flown under this program, the last being called ISIS-2, which was launched on April 1, 1971 and operated successfully for over 13 years. An experiment called the Ion Mass Spectrometer (IMS) was flown on the ISIS-2 spacecraft. It operated for 10 years providing a large data base of positive ion composition and ion flow velocities along the orbit of the satellite, the latter being circular at 1400 km with a 90 degree inclination. The data were processed and reside in the National Space Sciences Data Center.

  10. Detection of gaseous organophosphorus compounds using secondary ion mass spectrometry

    SciTech Connect

    Groenewold, G.S.; Todd, P.J.

    1985-04-01

    Molecular secondary ion mass spectrometry (SIMS) has been investigated for sensitivity and selectivity in the analysis of gaseous organophosphorus compounds. Abundant analyte ions were observed when the gaseous organophosphorus compounds were admitted into the secondary ion source, where a matrix was under primary ion bombardment. The best matrix for the detection of dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), and diisopropyl methylphosphonate (DIMP) was determined to be polyphosphoric acid. The abundance of secondary analyte ions was observed to be linear with the introduction rate of gaseous analyte. The introduction rate necessary to produce a 3:1 signal-to-noise ratio in the intensity of secondary protonated molecular ions from DMMP was estimated to be 4 x 10/sup -11/ mols/sup -1/. Substantially more analyte fragmentation is observed by using SIMS than by using methane chemical ionization mass spectrometry. Ten compounds representative of other compound classes were investigated in the same manner as the organic phosphonates; characteristic secondary protonated molecular ions were detected from amines only.

  11. Depth resolution improvement in secondary ion mass spectrometry analysis using metal cluster complex ion bombardment

    SciTech Connect

    Tomita, M.; Kinno, T.; Koike, M.; Tanaka, H.; Takeno, S.; Fujiwara, Y.; Kondou, K.; Teranishi, Y.; Nonaka, H.; Fujimoto, T.; Kurokawa, A.; Ichimura, S.

    2006-07-31

    Secondary ion mass spectrometry analyses were carried out using a metal cluster complex ion of Ir{sub 4}(CO){sub 7}{sup +} as a primary ion beam. Depth resolution was evaluated as a function of primary ion species, energy, and incident angle. The depth resolution obtained using cluster ion bombardment was considerably better than that obtained by oxygen ion bombardment under the same experimental condition due to reduction of atomic mixing in the depth. The authors obtained a depth resolution of {approx}1 nm under 5 keV, 45 deg. condition. Depth resolution was degraded by ion-bombardment-induced surface roughness at 5 keV with higher incident angles.

  12. Radio-frequency ion deflector for mass separation

    SciTech Connect

    Schlösser, Magnus Rudnev, Vitaly; Ureña, Ángel González

    2015-10-15

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

  13. Radio-frequency ion deflector for mass separation.

    PubMed

    Schlösser, Magnus; Rudnev, Vitaly; González Ureña, Ángel

    2015-10-01

    Electrostatic cylindrical deflectors act as energy analyzer for ion beams. In this article, we present that by imposing of a radio-frequency modulation on the deflecting electric field, the ion transmission becomes mass dependent. By the choice of the appropriate frequency, amplitude, and phase, the deflector can be used as mass filter. The basic concept of the new instrument as well as simple mathematic relations are described. These calculations and further numerical simulations show that a mass sensitivity is achievable. Furthermore, we demonstrate the proof-of-principle in experimental measurements, compare the results to those of from a 1 m linear time-of-flight spectrometer, and comment on the mass resolution of the method. Finally, some potential applications are indicated. PMID:26520948

  14. Augmenting Ion Trap Mass Spectrometers Using a Frequency Modulated Drift Tube Ion Mobility Spectrometer.

    PubMed

    Morrison, Kelsey A; Siems, William F; Clowers, Brian H

    2016-03-15

    Historically, high pressure ion mobility drift tubes have suffered from low ion duty cycles and this problem is magnified when such instrumentation is coupled with ion trap mass spectrometers. To significantly alleviate these issues, we outline the result from coupling an atmospheric pressure, dual-gate drift tube ion mobility spectrometer (IMS) to a linear ion trap mass spectrometer (LIT-MS) via modulation of the ion beam with a linear frequency chirp. The time-domain ion current, once Fourier transformed, reveals a standard ion mobility drift spectrum that corresponds to the standard mode of mobility analysis. By multiplexing the ion beam, it is possible to successfully obtain drift time spectra for an assortment of simple peptide and protein mixtures using an LIT-MS while showing improved signal intensity versus the more common signal averaging technique. Explored here are the effects of maximum injection time, solution concentration, total experiment time, and frequency swept on signal-to-noise ratios (SNRs) and resolving power. Increased inject time, concentration, and experiment time all generally led to an improvement in SNR, while a greater frequency swept increases the resolving power at the expense of SNR. Overall, chirp multiplexing of a dual-gate IMS system coupled to an LIT-MS improves ion transmission, lowers analyte detection limits, and improves spectral quality. PMID:26854901

  15. Advances in imaging secondary ion mass spectrometry for biological samples

    SciTech Connect

    Boxer, Steven G.; Kraft, Mary L.; Weber, Peter K.

    2008-12-16

    Imaging mass spectrometry combines the power of mass spectrometry to identify complex molecules based on mass with sample imaging. Recent advances in secondary ion mass spectrometry have improved sensitivity and spatial resolution, so that these methods have the potential to bridge between high-resolution structures obtained by X-ray crystallography and cyro-electron microscopy and ultrastructure visualized by conventional light microscopy. Following background information on the method and instrumentation, we address the key issue of sample preparation. Because mass spectrometry is performed in high vacuum, it is essential to preserve the lateral organization of the sample while removing bulk water, and this has been a major barrier for applications to biological systems. Furthermore, recent applications of imaging mass spectrometry to cell biology, microbial communities, and biosynthetic pathways are summarized briefly, and studies of biological membrane organization are described in greater depth.

  16. Advances in imaging secondary ion mass spectrometry for biological samples

    DOE PAGESBeta

    Boxer, Steven G.; Kraft, Mary L.; Weber, Peter K.

    2008-12-16

    Imaging mass spectrometry combines the power of mass spectrometry to identify complex molecules based on mass with sample imaging. Recent advances in secondary ion mass spectrometry have improved sensitivity and spatial resolution, so that these methods have the potential to bridge between high-resolution structures obtained by X-ray crystallography and cyro-electron microscopy and ultrastructure visualized by conventional light microscopy. Following background information on the method and instrumentation, we address the key issue of sample preparation. Because mass spectrometry is performed in high vacuum, it is essential to preserve the lateral organization of the sample while removing bulk water, and this hasmore » been a major barrier for applications to biological systems. Furthermore, recent applications of imaging mass spectrometry to cell biology, microbial communities, and biosynthetic pathways are summarized briefly, and studies of biological membrane organization are described in greater depth.« less

  17. Ion mobility spectrometer / mass spectrometer (IMS-MS).

    SciTech Connect

    Hunka Deborah Elaine; Austin, Daniel E.

    2005-07-01

    The use of Ion Mobility Spectrometry (IMS) in the Detection of Contraband Sandia researchers use ion mobility spectrometers for trace chemical detection and analysis in a variety of projects and applications. Products developed in recent years based on IMS-technology include explosives detection personnel portals, the Material Area Access (MAA) checkpoint of the future, an explosives detection vehicle portal, hand-held detection systems such as the Hound and Hound II (all 6400), micro-IMS sensors (1700), ordnance detection (2500), and Fourier Transform IMS technology (8700). The emphasis to date has been on explosives detection, but the detection of chemical agents has also been pursued (8100 and 6400). Combining Ion Mobility Spectrometry (IMS) with Mass Spectrometry (MS) is described. The IMS-MS combination overcomes several limitations present in simple IMS systems. Ion mobility alone is insufficient to identify an unknown chemical agent. Collision cross section, upon which mobility is based, is not sufficiently unique or predictable a priori to be able to make a confident peak assignment unless the compounds present are already identified. Molecular mass, on the other hand, is much more readily interpreted and related to compounds. For a given compound, the molecular mass can be determined using a pocket calculator (or in one's head) while a reasonable value of the cross-section might require hours of computation time. Thus a mass spectrum provides chemical specificity and identity not accessible in the mobility spectrum alone. In addition, several advanced mass spectrometric methods, such as tandem MS, have been extensively developed for the purpose of molecular identification. With an appropriate mass spectrometer connected to an ion mobility spectrometer, these advanced identification methods become available, providing greater characterization capability.

  18. Ion Mobility Spectrometer / Mass Spectrometer (IMS-MS).

    SciTech Connect

    Hunka, Deborah E; Austin, Daniel

    2005-10-01

    The use of Ion Mobility Spectrometry (IMS)in the Detection of Contraband Sandia researchers use ion mobility spectrometers for trace chemical detection and analysis in a variety of projects and applications. Products developed in recent years based on IMS-technology include explosives detection personnel portals, the Material Area Access (MAA) checkpoint of the future, an explosives detection vehicle portal, hand-held detection systems such as the Hound and Hound II (all 6400), micro-IMS sensors (1700), ordnance detection (2500), and Fourier Transform IMS technology (8700). The emphasis to date has been on explosives detection, but the detection of chemical agents has also been pursued (8100 and 6400).Combining Ion Mobility Spectrometry (IMS) with Mass Spectrometry (MS)The IMS-MS combination overcomes several limitations present in simple IMS systems. Ion mobility alone is insufficient to identify an unknown chemical agent. Collision cross section, upon which mobility is based, is not sufficiently unique or predictable a priori to be able to make a confident peak assignment unless the compounds present are already identified. Molecular mass, on the other hand, is much more readily interpreted and related to compounds. For a given compound, the molecular mass can be determined using a pocket calculator (or in one's head) while a reasonable value of the cross-section might require hours of computation time. Thus a mass spectrum provides chemical specificity and identity not accessible in the mobility spectrum alone. In addition, several advanced mass spectrometric methods, such as tandem MS, have been extensively developed for the purpose of molecular identification. With an appropriate mass spectrometer connected to an ion mobility spectrometer, these advanced identification methods become available, providing greater characterization capability.3 AcronymsIMSion mobility spectrometryMAAMaterial Access AreaMSmass spectrometryoaTOForthogonal acceleration time

  19. Time-of-flight secondary ion mass spectrometry with transmission of energetic primary cluster ions through foil targets

    SciTech Connect

    Hirata, K.; Saitoh, Y.; Chiba, A.; Yamada, K.; Matoba, S.; Narumi, K.

    2014-03-15

    We developed time-of-flight (TOF) secondary ion (SI) mass spectrometry that provides informative SI ion mass spectra without needing a sophisticated ion beam pulsing system. In the newly developed spectrometry, energetic large cluster ions with energies of the order of sub MeV or greater are used as primary ions. Because their impacts on the target surface produce high yields of SIs, the resulting SI mass spectra are informative. In addition, the start signals necessary for timing information on primary ion incidence are provided by the detection signals of particles emitted from the rear surface of foil targets upon transmission of the primary ions. This configuration allows us to obtain positive and negative TOF SI mass spectra without pulsing system, which requires precise control of the primary ions to give the spectra with good mass resolution. We also successfully applied the TOF SI mass spectrometry with energetic cluster ion impacts to the chemical structure characterization of organic thin film targets.

  20. Searching for photon rest-mass with ion interferometry

    NASA Astrophysics Data System (ADS)

    Christensen, Dan; Neyenhuis, Brian; Spencer, Ross; Durfee, Dallin

    2006-10-01

    We will discuss a proposed scheme to search for a non-zero photon rest mass. This scheme could be more than 100 times more sensitive than previous experiments. The experiment would use an ion interferometer to search for variations in Coulomb's inverse-square law predicted by the Proca equation. Analytical and numerical computations will be presented.

  1. 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. PMID:25601688

  2. Transient Ion-Pair Separations for Electrospray Mass Spectrometry.

    PubMed

    Liu, Hanghui; Lam, Lily; Chi, Bert; Kadjo, Akinde F; Dasgupta, Purnendu K

    2016-02-16

    We report a novel ion-pair chromatography (IPC) approach for liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS), where the eluent does not contain any ion-pairing reagent (IPR). The IPR is injected on the column, much like the sample, and moves down the column. Significant amounts of a high retention factor IPR is injected, resulting in a transient but reproducible regional coating that progresses along the column. The sample is injected after a brief interval. The sample components interact with the IPR coated region during their passage; the chosen eluent gradient elutes the analytes of interest into the mass spectrometer before the IPR. Following analyte elution, the gradient is steeply raised, the IPR is washed out, and the effluent is sent to waste via a diverter valve until it is fully removed. As the nature of the analyte retention continuously changes along the column and with time, we call this transient ion-pair separation (TIPS). As the IPR never enters the MS, TIPS addresses two major drawbacks of IPC for ESI-MS: it avoids both ion suppression and ion source contamination. The potential of the generic approach for other modes of separation is discussed. An illustrative separation of two small inorganic ions, iodate and nitrate, is demonstrated on a reverse phase column by a transient prior injection of hexadecyltrimethylammonium chloride as IPR. PMID:26765166

  3. Utilizing Ion-Mobility Data to Estimate Molecular Masses

    NASA Technical Reports Server (NTRS)

    Duong, Tuan; Kanik, Isik

    2008-01-01

    A method is being developed for utilizing readings of an ion-mobility spectrometer (IMS) to estimate molecular masses of ions that have passed through the spectrometer. The method involves the use of (1) some feature-based descriptors of structures of molecules of interest and (2) reduced ion mobilities calculated from IMS readings as inputs to (3) a neural network. This development is part of a larger effort to enable the use of IMSs as relatively inexpensive, robust, lightweight instruments to identify, via molecular masses, individual compounds or groups of compounds (especially organic compounds) that may be present in specific environments or samples. Potential applications include detection of organic molecules as signs of life on remote planets, modeling and detection of biochemicals of interest in the pharmaceutical and agricultural industries, and detection of chemical and biological hazards in industrial, homeland-security, and industrial settings.

  4. Measuring Neutrino Mass with Radioactive Ions in a Storage Ring

    SciTech Connect

    Lindroos, Mats; McElrath, Bob; Orme, Christopher; Schwetz, Thomas

    2010-03-30

    A method to measure the neutrino mass kinematically using beams of ions which undergo beta decay is proposed. The idea is to tune the ion beam momentum so that in most decays, the electron is forward moving with respect to the beam, and only in decays near the endpoint is the electron moving backwards. By counting the backward moving electrons one can observe the effect of neutrino mass on the beta spectrum close to the endpoint. In order to reach sensitivities for m{sub n}u<0.2 eV, it is necessary to control the ion momentum with a precision better than deltap/p<10{sup -5}, identify suitable nuclei with low Q-values (in the few to ten keV range), and one must be able to observe at least O(10{sup 18}) decays.

  5. High-Sensitivity Ion Mobility Spectrometry/Mass Spectrometry Using Electrodynamic Ion Funnel Interfaces

    PubMed Central

    Tang, Keqi; Shvartsburg, Alexandre A.; Lee, Hak-No; Prior, David C.; Buschbach, Michael A.; Li, Fumin; Tolmachev, Aleksey; Anderson, Gordon A.; Smith, Richard D.

    2007-01-01

    The utility of ion mobility spectrometry (IMS) for separation of mixtures and structural characterization of ions has been demonstrated extensively, including in the biological and nanoscience contexts. A major attraction of IMS is its speed, several orders of magnitude greater than that of condensed-phase separations. Nonetheless, IMS combined with mass spectrometry (MS) has remained a niche technique, substantially because of limited sensitivity resulting from ion losses at the IMS-MS junction. We have developed a new electrospray ionization (ESI)-IMS-QToF MS instrument that incorporates electrodynamic ion funnels at both front ESI-IMS and rear IMS-QToF interfaces. The front funnel is of the novel “hourglass” design that efficiently accumulates ions and pulses them into the IMS drift tubes. Even for drift tubes of two meter length, ion transmission through IMS and on to QToF is essentially lossless across the range of ion masses relevant to most applications. The RF ion focusing at the IMS terminus does not degrade IMS resolving power, which exceeds 100 (for singly-charged ions) and is close to the theoretical limit. The overall sensitivity of present ESI-IMS-MS system is comparable to that of commercial ESI-MS, which should make IMS-MS suitable for analyses of complex mixtures with ultra-high sensitivity and exceptional throughput. PMID:15889926

  6. High-Sensitivity Ion Mobility Spectrometry/Mass Spectrometry Using Electrodynamic Ion Funnel Interfaces

    SciTech Connect

    Tang, Keqi; Shvartsburg, Alexandre A.; Lee, Hak-No; Prior, David C.; Buschbach, Michael A.; Li, Fumin; Tolmachev, Aleksey V.; Anderson, Gordon A.; Smith, Richard D.

    2005-05-15

    The utility of ion mobility spectrometry (IMS) for separation of mixtures and structural characterization of ions has been demonstrated extensively, including in the biological and nanoscience contexts. A major attraction of IMS is its speed, several orders of magnitude above that of condensed-phase separations. Nonetheless, IMS combined with mass spectrometry (MS) has remained a niche technique, substantially due to limited sensitivity resulting from ion losses at the IMS-MS junction. We have developed a new electrospray ionization (ESI)-IMS-QToF MS instrument that incorporates electrodynamic ion funnels at both front ESI-IMS and back IMS-QToF interfaces. The front funnel is of the novel ''hourglass'' design that efficiently accumulates ions and pulses them into the IMS drift tubes. Even for drift tubes of two meter length, ion transmission through IMS and on to QToF is essentially lossless across the range of ion masses relevant to most applications. The RF ion focusing at IMS terminus does not degrade IMS resolving power, which exceeds 100 (for singly-charged ions) and is close to the theoretical limit. The overall sensitivity of present ESI-IMS-MS system is shown to be comparable to that of commercial ESI-MS, which should make IMS-MS suitable for analyses of complex mixtures with ultra-high sensitivity and exceptional throughput.

  7. Frequency-swept detector for ion cyclotron resonance mass spectrometers

    NASA Astrophysics Data System (ADS)

    Wronka, J.; Ridge, D. P.

    1982-04-01

    Design, construction, performance, and use of a frequency-swept bridge detector for ion cyclotron resonance mass spectrometry are described. Special features include characterization and simple automatic correction of phase shift to allow broadband detection. The result is a detection system that may be used either at constant field or constant frequency. Drift-mode operation is simplified in that it may be satisfactorily used without the various signal modulation schemes used in previous detectors. In the trapped mode the detector may be pulsed to control the timing of ion detection. This detector makes it possible to do frequency-swept double resonance experiments which provide spectra of all the product ions of a given reactant ion. Circuit schematics and typical frequency- and field-swept spectra are shown.

  8. Cryogenic Ion Mobility-Mass Spectrometry: Tracking Ion Structure from Solution to the Gas Phase.

    PubMed

    Servage, Kelly A; Silveira, Joshua A; Fort, Kyle L; Russell, David H

    2016-07-19

    Electrospray ionization (ESI) combined with ion mobility-mass spectrometry (IM-MS) is adding new dimensions, that is, structure and dynamics, to the field of biological mass spectrometry. There is increasing evidence that gas-phase ions produced by ESI can closely resemble their solution-phase structures, but correlating these structures can be complicated owing to the number of competing effects contributing to structural preferences, including both inter- and intramolecular interactions. Ions encounter unique hydration environments during the transition from solution to the gas phase that will likely affect their structure(s), but many of these structural changes will go undetected because ESI-IM-MS analysis is typically performed on solvent-free ions. Cryogenic ion mobility-mass spectrometry (cryo-IM-MS) takes advantage of the freeze-drying capabilities of ESI and a cryogenically cooled IM drift cell (80 K) to preserve extensively solvated ions of the type [M + xH](x+)(H2O)n, where n can vary from zero to several hundred. This affords an experimental approach for tracking the structural evolution of hydrated biomolecules en route to forming solvent-free gas-phase ions. The studies highlighted in this Account illustrate the varying extent to which dehydration can alter ion structure and the overall impact of cryo-IM-MS on structural studies of hydrated biomolecules. Studies of small ions, including protonated water clusters and alkyl diammonium cations, reveal structural transitions associated with the development of the H-bond network of water molecules surrounding the charge carrier(s). For peptide ions, results show that water networks are highly dependent on the charge-carrying species within the cluster. Specifically, hydrated peptide ions containing lysine display specific hydration behavior around the ammonium ion, that is, magic number clusters with enhanced stability, whereas peptides containing arginine do not display specific hydration around the

  9. Combined electron and focused ion beam system for improvement of secondary ion yield in secondary ion mass spectrometry instrument

    SciTech Connect

    Ji, L.; Ji, Q.; Leung, K.-N.; Gough, R. A.

    2006-10-16

    Using a combined electron and focused ion beam system to improve performance of secondary ion mass spectrometry instruments has been investigated experimentally. The secondary ion yield for an Al target has been enhanced to about one order of magnitude higher with the postionization induced by the low energy electrons in the combined beam. It can be further improved with the increase of electron beam current. When the combined beam is applied to insulating targets, sample charging is also eliminated. For Teflon targets, the secondary ion signal is increased by more than a factor of 20.

  10. Coulomb crystal mass spectrometry in a digital ion trap

    NASA Astrophysics Data System (ADS)

    Deb, Nabanita; Pollum, Laura L.; Smith, Alexander D.; Keller, Matthias; Rennick, Christopher J.; Heazlewood, Brianna R.; Softley, Timothy P.

    2015-03-01

    We present a mass spectrometric technique for identifying the masses and relative abundances of Coulomb-crystallized ions held in a linear Paul trap. A digital radio-frequency wave form is employed to generate the trapping potential, as this can be cleanly switched off, and static dipolar fields are subsequently applied to the trap electrodes for ion ejection. Close to 100% detection efficiency is demonstrated for Ca+ and CaF+ ions from bicomponent Ca+-CaF+ Coulomb crystals prepared by the reaction of Ca+ with CH3F . A quantitative linear relationship is observed between ion number and the corresponding integrated time-of-flight (TOF) peak, independent of the ionic species. The technique is applicable to a diverse range of multicomponent Coulomb crystals—demonstrated here for Ca+-NH 3+ -NH 4+ and Ca+-CaOH +-CaOD + crystals—and will facilitate the measurement of ion-molecule reaction rates and branching ratios in complicated reaction systems.

  11. Negative thermal ion mass spectrometry of oxygen in phosphates

    NASA Astrophysics Data System (ADS)

    Holmden, C.; Papanastassiou, D. A.; Wasserburg, G. J.

    1997-06-01

    A novel technique for the precise measurement of oxygen isotopes by negative thermal ion mass spectrometry (NTIMS) is presented. The technique is ideally suited to the analysis of oxygen isotopes in phosphates which form intense P03 ion beams. Since P is monoisotopic, the mass spectrum for P0 3- at 79, 80, and 81 corresponds to 1660, 170, and 180. Natural and synthetic phosphates are converted and loaded on the mass spectrometer filament as Ag 3PO 4 precipitated directly from ammoniacal solution. To lower the work function of the filament, BaCl, is added in a 1:1 molar ratio of PO 4:Ba. Using these procedures, Br - mass interference (at 79 and 81 amu) is eliminated for typical analyses. Experiments with 180-enriched water show less than 1 % O-exchange between sample PO 4 and adsorbed water, and there is no O-exchange with trace OZ present in the mass spectrometer source chamber. The ionization efficiency of PO 4, as P0 3- is >10% compared to 0.01% for both conventional dual inlet Gas Isotope Ratio Mass Spectrometry (GIRMS) and secondary ion mass spectrometry (SIMS). Therefore, NTIMS offers exceptional sensitivity enabling routine and precise oxygen isotope analysis of sub-microgram samples of PO 4, (<21 nmoles equivalent CO 2 gas) without need for lengthy chemical pre-treatment reproducibility of the sample. Overall external precision is ±1%c (2σ) for 18O/16 O and 170/15O with of instrumental isotope fractionation (calculated from 18O/16O of ±0.5%c amu -1. Small phosphate samples including single mineral grains from meteorites, or apatite microfossils, can be analyzed by this technique.

  12. Compact Ion and Neutral Mass Spectrometer with Ion Drifts, Temperatures and Neutral Winds

    NASA Astrophysics Data System (ADS)

    Paschalidis, Nikolaos

    2016-07-01

    In situ measurements of atmospheric neutral and ion composition and density, temperatures, ion drifts and neutral winds, are in high demand to study the dynamics of the ionosphere-theremosphere-mesosphere system. This paper presents a compact Ion and Neutral Mass Spectrometer (INMS) with impended ion drifts and temperature, and neutral winds capability for in situ measurements of ions and neutrals H, He, N, O, N2, O2. The mass resolution M/dM is approximately 10 at an incoming energy range of 0-20eV. The goal is to resolve ion drifts in the range 0 to 3000m/sec with a resolution better than 50m/sec, and neutral winds in the range of 0 to 1000m/sec with similar resolution. For temperatures the goal is to cover a dynamic range of 0 to 5000K. The INMS is based on front end optics for ions and neutrals, pre acceleration, gated time of flight, top hat ESA, MCP detectors and compact electronics. The instrument is redundant for ions and neutrals with the ion and neutral sensor heads on opposite sides and with full electronics in the middle. The ion front end includes RPA for temperature scanning and neutral front end includes angular modulation and thermionic ionization and ion blocking grids. The electronics include fast electric gating, TOF electronics, TOF binning and C&DH digital electronics. The data package includes 400 mass bins each for ions and neutrals and key housekeeping data for instrument health and calibration. The data sampling can be commanded from 0.1 to 10 sec with 1sec nominal setting. The instrument has significant onboard storage capability and a data compression scheme. The mass spectrometer version of the instrument has been flown on the Exocube mission. The instrument occupied 1.5U volume, weighed only 560 g and required nominal power of 1.6W The ExoCube mission was designed to acquire global knowledge of in-situ densities of [H], [He], [O] and H+, He+, O+ in the upper ionosphere and lower exosphere in combination with incoherent scatter radar and

  13. Evolution of instrumentation for the study of gas-phase ion/ion chemistry via mass spectrometry.

    PubMed

    Xia, Yu; McLuckey, Scott A

    2008-02-01

    The scope of gas-phase ion/ion chemistry accessible to mass spectrometry is largely defined by the available tools. Due to the development of novel instrumentation, a wide range of reaction phenomenologies has been noted, many of which have been studied extensively and exploited for analytical applications. This perspective presents the development of mass spectrometry-based instrumentation for the study of the gas-phase ion/ion chemistry in which at least one of the reactants is multiply charged. The instrument evolution is presented within the context of three essential elements required for any ion/ion reaction study: the ionization source(s), the reaction vessel or environment, and the mass analyzer. Ionization source arrangements have included source combinations that allow for reactions between multiply charged ions of one polarity and singly charged ions of opposite polarity, arrangements that enable the study of reactions of multiply charged ions of opposite polarity and, most recently, arrangements that allow for ion formation from more than two ion sources. Gas-phase ion/ion reaction studies have been performed at near atmospheric pressure in flow reactor designs and within electrodynamic ion traps operated in the mTorr range. With ion trap as a reaction vessel, ionization and reaction processes can be independently optimized and ion/ion reactions can be implemented within the context of MSn experiments. Spatial separation of the reaction vessel from the mass analyzer allows for the use of any form of mass analysis in conjunction with ion/ion reactions. Time-of-flight mass analysis, for example, has provided significant improvements in mass analysis figures of merit relative to mass filters and ion traps. PMID:18083527

  14. Evolution of Instrumentation for the Study of Gas-Phase Ion/Ion Chemistry via Mass Spectrometry

    PubMed Central

    Xia, Yu; McLuckey, Scott A.

    2008-01-01

    The scope of gas phase ion/ion chemistry accessible to mass spectrometry is largely defined by the available tools. Due to the development of novel instrumentation, a wide range of reaction phenomenologies have been noted, many of which have been studied extensively and exploited for analytical applications. This perspective presents the development of mass spectrometry-based instrumentation for the study of the gas phase ion/ion chemistry in which at least one of the reactants is multiply-charged. The instrument evolution is presented within the context of three essential elements required for any ion/ion reaction study: the ionization source(s), the reaction vessel or environment, and the mass analyzer. Ionization source arrangements have included source combinations that allow for reactions between multiply charged ions of one polarity and singly charged ions of opposite polarity, arrangements that enable the study of reactions of multiply charged ions of opposite polarity, and most recently, arrangements that allow for ion formation from more than two ion sources. Gas phase ion/ion reaction studies have been performed at near atmospheric pressure in flow reactor designs and within electrodynamic ion traps operated in the mTorr range. With ion trap as a reaction vessel, ionization and reaction processes can be independently optimized and ion/ion reactions can be implemented within the context of MSn experiments. Spatial separation of the reaction vessel from the mass analyzer allows for the use of any form of mass analysis in conjunction with ion/ion reactions. Time-of-flight mass analysis, for example, has provided significant improvements in mass analysis figures of merit relative to mass filters and ion traps. PMID:18083527

  15. Automatic detection of mass-resolved ion conics

    NASA Technical Reports Server (NTRS)

    Doherty, Mark F.; Bjorklund, Carolyn M.; Peterson, William K.; Collin, Henry L.

    1993-01-01

    A processing algorithm to automatically detect a specific type of ion distribution (called the ion conic distribution) in data obtained from a space-based mass spectrometer has been devised. Automation of this task is necessary due to the sparseness of conic events within the very large databases typical of space plasma instruments. This paper reports on the algorithm used to perform this automated analysis, along with a description of the methods used to verify the algorithm and a summary of initial results on the characterization of the near-earth space plasma.

  16. Linear electric field time-of-flight ion mass spectrometer

    DOEpatents

    Funsten, Herbert O.; Feldman, William C.

    2008-06-10

    A linear electric field ion mass spectrometer having an evacuated enclosure with means for generating a linear electric field located in the evacuated enclosure and means for injecting a sample material into the linear electric field. A source of pulsed ionizing radiation injects ionizing radiation into the linear electric field to ionize atoms or molecules of the sample material, and timing means determine the time elapsed between ionization of atoms or molecules and arrival of an ion out of the ionized atoms or molecules at a predetermined position.

  17. Mass-spectrometric observation of ion ejection from clusters

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Dubov, D. Iu.; Gileva, V. P.

    1989-08-01

    Results of mass spectrometry measurements in clustered molecular beams of water and nitrogen oxide are reported. The clusters were formed under conditions of free expansion of N2O and superheated steam through a sonic nozzle. It is found that, for a mean cluster size of less than 100, the true cluster concentration in the beam is distorted by the evaporation of molecules from ionized clusters. The evaporation intensity depends to a large degree on the ionizing electron energy. For the cluster sizes investigated (100 or less), the observed density of the microcluster ions is found to be related to ion ejection from the clusters.

  18. Study of coal structure using secondary ion mass spectrometry

    SciTech Connect

    Tingey, G.L.; Lytle, J.M.; Baer, D.R.; Thomas, M.T.

    1980-12-01

    Secondary-ion Mass Spectrometry (SIMS) is examined as a tool for studying the chemical structure of coal. SIMS has potential for analysis of coal because of the following characteristics: sensitivity to chemical structure; high sensitivity to all masses; application to solids; excellent depth resolution; and reasonable spatial resolution. SIMS spectra of solid coals show differences with respect to coal rank, the spectra of high rank coal being similar to that of graphite, and the spectra of low rank coal being similar to that of wood. Some functional group analysis is also possible using SIMS. Low rank coals show a larger peak at 15 amu indicating more methyl groups than found in the higher rank coals. Fragments with two and three carbon atoms have also been examined; much larger fragments are undoubtedly present but were not evaluated in this study. Examination of these groups, which are expected to contain valuable information on coal structure, is planned for future work. It has been observed that mineral atoms present in the coal have large secondary ion yields which complicate the interpretation of the spectra. Studies on mineral-free coals and model compounds are therefore recommended to facilitate determination of organic coal structure. In addition, mass spectrometry with much greater mass resolution will aid in distinguishing between various ion species.

  19. A glow discharge ion source with fourier transform ion cyclotron resonance mass spectrometric detection.

    PubMed

    Barhick, C M; Eyler, J R

    1992-02-01

    A glow discharge (CD) ion source has been coupled to a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer using a four-element electrostatic lens to accelerate and focus ions generated external to the instrument's high magnetic field into its analyzer cell. Like other CD mass spectrometers, GD-FT-ICR can provide a quantitative measure of bulk analyte concentration with good precision and accuracy. Although detection limits currently attainable are several orders of magnitude higher than the commercially available magnetic sector-based instrument, CD-FT-ICR holds promise for ultrahigh resolving power elemental mass analysis. Several schemes are proposed to lower the detection limits of the technique while still providing high enough resolution to resolve isobaric interferences. PMID:24242880

  20. Hybrid quadrupole mass filter/quadrupole ion trap/time-of-flight-mass spectrometer for infrared multiple photon dissociation spectroscopy of mass-selected ions

    SciTech Connect

    Gulyuz, Kerim; Stedwell, Corey N.; Wang Da; Polfer, Nick C.

    2011-05-15

    We present a laboratory-constructed mass spectrometer optimized for recording infrared multiple photon dissociation (IRMPD) spectra of mass-selected ions using a benchtop tunable infrared optical parametric oscillator/amplifier (OPO/A). The instrument is equipped with two ionization sources, an electrospray ionization source, as well as an electron ionization source for troubleshooting. This hybrid mass spectrometer is composed of a quadrupole mass filter for mass selection, a reduced pressure ({approx}10{sup -5} Torr) quadrupole ion trap (QIT) for OPO irradiation, and a reflectron time-of-flight drift tube for detecting the remaining precursor and photofragment ions. A helium gas pulse is introduced into the QIT to temporarily increase the pressure and hence enhance the trapping efficiency of axially injected ions. After a brief pump-down delay, the compact ion cloud is subjected to the focused output from the continuous wave OPO. In a recent study, we implemented this setup in the study of protonated tryptophan, TrpH{sup +}, as well as collision-induced dissociation products of this protonated amino acid [W. K. Mino, Jr., K. Gulyuz, D. Wang, C. N. Stedwell, and N. C. Polfer, J. Phys. Chem. Lett. 2, 299 (2011)]. Here, we give a more detailed account on the figures of merit of such IRMPD experiments. The appreciable photodissociation yields in these measurements demonstrate that IRMPD spectroscopy of covalently bound ions can be routinely carried out using benchtop OPO setups.

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

    PubMed

    Zhou, Xiaoyu; Ouyang, Zheng

    2016-07-19

    Ion trajectory simulation is an important and useful tool in instrumentation development for mass spectrometry. Accurate simulation of the ion motion through the mass spectrometer with atmospheric pressure ionization source has been extremely challenging, due to the complexity in gas hydrodynamic flow field across a wide pressure range as well as the computational burden. In this study, we developed a method of generating the gas flow field for an entire mass spectrometer with an atmospheric pressure interface. In combination with the electric force, for the first time simulation of ion trajectories from an atmospheric pressure ion source to a mass analyzer in vacuum has been enabled. A stage-by-stage ion repopulation method has also been implemented for the simulation, which helped to avoid an intolerable computational burden for simulations at high pressure regions while it allowed statistically meaningful results obtained for the mass analyzer. It has been demonstrated to be suitable to identify a joint point for combining the high and low pressure fields solved individually. Experimental characterization has also been done to validate the new method for simulation. Good agreement was obtained between simulated and experimental results for ion transfer though an atmospheric pressure interface with a curtain gas. PMID:27340893

  2. Electron Flood Charge Compensation Device for Ion Trap Secondary Ion Mass Spectrometry

    SciTech Connect

    Appelhans, Anthony David; Ward, Michael Blair; Olson, John Eric

    2002-11-01

    During secondary ion mass spectrometry (SIMS) analyses of organophosphorous compounds adsorbed onto soils, the measured anion signals were lower than expected and it was hypothesized that the low signals could be due to sample charging. An electron flood gun was designed, constructed and used to investigate sample charging of these and other sample types. The flood gun was integrated into one end cap of an ion trap secondary ion mass spectrometer and the design maintained the geometry of the self-stabilizing extraction optics used in this instrument. The SIMION ion optics program was used to design the flood gun, and experimental results agreed with the predicted performance. Results showed the low anion signals from the soils were not due to sample charging. Other insulating and conducting samples were tested using both a ReO4- and a Cs+ primary ion beam. The proximity of the sample and electron source to the ion trap aperture resulted in generation of background ions in the ion trap via electron impact (EI) ionization during the period the electron gun was flooding the sample region. When using the electron gun with the ReO4- primary beam, the required electron current was low enough that the EI background was negligible; however, the high electron flood current required with the Cs+ beam produced background EI ions that degraded the quality of the mass spectra. The consequences of the EI produced cations will have to be evaluated on a sample-by-sample basis when using electron flood. It was shown that the electron flood gun could be intentionally operated to produce EI spectra in this instrument. This offers the opportunity to measure, nearly simultaneously, species evaporating from a sample, via EI, and species bound to the surface, via SIMS.

  3. Supercharging with Trivalent Metal Ions in Native Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Flick, Tawnya G.; Williams, Evan R.

    2012-11-01

    Addition of 1.0 mM LaCl3 to aqueous ammonium acetate solutions containing proteins in their folded native forms can result in a significant increase in the molecular ion charging obtained with electrospray ionization as a result of cation adduction. In combination with m-nitrobenzyl alcohol, molecular ion charge states that are greater than the number of basic sites in the protein can be produced from these native solutions, even for lysozyme, which is conformationally constrained by four intramolecular disulfide bonds. Circular dichroism spectroscopy indicates that the conformation of ubiquitin is not measurably affected with up to 1.0 M LaCl3, but ion mobility data indicate that the high charge states that are formed when 1.0 mM LaCl3 is present are more unfolded than the low charge states formed without this reagent. These and other results indicate that the increased charging is a result of La3+ preferentially adducting onto compact or more native-like conformers during ESI and the gas-phase ions subsequently unfolding as a result of increased Coulomb repulsion. Electron capture dissociation of these high charge-state ions formed from these native solutions results in comparable sequence coverage to that obtained for ions formed from denaturing solutions without supercharging reagents, making this method a potentially powerful tool for obtaining structural information in native mass spectrometry.

  4. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  5. Chemical noise reduction via mass spectrometry and ion/ion charge inversion: amino acids.

    PubMed

    Hassell, Kerry M; LeBlanc, Yves C; McLuckey, Scott A

    2011-05-01

    Charge inversion ion/ion reactions can provide a significant reduction in chemical noise associated with mass spectra derived from complex mixtures for species composed of both acidic and basic sites, provided the ions derived from the matrix largely undergo neutralization. Amino acids constitute an important class of amphoteric compounds that undergo relatively efficient charge inversion. Precipitated plasma constitutes a relatively complex biological matrix that yields detectable signals at essentially every mass-to-charge value over a wide range. This chemical noise can be dramatically reduced using multiply charged reagent ions that can invert the charge of species amenable to the transfer of multiple charges upon a single interaction and by detecting product ions of opposite polarity. The principle is illustrated here with amino acids present in precipitated plasma subjected to ionization in the positive mode, reaction with anions derived from negative nanoelectrospray ionization of poly (amido amine) dendrimer generation 3.5, and mass analysis in the negative ion mode. PMID:21456599

  6. DETERMINATION OF ION AND NEUTRAL LOSS COMPOSITIONS AND DECONVOLUTION OF PRODUCT ION MASS SPECTRA USING AN ORTHOGONAL ACCELERATION, TIME-OF-FLIGHT MASS SPECTROMETER AND AN ION CORRELATION PROGRAM

    EPA Science Inventory

    Exact masses of monoisotopic ions and the relative isotopic abundances (RIAs) of ions greater in mass by 1 and 2 Da than the monoisotopic ion are independent and complementary physical properties useful for istinguishing among ion compositions possible for a given nominal mass. U...

  7. Compact ExB mass separator for heavy ion beams

    SciTech Connect

    Wada, M.; Hashino, T.; Hirata, F.; Kasuya, T.; Sakamoto, Y.; Nishiura, M.

    2008-02-15

    A compact ExB mass separator that deflects beam by 30 deg. has been designed and built to prove its principle of operation. The main part of the separator is contained in a shielding box of 11 cm long, 9 cm wide, and 1.5 cm high. An electromagnet of 7 cm pole diameter produced variable magnetic field in the mass separation region instead of a couple of permanent magnets which is to be used in the final design. The experimental result agreed well with the theoretical prediction, and larger mass ions is bent with less magnetic field with the aid of the deflection electric field. The reduction in resolving power for mass separation due to the deflection electric field has been investigated experimentally.

  8. Developing liquid chromatography ion mobility mass spectometry techniques.

    PubMed

    Valentine, Stephen J; Liu, Xiaoyun; Plasencia, Manolo D; Hilderbrand, Amy E; Kurulugama, Ruwan T; Koeniger, Stormy L; Clemmer, David E

    2005-08-01

    When a packet of ions in a buffer gas is exposed to a weak electric field, the ions will separate according to differences in their mobilities through the gas. This separation forms the basis of the analytical method known as ion mobility spectroscopy and is highly efficient, in that it can be carried out in a very short time frame (micro- to milliseconds). Recently, efforts have been made to couple the approach with liquid-phase separations and mass spectrometry in order to create a high-throughput and high-coverage approach for analyzing complex mixtures. This article reviews recent work to develop this approach for proteomics analyses. The instrumentation is described briefly. Several multidimensional data sets obtained upon analyzing complex mixtures are shown in order to illustrate the approach as well as provide a view of the limitations and required future work. PMID:16097888

  9. Servo-amplifiers for ion current measurement in mass spectrometry

    USGS Publications Warehouse

    Stacey, J.S.; Russell, R.D.; Kollar, F.

    1965-01-01

    A servo-voltmeter can provide a useful alternative to the d.c. amplifier or vibrating reed electrometer for the accurate measurement of mass spectrometer ion currents, and has some advantages which recommend its use in certain applications. A generalized analysis based on servomechanism theory is presented as an aid for understanding the design criteria for this type of device. Two existing systems are described and their operation and performance are examined.

  10. Ion/molecule reactions performed in a miniature cylindrical ion trap mass spectrometer.

    PubMed

    Riter, Leah S; Meurer, Eduardo C; Handberg, Eric S; Laughlin, Brian C; Chen, Hao; Patterson, Garth E; Eberlin, Marcos N; Cooks, R Graham

    2003-09-01

    A recently constructed miniature mass spectrometer, based on a cylindrical ion trap (CIT) mass analyzer, is used to perform ion/molecule reactions in order to improve selectivity for in situ analysis of explosives and chemical warfare agent simulants. Six different reactions are explored, including several of the Eberlin reaction type (M. N. Eberlin and R. G. Cooks, Org. Mass Spectrom., 1993, 28, 679-687) as well as novel gas-phase Meerwein reactions. The reactions include (1) Eberlin transacetalization of the benzoyl, 2,2-dimethyloximinium, and 2,2-dimethylthiooximinium cations with 2,2-dimethyl-1,3-dioxolane to form 2-phenyl-1,3-dioxolanylium cations, 2,2-dimethylamine-1,3-dioxolanylium cations and the 2,2-dimethylamin-1,3-oxathiolanylium cations, respectively; (2) Eberlin reaction of the phosphonium ion CH3P(O)OCH3+, formed from the chemical warfare agent simulant dimethyl methylphosphonate (DMMP), with 1,4-dioxane to yield the 1,3,2-dioxaphospholanium ion, a new characteristic reaction for phosphate ester detection; (3) the novel Meerwein reaction of the ion CH3P(O)OCH3+ with propylene sulfide forming 1,3,2-oxathionylphospholanium ion; (4) the Meerwein reaction of the benzoyl cation with propylene oxide and propylene sulfide to form 4-methyl-2-phenyl-1,3-dioxolane and its thio analog, respectively; (5) ketalization of the benzoyl cation with ethylene glycol to form the 2-phenyl-1,3-dioxolanylium cation; (6) addition/NO2 elimination involving benzonitrile radical cation in reaction with nitrobenzene to form an arylated nitrile, a diagnostic reaction for explosives detection and (7) simple methanol addition to the C7H7+ ion, formed by NO2 loss from the molecular ion of p-nitrotoluene to form an intact adduct. Evidence is provided that these reactions occur to give the products described and their potential analytical utility is discussed. PMID:14529016

  11. 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. PMID:26819912

  12. 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

  13. SCAPS, a two-dimensional ion detector for mass spectrometer

    NASA Astrophysics Data System (ADS)

    Yurimoto, Hisayoshi

    2014-05-01

    Faraday Cup (FC) and electron multiplier (EM) are of the most popular ion detector for mass spectrometer. FC is used for high-count-rate ion measurements and EM can detect from single ion. However, FC is difficult to detect lower intensities less than kilo-cps, and EM loses ion counts higher than Mega-cps. Thus, FC and EM are used complementary each other, but they both belong to zero-dimensional detector. On the other hand, micro channel plate (MCP) is a popular ion signal amplifier with two-dimensional capability, but additional detection system must be attached to detect the amplified signals. Two-dimensional readout for the MCP signals, however, have not achieve the level of FC and EM systems. A stacked CMOS active pixel sensor (SCAPS) has been developed to detect two-dimensional ion variations for a spatial area using semiconductor technology [1-8]. The SCAPS is an integrated type multi-detector, which is different from EM and FC, and is composed of more than 500×500 pixels (micro-detectors) for imaging of cm-area with a pixel of less than 20 µm in square. The SCAPS can be detected from single ion to 100 kilo-count ions per one pixel. Thus, SCAPS can be accumulated up to several giga-count ions for total pixels, i.e. for total imaging area. The SCAPS has been applied to stigmatic ion optics of secondary ion mass spectrometer, as a detector of isotope microscope [9]. The isotope microscope has capabilities of quantitative isotope images of hundred-micrometer area on a sample with sub-micrometer resolution and permil precision, and of two-dimensional mass spectrum on cm-scale of mass dispersion plane of a sector magnet with ten-micrometer resolution. The performance has been applied to two-dimensional isotope spatial distribution for mainly hydrogen, carbon, nitrogen and oxygen of natural (extra-terrestrial and terrestrial) samples and samples simulated natural processes [e.g. 10-17]. References: [1] Matsumoto, K., et al. (1993) IEEE Trans. Electron Dev. 40

  14. In situ analysis of ion-induced polymer surface modification using secondary ion mass spectroscopy

    NASA Astrophysics Data System (ADS)

    Okuji, Shigeto; Kitazawa, Hideaki; Takeda, Yoshihiko

    2016-06-01

    We have investigated the surface modification process consisting of ion irradiation immediately followed by exposure to ambient gas for three types of polymers having the same main chain, sbnd Csbnd Csbnd , but different atoms bound to the main chain, using in situ secondary ion mass spectroscopy. The polymers' surface was irradiated with 30 keV Au ions at a total fluence for up to 1 × 1017 cm-2 and exposed to ambient gas in a ultra-high-vacuum chamber (1 × 10-6 Pa) for 30 min after the ion irradiation. Low density polyethylene mainly exhibited a hydrogen dissociation during the ion irradiation and a recombination with hydrogen atoms by the exposure, polytetrafluoroethylene mainly showed a main chain scission and no recombination during the exposure, and polyvinylidene difluoride lost hydrogen and fluorine atoms by the ion irradiation and partially recombined with hydrogen and fluorine atoms upon the exposure. The deposited energy density on the polymer surfaces reflects the dependence of the modification on the incident ion species, Au or Ga ions.

  15. 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.

  16. Identification of carbohydrate anomers using ion mobility-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hofmann, J.; Hahm, H. S.; Seeberger, P. H.; Pagel, K.

    2015-10-01

    Carbohydrates are ubiquitous biological polymers that are important in a broad range of biological processes. However, owing to their branched structures and the presence of stereogenic centres at each glycosidic linkage between monomers, carbohydrates are harder to characterize than are peptides and oligonucleotides. Methods such as nuclear magnetic resonance spectroscopy can be used to characterize glycosidic linkages, but this technique requires milligram amounts of material and cannot detect small amounts of coexisting isomers. Mass spectrometry, on the other hand, can provide information on carbohydrate composition and connectivity for even small amounts of sample, but it cannot be used to distinguish between stereoisomers. Here, we demonstrate that ion mobility-mass spectrometry--a method that separates molecules according to their mass, charge, size, and shape--can unambiguously identify carbohydrate linkage-isomers and stereoisomers. We analysed six synthetic carbohydrate isomers that differ in composition, connectivity, or configuration. Our data show that coexisting carbohydrate isomers can be identified, and relative concentrations of the minor isomer as low as 0.1 per cent can be detected. In addition, the analysis is rapid, and requires no derivatization and only small amounts of sample. These results indicate that ion mobility-mass spectrometry is an effective tool for the analysis of complex carbohydrates. This method could have an impact on the field of carbohydrate synthesis similar to that of the advent of high-performance liquid chromatography on the field of peptide assembly in the late 1970s.

  17. Final Report - Ion Production and Transport in Atmospheric Pressure Ion Source Mass Spectrometers

    SciTech Connect

    Farnsworth, Paul B.; Spencer, Ross L.

    2014-05-14

    This document is the final report on a project that focused in the general theme of atmospheric-pressure ion production and transport for mass spectrometry. Within that general theme there were two main projects: the fundamental study of the transport of elemental ions through the vacuum interface of an inductively coupled plasma mass spectrometer (ICPMS), and fundamental studies of the ionization mechanisms in ambient desorption/ionization (ADI) sources for molecular mass spectrometry. In both cases the goal was to generate fundamental understanding of key instrumental processes that would lead to the development of instruments that were more sensitive and more consistent in their performance. The emphasis on consistency derives from the need for instruments that have the same sensitivity, regardless of sample type. In the jargon of analytical chemistry, such instruments are said to be free from matrix effects. In the ICPMS work each stage of ion production and of ion transport from the atmospheric pressure to the high-vacuum mass analyzer was studied. Factors controlling ion transport efficiency and consistency were identified at each stage of pressure reduction. In the ADI work the interactions between an electrospray plume and a fluorescent sample on a surface were examined microscopically. A new mechanism for analyte ion production in desorption electrospray ionization (DESI) was proposed. Optical spectroscopy was used to track the production of reactive species in plasmas used as ADI sources. Experiments with mixed-gas plasmas demonstrated that the addition of a small amount of hydrogen to a helium ADI plasma could boost the sensitivity for some analytes by over an order of magnitude.

  18. Pulsed-gas glow discharge for ultrahigh mass resolution measurements with Fourier transform ion cyclotron resonance mass spectrometry

    SciTech Connect

    Watson, C.H.; Eyler, J.R.; Barshick, C.M.; Wronka, J.; Laukien, F.H.

    1996-02-01

    A new pulsed-gas glow discharge (GD) source has been developed for use with an external ion source Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. With pulsed argon gas introduction into the GD source, the gas load and pressure in the mass analyzer region were greatly reduced; this resulted in improved mass resolution. Mass resolution of greater than 145000 (fwhm) has been achieved for Cu{sup +} ions from a brass sample, the highest reported for any type of GD mass spectrometer. The pulsed-gas GD source promises analytical usefulness for ultrahigh resolution measurements in GD mass spectrometry. 16 refs., 3 figs.

  19. Dynamically Multiplexed Ion Mobility Time-of-Flight Mass Spectrometry

    PubMed Central

    Belov, Mikhail E.; Clowers, Brian H.; Prior, David C.; Danielson, William F.; Liyu, Andrei V.; Petritis, Brianne O.; Smith, Richard D.

    2010-01-01

    Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry (IMS-TOFMS) has been increasingly used in analysis of complex biological samples. A major challenge is to transform IMS-TOFMS to a high-sensitivity high-throughput platform for e.g. proteomics applications. In this work, we have developed and integrated three advanced technologies, including efficient ion accumulation in the ion funnel trap prior to IMS separation, multiplexing (MP) of ion packet introduction into the IMS drift tube and signal detection with an analog-to-digital converter (ADC), into the IMS-TOFMS system for the high-throughput analysis of highly complex proteolytic digests of e.g. blood plasma. To better address variable sample complexity, we have developed and rigorously evaluated a novel dynamic MP approach that ensures correlation of the analyzer performance with an ion source function, and provides the improved dynamic range and sensitivity throughout the experiment. The MP IMS-TOF MS instrument has been shown to reliably detect peptides at a concentration of 1 nM in the presence of highly complex matrix, as well as to provide a three orders of magnitude dynamic range and a mass measurement accuracy of better than 5 ppm. When matched against human blood plasma database, the detected IMS-TOF features were found to yield ~ 700 unique peptide identifications at a false discovery rate (FDR) of ~ 7.5 %. Accounting for IMS information gave rise to a projected FDR of ~ 4 %. Signal reproducibility was found to be greater than 80 %, while the variations in the number of unique peptide identifications were < 15 %. A single sample analysis was completed in 15 min that constitutes almost an order of magnitude improvement compared to a more conventional LC-MS approach. PMID:18582088

  20. Dynamically multiplexed ion mobility time-of-flight mass spectrometry.

    PubMed

    Belov, Mikhail E; Clowers, Brian H; Prior, David C; Danielson, William F; Liyu, Andrei V; Petritis, Brianne O; Smith, Richard D

    2008-08-01

    Ion mobility spectrometry-time-of-flight mass spectrometry (IMS-TOFMS) has been increasingly used in analysis of complex biological samples. A major challenge is to transform IMS-TOFMS to a high-sensitivity, high-throughput platform, for example, for proteomics applications. In this work, we have developed and integrated three advanced technologies, including efficient ion accumulation in an ion funnel trap prior to IMS separation, multiplexing (MP) of ion packet introduction into the IMS drift tube, and signal detection with an analog-to-digital converter, into the IMS-TOFMS system for the high-throughput analysis of highly complex proteolytic digests of, for example, blood plasma. To better address variable sample complexity, we have developed and rigorously evaluated a novel dynamic MP approach that ensures correlation of the analyzer performance with an ion source function and provides the improved dynamic range and sensitivity throughout the experiment. The MP IMS-TOFMS instrument has been shown to reliably detect peptides at a concentration of 1 nM in the presence of a highly complex matrix, as well as to provide a 3 orders of magnitude dynamic range and a mass measurement accuracy of better than 5 ppm. When matched against human blood plasma database, the detected IMS-TOF features were found to yield approximately 700 unique peptide identifications at a false discovery rate (FDR) of approximately 7.5%. Accounting for IMS information gave rise to a projected FDR of approximately 4%. Signal reproducibility was found to be greater than 80%, while the variations in the number of unique peptide identifications were <15%. A single sample analysis was completed in 15 min that constitutes almost 1 order of magnitude improvement compared to a more conventional LC-MS approach. PMID:18582088

  1. Dynamically Multiplexed Ion Mobility Time-of-Flight Mass Spectrometry

    SciTech Connect

    Belov, Mikhail E.; Clowers, Brian H.; Prior, David C.; Danielson, William F.; Liyu, Andrei V.; Petritis, Brianne O.; Smith, Richard D.

    2008-08-01

    Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry (IMS-TOFMS) has been increasingly used in analysis of complex biological samples. A major challenge is to transform IMS-TOFMS to a high-sensitivity high-throughput platform for e.g. proteomics applications. In this work, we have developed and integrated three advanced technologies, enabling (1) efficient ion accumulation in the ion funnel trap prior to IMS separation, (2) multiplexing (MP) of ion packet introduction into the IMS drift tube and (3) signal detection with an analog-to-digital converter (ADC), into the IMS-TOFMS system for the high-throughput analysis of highly complex proteolytic digests of e.g. blood plasma. To better address variable sample complexity, we have additionally developed and rigorously evaluated a new dynamic MP approach that ensures correlation of the analyzer performance with an ion source function, and provides the improved dynamic range and sensitivity. The MP IMS-TOF MS instrument has been shown to reliably detect peptides at a concentration of 1 nM in a highly complex matrix, as well as to provide a four orders of magnitude dynamic range and a mass measurement accuracy of better than 5 ppm. When matched against human blood plasma database, the detected IMS-TOF features yielded ~ 700 unique peptide identifications at a false discovery rate (FDR) of ~ 7.5 %. Accounting for IMS information gave rise to a projected FDR of ~ 4 %. Signal reproducibility was found to be greater than 80 %, while the variations in the number of unique peptide identifications were < 15 %. A single sample analysis was completed in 15 min, corresponding to approximately an order of magnitude improvement compared to a more conventional LC-MS approach.

  2. Infrared and Mass Analyzed Ion Kinetic Energy Spectroscopy of Cluster Ions

    NASA Astrophysics Data System (ADS)

    Feinberg, Thomas Neal

    A new method for obtaining mass analyzed kinetic energy spectroscopy for the study of cluster ions was tested. The experiments utilized an MS/MS instrument (Quadrupole/Electric Sector Analyzer) coupled to a cluster beam source. The ion source consisted of a molecular beam excited by high energy electron impact. Experiments were conducted using argon and argon/ethene gas mixtures in the ion source. Kinetic energy spectra of collision induced dissociation products and carbon dioxide laser photodissociation products were analyzed. The results for argon dimers showed a laser polarization effect on the measurement of the kinetic energy of the fragment argon ions in the infrared photodissociation event. When ionization occurred within the supersonic expansion zone, the polarization effects were no longer observed. Ethene gas in the ion source produced a variety of ions; some of these showed photodissociation efficiencies within the region of the monomer nu_7 vibrational mode. The spectroscopy and collision induced dissociation data are consistent with a structure consisting of a central core ion surrounded by one or more ethene molecules.

  3. Precision mass measurements at TITAN with radioactive ions

    NASA Astrophysics Data System (ADS)

    Kwiatkowski, A. A.; Macdonald, T. D.; Andreoiu, C.; Bale, J. C.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Ettenauer, S.; Gallant, A. T.; Grossheim, A.; Lennarz, A.; Mané, E.; Pearson, M. R.; Schultz, B. E.; Simon, M. C.; Simon, V. V.; Dilling, J.

    2013-12-01

    Measurements of the atomic mass further our understanding in many disciplines from metrology to physics beyond the standard model. The accuracy and precision of Penning trap mass spectrometry have been well demonstrated at TITAN, including measurements of neutron-rich calcium and potassium isotopes to investigate three-body forces in nuclear structure and within the island of inversion to study the mechanism of shell quenching and deformation. By charge breeding ions, TITAN has enhanced the precision of the measurement technique. The precision achieved in the measurement of the superallowed β-emitter 74Rb in the 8+ charge state rivaled earlier measurements with singly charged ions in a fraction of the time. By breeding 78Rb to the same charge state, the ground state could be easily distinguished from the isomer. Further developments led to threshold charge breeding, which permitted capturing and measuring isobarically and elementally pure ion samples in the Penning trap. This was demonstrated via the Q-value determination of 71Ge. An overview of the TITAN facility and recent results are presented herein.

  4. Development of a quadrupole ion trap mass spectrometer

    NASA Astrophysics Data System (ADS)

    Hebert, Joseph Ellis

    Because of its potential to be made portable the quadrupole ion trap (QPIT) is a prime candidate for specialized applications such as atmospheric studies, other field measurements, or measurements anywhere a laboratory instrument would be prohibitively inconvenient. To utilize the QPIT in such ways it is necessary to design and construct custom built instruments. A QPIT mass spectrometer was constructed as the foundation for such future development. Two ionization schemes were employed. Direct electron bombardment was used for in situ ion production, and UV photoionization was used to produce ions external to the trap. Calibration measurements determined that the system performed as theory dictated. It was also demonstrated that the system was capable of sampling the atmosphere and detecting the presence of an atmospheric contaminant. Finally, DC bias foils were invented as a novel approach to mass isolation in the trap. The use of DC bias foils was demonstrated to be an exceptionally easy and inexpensive method of controlling the contents of the QPIT.

  5. Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Karr, Dane; Pearson, Richard; Valero, Gustavo; Wong, Carla

    1995-01-01

    Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

  6. Trace level perchlorate analysis by ion chromatography-mass spectrometry.

    PubMed

    Mathew, Johnson; Gandhi, Jay; Hedrick, Joe

    2005-08-26

    Perchlorate is commonly used as an oxidant in solid fuel propellant for rockets and missiles. Recently perchlorate contamination was found in many aquifers associated with Colorado River and other sites. Perchlorate was also found at elevated level in crops that use contaminated water for irrigation. Ion chromatography with conductivity detection could be used to measure perchlorate levels in drinking and wastewaters as per United States Environmental Protection Agency method 314, but at lower levels and with complexity of the matrix there could be false positive and/or false negative. This study was done to demonstrate the detection of perchlorate with lower detection limit with high ionic matrix by ion chromatography-mass spectrometry. PMID:16106848

  7. In situ secondary ion mass spectrometry analysis. 1992 Summary report

    SciTech Connect

    Groenewold, G.S.; Applehans, A.D.; Ingram, J.C.; Delmore, J.E.; Dahl, D.A.

    1993-01-01

    The direct detection of tributyl phosphate (TBP) on rocks using molecular beam surface analysis [MBSA or in situ secondary ion mass spectrometry (SIMS)] is demonstrated. Quantities as low as 250 ng were detected on basalt and sandstone with little or no sample preparation. Detection of TBP on soil has proven to be more problematic and requires further study. Ethylenediaminetetraacetic acid (EDTA) is more difficult to detect because it is very reactive with surfaces of interest. Nevertheless, it is possible to detect EDTA if the acidity of the surface is controlled. The detection of EDTA-metal complexes is currently an open question, but evidence is presented for the detection of ions arising from a EDTA-lead complex. Carboxylic acids (i.e., citric, ascorbic, malic, succinic, malonic, and oxalic) give characteristic SIM spectra, but their detection on sample surfaces awaits evaluation.

  8. Improved Isobaric Tandem Mass Tag Quantification by Ion Mobility-Mass Spectrometry

    PubMed Central

    Li, Lingjun

    2014-01-01

    Isobaric tandem mass tags are an attractive alternative to mass difference tags and label free approaches for quantitative proteomics due to the high degree of multiplexing that can be performed with their implementation. A drawback of tandem mass tags are that the co-isolation and co-fragmentation of labeled peptide precursors can result in chimeric MS/MS spectra that can underestimate the fold-change expression of each peptide. Two methods (QuantMode and MS3) have addressed this concern for ion trap and orbitrap instruments, but there is still a need to solve this problem for quadrupole time-of-flight (Q-TOF) instruments. Ion mobility (IM) separations coupled to Q-TOF instruments have the potential to mitigate MS/MS spectra chimeracy since IM-MS has the ability to separate ions based on charge, m/z, and collision cross section (CCS). This work presents results that showcase the power of IM-MS to improve tandem mass tag peptide quantitation accuracy by resolving co-isolated differently charged and same charged peptides prior to MS/MS fragmentation. PMID:24677527

  9. Relative sensitivity factors for submicron secondary ion mass spectrometry with gallium primary ion beam

    NASA Astrophysics Data System (ADS)

    Satosh, Hitomi; Owari, Masanori; Nihei, Yoshimasa

    1993-08-01

    Relative sensitivity factors (RSFs) of thirteen elements in the oxide glass matrix in secondary ion mass spectrometry (SIMS) excited by a gallium focused ion beam were determined. RSFs were obtained by analyzing powder particles of standard glass samples. Whole volumes of each particles were analyzed in the 'shave-off' mode in order to avoid topographic effects. Reproducibility of RSFs was good, and sample-to-sample scattering of values was relatively small. Dependence of RSFs on the first ionization potential was shown to be reasonable. In order to with the data obtained through the bulk chemical analysis.

  10. Ion trap mass spectrometric detection of laser desorbed ions from derivatized fused silica fibers

    SciTech Connect

    Garrett, A.W.; Earl, W.L.; Cisper, M.E.; Nogar, N.S.; Hemberger, P.H.

    1994-12-31

    Solid-phase microextraction of analytes from complex matrices using fused silica fibers has many advantages over traditional chemical sample preparation technique. Microextraction requires small sample sizes little sample preparation (providing rapid sample turnaround time), and greatly reduces the amount of chemical waste generated in sample preparation. These advantages make fused silica fibers attractive for direct sampling and detection experiments using laser desorption ion trap mass spectrometry (LITMS). The drawback is the very small area ({approximately}1 mm{sup 2}) exposed to laser irradiation, which limits the amount of material desorbed into the ion trap.

  11. Separation of steroid isomers by ion mobility mass spectrometry.

    PubMed

    Ahonen, Linda; Fasciotti, Maíra; Gennäs, Gustav Boije Af; Kotiaho, Tapio; Daroda, Romeu J; Eberlin, Marcos; Kostiainen, Risto

    2013-10-01

    Ion mobility mass spectrometry performed in a compact traveling wave cell (TWIM-MS) is shown to provide a reliable, fast and repeatable method to separate derivatized steroid isomers. Three steroid isomer pairs were analyzed in their native form and as their p-toluenesulfonyl isocyanate derivatives. The native steroids were separated from each other, but no separation could be attained for the isomers. The derivatized steroid isomers were, however, properly separated by TWIM-MS with peak-to-peak resolutions close to or as high as baseline resolution (Rp-p=0.77-1.08). PMID:23992881

  12. Continuous time-of-flight ion mass spectrometer

    DOEpatents

    Funsten, Herbert O.; Feldman, William C.

    2004-10-19

    A continuous time-of-flight mass spectrometer having an evacuated enclosure with means for generating an electric field located in the evacuated enclosure and means for injecting a sample material into the electric field. A source of continuous ionizing radiation injects ionizing radiation into the electric field to ionize atoms or molecules of the sample material, and timing means determine the time elapsed between arrival of a secondary electron out of said ionized atoms or molecules at a first predetermined location and arrival of a sample ion out of said ionized atoms or molecules at a second predetermined location.

  13. Ion Mobility Separation of Isomeric Carbohydrate Precursor Ions and Acquisition of their Independent Tandem Mass Spectra

    PubMed Central

    Zhu, Maolei; Bendiak, Brad; Clowers, Brian; Hill, Herbert H.

    2010-01-01

    The rapid separation of isomeric precursor ions of oligosaccharides prior to their analysis by MSn was demonstrated using an ambient pressure ion mobility spectrometer (IMS) interfaced with a quadrupole ion trap. Separations were not limited to specific types of isomers; representative isomers differing solely in the stereochemistry of sugars, in their anomeric configurations, and in their overall branching patterns and linkage positions could be resolved in the millisecond time frame. Physical separation of precursor ions permitted independent mass spectra of individual oligosaccharide isomers to be acquired to at least MS3, the number of stages of dissociation limited only practically by the abundance of specific product ions. IMS-MSn analysis was particularly valuable in the evaluation of isomeric oligosaccharides that yielded identical sets of product ions in MS/MS experiments, revealing pairs of isomers that would otherwise not be known to be present in a mixture if evaluated solely by MS dissociation methods alone. A practical example of IMS-MSn analysis of a set of isomers included within a single HPLC fraction of oligosaccharides released from bovine submaxillary mucin is described. PMID:19562326

  14. Ion Trap with Narrow Aperture Detection Electrodes for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nagornov, Konstantin O.; Kozhinov, Anton N.; Tsybin, Oleg Y.; Tsybin, Yury O.

    2015-05-01

    The current paradigm in ion trap (cell) design for Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the ion detection with wide aperture detection electrodes. Specifically, excitation and detection electrodes are typically 90° wide and positioned radially at a similar distance from the ICR cell axis. Here, we demonstrate that ion detection with narrow aperture detection electrodes (NADEL) positioned radially inward of the cell's axis is feasible and advantageous for FT-ICR MS. We describe design details and performance characteristics of a 10 T FT-ICR MS equipped with a NADEL ICR cell having a pair of narrow aperture (flat) detection electrodes and a pair of standard 90° excitation electrodes. Despite a smaller surface area of the detection electrodes, the sensitivity of the NADEL ICR cell is not reduced attributable to improved excite field distribution, reduced capacitance of the detection electrodes, and their closer positioning to the orbits of excited ions. The performance characteristics of the NADEL ICR cell are comparable with the state-of-the-art FT-ICR MS implementations for small molecule, peptide, protein, and petroleomics analyses. In addition, the NADEL ICR cell's design improves the flexibility of ICR cells and facilitates implementation of advanced capabilities (e.g., quadrupolar ion detection for improved mainstream applications). It also creates an intriguing opportunity for addressing the major bottleneck in FTMS—increasing its throughput via simultaneous acquisition of multiple transients or via generation of periodic non-sinusoidal transient signals.

  15. Imaging ion and molecular transport at subcellular resolution by secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chandra, Subhash; Morrison, George H.

    1995-05-01

    The transport of K+, Na+, and Ca2+ were imaged in individual cells with a Cameca IMS-3f ion microscope. Strict cryogenic frozen freeze-dry sample preparations were employed. Ion redistribution artifacts in conventional chemical preparations are discussed. Cryogenically prepared freeze-fractured freeze-dried cultured cells allowed the three-dimensional ion microscopic imaging of elements. As smaller structures in calcium images can be resolved with the 0.5 [mu]m spatial resolution, correlative techniques are needed to confirm their identity. The potentials of reflected light microscopy, scanning electron microscopy and laser scanning confocal microscopy are discussed for microfeature recognition in freeze-fractured freeze-dried cells. The feasibility of using frozen freeze-dried cells for imaging molecular transport at subcellular resolution was tested. Ion microscopy successfully imaged the transport of the isotopically tagged (13C, 15N) amino acid, -arginine. The labeled amino acid was imaged at mass 28 with a Cs+ primary ion beam as the 28(13C15N)- species. After a 4 h exposure of LLC-PK1 kidney cells to 4 mM labeled arginine, the amino acid was localized throughout the cell with a preferential incorporation into the nucleus and nucleolus. An example is also shown of the ion microscopic imaging of sodium borocaptate, an experimental therapeutic drug for brain tumors, in cryogenically prepared frozen freeze-dried Swiss 3T3 cells.

  16. Light ion mass spectrometer for space-plasma investigations

    NASA Technical Reports Server (NTRS)

    Reasoner, D. L.; Chappell, C. R.; Fields, S. A.; Lewter, W. J.

    1982-01-01

    Direct satellite measurements and ground-based techniques have given a comprehensive view of the density distribution of the cold plasma population in the earth's magnetosphere. There were, however, no direct measurements of the low-energy plasma mass composition, temperature, density, pitch-angle distribution, or plasma flow velocity. A description is presented of the evolution and development of an instrument, the Light Ion Mass Spectrometer (LIMS), designed to make these low-energy plasma measurements. The instrument was developed for flight on the spacecraft SCA-THA, a satellite to study satellite charging at high altitudes. This satellite, whose primary mission was to study spacecraft-plasma interactions and electrostatic charging, was launched into a near-geosynchronous orbit. The design requirements regarding the instrument are discussed, and attention is given to the calibration procedures, the flight configuration, and some examples of flight data.

  17. Loss of atomic oxygen in mass spectrometer ion sources.

    NASA Technical Reports Server (NTRS)

    Lake, L. R.; Nier, A. O.

    1973-01-01

    A gas beam consisting of a mixture of atomic and molecular oxygen has been directed at the ion source of a mass spectrometer like those used in sounding rockets for determining the neutral composition of the lower thermosphere. The loss of atomic oxygen on mass spectrometer surfaces was evaluated by flagging the beam in several ways and comparing the experimental results with predicted values. The results obtained suggest that in rocket flights using similar instruments the atomic oxygen densities computed assuming no-loss conditions may be low by a factor of 2.5. Studies made using a beam containing tracer O-18 indicate that carbon dioxide observed when atomic oxygen enters the source is formed in a reaction involving atomic oxygen from the beam and carbon monoxide from the surfaces bombarded.

  18. Ion and electron bombardment-related ion emission during the analysis of diamond using secondary ion mass spectrometry

    SciTech Connect

    Guzman de la Mata, Berta; Dowsett, Mark G.

    2007-02-01

    In recent years, the ability to grow single crystal layers of both doped and pure diamonds has improved, and devices for applications in high power electronics and microelectronics are being developed, most of them based on boron doped diamond. In this work, convoluted angular and energy spectra (so-called secondary ion mass spectrometry energy spectra) have been measured for {sup 11}B{sup +}, {sup 12}C{sup +}, {sup 16}O{sup +}, CO{sup +} and CO{sub 2}{sup +} ions ejected from a single crystal boron doped diamond layer under ultralow energy oxygen and electron beam bombardment. A low energy tail was observed in the {sup 12}C{sup +}, CO{sup +}, and CO{sub 2}{sup +} signals, corresponding to ions produced in the gas phase. Changing the bombardment conditions, we have identified interaction with the electron beam as the main ionization mechanism. In the case of {sup 12}C{sup +} it appears that the gas phase ions are produced by electron stimulated desorption and postionization of surface species created by the oxygen beam. We have detected high signals for CO{sup +} and CO{sub 2}{sup +} ionized in the gas phase, which supports a mechanism previously suggested to explain the anomalously fast diamond erosion under oxygen ion beam bombardment. We also observe that some species appearing in the mass spectrum are produced by electron stimulated desorption and this needs to be remembered when analyzing these on insulating diamond with charge compensation.

  19. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

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

  20. Non-mass-analyzed ion implantation from a solid phosphorus source

    NASA Technical Reports Server (NTRS)

    Spitzer, M. B.; Bunker, S. N.

    1982-01-01

    A phosphorus ion beam, extracted from a Freeman ion source charged with elemental phosphorus, has been investigated for use in solar cell fabrication. Mass spectroscopy of the beam indicates the absence of both minority-carrier lifetime degrading impurities and hydrogen. The ion beam, without mass analysis, was used for ion implantation of solar cells, and performance for all cells was found to be equivalent to mass-analyzed controls.

  1. Interfacing an aspiration ion mobility spectrometer to a triple quadrupole mass spectrometer

    SciTech Connect

    Adamov, Alexey; Viidanoja, Jyrki; Kaerpaenoja, Esko; Paakkanen, Heikki; Ketola, Raimo A.; Kostiainen, Risto; Sysoev, Alexey; Kotiaho, Tapio

    2007-04-15

    This article presents the combination of an aspiration-type ion mobility spectrometer with a mass spectrometer. The interface between the aspiration ion mobility spectrometer and the mass spectrometer was designed to allow for quick mounting of the aspiration ion mobility spectrometer onto a Sciex API-300 triple quadrupole mass spectrometer. The developed instrumentation is used for gathering fundamental information on aspiration ion mobility spectrometry. Performance of the instrument is demonstrated using 2,6-di-tert-butyl pyridine and dimethyl methylphosphonate.

  2. Incoherent scatter radar measurement of the average ion mass and temperature of a nighttime sporadic layer

    SciTech Connect

    Tepley, C.A.; Mathews, J.D.

    1985-04-01

    We report the results of incoherent scatter radar, total power, and ion line observations of a nighttime sporadic layer centered at 92-km altitude. The height variation of the absolute widths of the ion line yields a layer temperature of 210/sup 0/ +- 5 /sup 0/K and a mean ion mass of 50 +- 10 amu. This ion mass, when compared with average meteor composition, indicates that the layer is composed totally of metallic ions.

  3. Nanowire dopant measurement using secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chia, A. C. E.; Dhindsa, N.; Boulanger, J. P.; Wood, B. A.; Saini, S. S.; LaPierre, R. R.

    2015-09-01

    A method is presented to improve the quantitative determination of dopant concentration in semiconductor nanowire (NW) arrays using secondary ion mass spectrometry (SIMS). SIMS measurements were used to determine Be dopant concentrations in a Be-doped GaAs thin film and NW arrays of various pitches that were dry-etched from the same film. A comparison of these measurements revealed a factor of 3 to 12 difference, depending on the NW array pitch, between the secondary Be ion yields of the film and the NW arrays, despite being identically doped. This was due to matrix effects and ion beam mixing of Be from the NWs into the surrounding benzocyclobutene that was used to fill the space between the NWs. This indicates the need for etched NWs to be used as doping standards instead of 2D films when evaluating NWs of unknown doping by SIMS. Using the etched NWs as doping standards, NW arrays of various pitches grown by the vapour-liquid-solid mechanism were characterized by SIMS to yield valuable insights into doping mechanisms.

  4. Nanowire dopant measurement using secondary ion mass spectrometry

    SciTech Connect

    Chia, A. C. E.; Boulanger, J. P.; Wood, B. A.; LaPierre, R. R.; Dhindsa, N.; Saini, S. S.

    2015-09-21

    A method is presented to improve the quantitative determination of dopant concentration in semiconductor nanowire (NW) arrays using secondary ion mass spectrometry (SIMS). SIMS measurements were used to determine Be dopant concentrations in a Be-doped GaAs thin film and NW arrays of various pitches that were dry-etched from the same film. A comparison of these measurements revealed a factor of 3 to 12 difference, depending on the NW array pitch, between the secondary Be ion yields of the film and the NW arrays, despite being identically doped. This was due to matrix effects and ion beam mixing of Be from the NWs into the surrounding benzocyclobutene that was used to fill the space between the NWs. This indicates the need for etched NWs to be used as doping standards instead of 2D films when evaluating NWs of unknown doping by SIMS. Using the etched NWs as doping standards, NW arrays of various pitches grown by the vapour-liquid-solid mechanism were characterized by SIMS to yield valuable insights into doping mechanisms.

  5. Design and performance of an instrument for electron impact tandem mass spectrometry and action spectroscopy of mass/charge selected macromolecular ions stored in RF ion trap*

    NASA Astrophysics Data System (ADS)

    Ranković, Milos Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

    2016-06-01

    A new apparatus was designed, coupling an electron gun with a linear quadrupole ion trap mass spectrometer, to perform m/ z (mass over charge) selected ion activation by electron impact for tandem mass spectrometry and action spectroscopy. We present in detail electron tracing simulations of a 300 eV electron beam inside the ion trap, design of the mechanical parts, electron optics and electronic circuits used in the experiment. We also report examples of electron impact activation tandem mass spectra for Ubiquitin protein, Substance P and Melittin peptides, at incident electron energies in the range from 280 eV to 300 eV.

  6. Electrospray Ionization Ion Mobility Mass Spectrometry of Human Brain Gangliosides.

    PubMed

    Sarbu, Mirela; Robu, Adrian C; Ghiulai, Roxana M; Vukelić, Željka; Clemmer, David E; Zamfir, Alina D

    2016-05-17

    The progress of ion mobility spectrometry (IMS), together with its association to mass spectrometry (MS), opened new directions for the identification of various metabolites in complex biological matrices. However, glycolipidomics of the human brain by IMS MS represents an area untouched up to now, because of the difficulties encountered in brain sampling, analyte extraction, and IMS MS method optimization. In this study, IMS MS was introduced in human brain ganglioside (GG) research. The efficiency of the method in clinical glycolipidomics was demonstrated on a highly complex mixture extracted from a normal fetal frontal lobe (FL37). Using this approach, a remarkably rich molecular ion pattern was discovered, which proved the presence of a large number of glycoforms and an unpredicted diversity of the ceramide chains. Moreover, the results showed for the first time the occurrence of GGs in the human brain with a much higher degree of sialylation than previously reported. Using IMS MS, the entire series starting from mono- up to octasialylated GGs was detected in FL37. These findings substantiate early clinical reports on the direct correlation between GG sialylation degree and brain developmental stage. Using IMS CID MS/MS, applied here for the first time to gangliosides, a novel, tetrasialylated O-GalNAc modified species with a potential biomarker role in brain development was structurally characterized. Under variable collision energy, a high number of sequence ions was generated for the investigated GalNAc-GQ1(d18:1/18:0) species. Several fragment ions documented the presence of the tetrasialo element attached to the inner Gal, indicating that GalNAc-GQ1(d18:1/18:0) belongs to the d series. PMID:27088833

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

    PubMed

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

    2016-06-01

    The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration. PMID:26861497

  8. Low-mass ions produced from peptides by high-energy collision-induced dissociation in tandem mass spectrometry.

    PubMed

    Falick, A M; Hines, W M; Medzihradszky, K F; Baldwin, M A; Gibson, B W

    1993-11-01

    High-energy collision-induced dissociation (CID) mass spectrometry provides a rapid and sensitive means for determining the primary sequence of peptides. The low-mass region (below mass 300) of a large number of tandem CID spectra of peptides has been analyzed. This mass region contains several types of informative fragment ions, including dipeptide ions, immonium ions, and other related ions. Useful low-mass ions are also present in negative-ion CID spectra. Immonium ions (general structure [H2N=CH-R](+), where R is the amino acid side chain) and related ions characteristic of specific amino acid residues give information as to the presence or absence of these residues in the peptide being analyzed. Tables of observed immonium and reiated ions for the 20 standard amino acids and for a number of modified amino acids are presented. A database consisting of 228 high-energy CID spectra of peptides has been established, and the frequency of occurrence of various ions indicative of specific ammo acid residues has been determined. Two model computer-aided schemes for analysis of the ammo-acid content of unknown peptides have been developed and tested against the database. PMID:24227532

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

    SciTech Connect

    Lentz, Nicholas B.

    2007-01-01

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

  10. Laser-induced fluorescence of Ba+ ions trapped and mass-selected in a Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Li, G Z; Vining, B A; Guan, S; Marshall, A G

    1996-01-01

    We present the design and preliminary results from a Fourier transform ion cyclotron resonance (ICR) mass spectrometer developed for the direct detection of UV/visible laser-induced fluorescence of trapped, mass-selected, gas-phase ions. A 3 T superconducting magnet and an open-ended multi-section cylindrical Penning trap capture and confine ions created by electron impact or laser desorption. Azimuthal quadrupolar excitation in the presence of ion/neutral collisions cools, axializes and mass selects ions as they fill the trap. A pulsed dye laser pumped by an Nd:YAG laser provides electronic energy excitation. A Brewster window and baffles on each side of the vacuum chamber reduce the scattered light from the excitation laser. Laser-induced fluorescence is collected from mirrors and lenses and directed through a quartz window and fiber-optic bundle to a photomultiplier. The ICR and optical events are controlled by a modular ICR data station and GPIB and RS-232 interfaces. An excitation spectrum is demonstrated for atomic Ba+ ions, and should extend to laser-induced fluorescence of virtually any stable positive or negative gas-phase ions of arbitrary molecular weight: molecular or quasimolecular ions, fragment ions, adduct ions, and ions formed from ion/molecule reactions. PMID:8953788

  11. High latitude minor ion enhancements: A clue for studies of magnetosphere-atmosphere coupling. [using OGO 6 ion mass spectrometer

    NASA Technical Reports Server (NTRS)

    Taylor, H. A., Jr.

    1973-01-01

    Unexpectedly abrupt and pronounced distributions of the thermal molecular ions NO(+), O2(+) and N2(+) were observed at mid and high latitudes by the OGO-6 ion mass spectrometer. These minor ions may reach concentration levels exceeding 1000 ions/cu cm at altitudes as great as 1000 km, suggestive of scale heights well in excess of those inferred from low and mid-latitude measurements, under relatively undisturbed conditions. The high latitude ion enhancements were observed to be narrowly defined in time and space, with molecular ion concentrations changing by as much as an order of magnitude between successive orbits.

  12. CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry.

    PubMed

    Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J; Winograd, Nicholas

    2016-09-01

    The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure. Graphical Abstract ᅟ. PMID:27324648

  13. CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J.; Winograd, Nicholas

    2016-06-01

    The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure.

  14. CO2 Cluster Ion Beam, an Alternative Projectile for Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tian, Hua; Maciążek, Dawid; Postawa, Zbigniew; Garrison, Barbara J.; Winograd, Nicholas

    2016-09-01

    The emergence of argon-based gas cluster ion beams for SIMS experiments opens new possibilities for molecular depth profiling and 3D chemical imaging. These beams generally leave less surface chemical damage and yield mass spectra with reduced fragmentation compared with smaller cluster projectiles. For nanoscale bioimaging applications, however, limited sensitivity due to low ionization probability and technical challenges of beam focusing remain problematic. The use of gas cluster ion beams based upon systems other than argon offer an opportunity to resolve these difficulties. Here we report on the prospects of employing CO2 as a simple alternative to argon. Ionization efficiency, chemical damage, sputter rate, and beam focus are investigated on model compounds using a series of CO2 and Ar cluster projectiles (cluster size 1000-5000) with the same mass. The results show that the two projectiles are very similar in each of these aspects. Computer simulations comparing the impact of Ar2000 and (CO2)2000 on an organic target also confirm that the CO2 molecules in the cluster projectile remain intact, acting as a single particle of m/z 44. The imaging resolution employing CO2 cluster projectiles is improved by more than a factor of two. The advantage of CO2 versus Ar is also related to the increased stability which, in addition, facilitates the operation of the gas cluster ion beams (GCIB) system at lower backing pressure.

  15. Why is sideband mass spectrometry possible with ions in a Penning trap?

    PubMed

    Gabrielse, G

    2009-05-01

    Many masses, particularly the masses of unstable nuclei, are measured with ions in Penning traps by determining the frequency of a driving force that most efficiently couples two of the three motions of trapped ions. A missing explanation of why such sideband mass spectroscopy works, contrary to simple estimates, begins with the established Brown-Gabrielse invariance theorem. PMID:19518777

  16. Why Is Sideband Mass Spectrometry Possible with Ions in a Penning Trap?

    SciTech Connect

    Gabrielse, G.

    2009-05-01

    Many masses, particularly the masses of unstable nuclei, are measured with ions in Penning traps by determining the frequency of a driving force that most efficiently couples two of the three motions of trapped ions. A missing explanation of why such sideband mass spectroscopy works, contrary to simple estimates, begins with the established Brown-Gabrielse invariance theorem.

  17. Ion Mass Spectrometer for Sporadic-E Rocket Experiments

    NASA Technical Reports Server (NTRS)

    Heelis, R. A.; Earle, G. D.; Pfaff, Robert

    2000-01-01

    NASA grant NAG5-5086 provided funding for the William B. Hanson Center for Space Sciences at the University of Texas at Dallas (UTD) to design, fabricate, calibrate, and ultimately fly two ion mass spectrometer instruments on a pair of sounding rocket payloads. Drs. R.A. Heelis and G.D. Earle from UTD were co-investigators on the project. The principal investigator for both rocket experiments was Dr. Robert Pfaff of the Goddard Space Flight Center. The overall project title was "Rocket/Radar Investigation of Lower Ionospheric Electrodynamics Associated with Intense Mid-Latitude Sporadic-E Layers". This report describes the overall objectives of the project, summarizes the instrument design and flight experiment details, and presents representative data obtained during the flights.

  18. Secondary-ion mass spectrometry of genetically encoded targets.

    PubMed

    Vreja, Ingrid C; Kabatas, Selda; Saka, Sinem K; Kröhnert, Katharina; Höschen, Carmen; Opazo, Felipe; Diederichsen, Ulf; Rizzoli, Silvio O

    2015-05-01

    Secondary ion mass spectrometry (SIMS) is generally used in imaging the isotopic composition of various materials. It is becoming increasingly popular in biology, especially for investigations of cellular metabolism. However, individual proteins are difficult to identify in SIMS, which limits the ability of this technology to study individual compartments or protein complexes. We present a method for specific protein isotopic and fluorescence labeling (SPILL), based on a novel click reaction with isotopic probes. Using this method, we added (19) F-enriched labels to different proteins, and visualized them by NanoSIMS and fluorescence microscopy. The (19) F signal allowed the precise visualization of the protein of interest, with minimal background, and enabled correlative studies of protein distribution and cellular metabolism or composition. SPILL can be applied to biological systems suitable for click chemistry, which include most cell-culture systems, as well as small model organisms. PMID:25783034

  19. Interrogating viral capsid assembly with ion mobility-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Uetrecht, Charlotte; Barbu, Ioana M.; Shoemaker, Glen K.; van Duijn, Esther; Heck, Albert J. R.

    2011-02-01

    Most proteins fulfil their function as part of large protein complexes. Surprisingly, little is known about the pathways and regulation of protein assembly. Several viral coat proteins can spontaneously assemble into capsids in vitro with morphologies identical to the native virion and thus resemble ideal model systems for studying protein complex formation. Even for these systems, the mechanism for self-assembly is still poorly understood, although it is generally thought that smaller oligomeric structures form key intermediates. This assembly nucleus and larger viral assembly intermediates are typically low abundant and difficult to monitor. Here, we characterised small oligomers of Hepatitis B virus (HBV) and norovirus under equilibrium conditions using native ion mobility mass spectrometry. This data in conjunction with computational modelling enabled us to elucidate structural features of these oligomers. Instead of more globular shapes, the intermediates exhibit sheet-like structures suggesting that they are assembly competent. We propose pathways for the formation of both capsids.

  20. Secondary-Ion Mass Spectrometry of Genetically Encoded Targets**

    PubMed Central

    Vreja, Ingrid C; Kabatas, Selda; Saka, Sinem K; Kröhnert, Katharina; Höschen, Carmen; Opazo, Felipe; Diederichsen, Ulf; Rizzoli, Silvio O

    2015-01-01

    Secondary ion mass spectrometry (SIMS) is generally used in imaging the isotopic composition of various materials. It is becoming increasingly popular in biology, especially for investigations of cellular metabolism. However, individual proteins are difficult to identify in SIMS, which limits the ability of this technology to study individual compartments or protein complexes. We present a method for specific protein isotopic and fluorescence labeling (SPILL), based on a novel click reaction with isotopic probes. Using this method, we added 19F-enriched labels to different proteins, and visualized them by NanoSIMS and fluorescence microscopy. The 19F signal allowed the precise visualization of the protein of interest, with minimal background, and enabled correlative studies of protein distribution and cellular metabolism or composition. SPILL can be applied to biological systems suitable for click chemistry, which include most cell-culture systems, as well as small model organisms. PMID:25783034

  1. Anomalous Ion Charge State Behavior In Interplanetary Coronal Mass Ejections

    NASA Astrophysics Data System (ADS)

    Kocher, M.; Lepri, S. T.; Landi, E.; Zhao, L.

    2015-12-01

    A recent analysis of solar wind charge state composition measurements from the ACE/SWICS instrument showed that the expected correlation between the frozen-in values of the O7/O6 and C6/C5 ratios was violated in ~5% of the slow solar wind in the 1998-2011 period (Zhao et al. 2015). In this work we determine that such anomalous behavior is also found in over 40% of Interplanetary Coronal Mass Ejections (ICMEs), as identified by Richardson and Cane (2010). An analysis of the plasma composition during these events reveals significant depletions in densities of fully stripped ions of Carbon, Oxygen, and Nitrogen. We argue that these events are indicators of ICME plasma acceleration via magnetic reconnection near the freeze-in region of Carbon and Oxygen above the solar corona.

  2. System for studying a sample of material using a heavy ion induced mass spectrometer source

    DOEpatents

    Fries, D.P.; Browning, J.F.

    1998-07-21

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high (n,f) reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu. 3 figs.

  3. System for studying a sample of material using a heavy ion induced mass spectrometer source

    DOEpatents

    Fries, David P.; Browning, James F.

    1998-01-01

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high n,f reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu.

  4. Method for studying a sample of material using a heavy ion induced mass spectrometer source

    DOEpatents

    Fries, David P.; Browning, James F.

    1999-01-01

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high n,f reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu.

  5. Method for studying a sample of material using a heavy ion induced mass spectrometer source

    DOEpatents

    Fries, D.P.; Browning, J.F.

    1999-02-16

    A heavy ion generator is used with a plasma desorption mass spectrometer to provide an appropriate neutron flux in the direction of a fissionable material in order to desorb and ionize large molecules from the material for mass analysis. The heavy ion generator comprises a fissionable material having a high n,f reaction cross section. The heavy ion generator also comprises a pulsed neutron generator that is used to bombard the fissionable material with pulses of neutrons, thereby causing heavy ions to be emitted from the fissionable material. These heavy ions impinge on a material, thereby causing ions to desorb off that material. The ions desorbed off the material pass through a time-of-flight mass analyzer, wherein ions can be measured with masses greater than 25,000 amu. 3 figs.

  6. Decomposition of cyclohexane ion induced by intense femtosecond laser fields by ion-trap time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yamazaki, Takao; Watanabe, Yusuke; Kanya, Reika; Yamanouchi, Kaoru

    2016-01-01

    Decomposition of cyclohexane cations induced by intense femtosecond laser fields at the wavelength of 800 nm is investigated by ion-trap time-of-flight mass spectrometry in which cyclohexane cations C6H12+ stored in an ion trap are irradiated with intense femtosecond laser pulses and the generated fragment ions are recorded by time-of-flight mass spectrometry. The various fragment ion species, C5Hn+ (n = 7, 9), C4Hn+ (n = 5-8), C3Hn+ (n = 3-7), C2Hn+ (n = 2-6), and CH3+, identified in the mass spectra show that decomposition of C6H12+ proceeds efficiently by the photo-irradiation. From the laser intensity dependences of the yields of the fragment ion species, the numbers of photons required for producing the respective fragment ions are estimated.

  7. Ion Energy Distribution Control Using Ion Mass Ratios in Inductively Coupled Plasmas With a Pulsed DC Bias on the Substrate

    NASA Astrophysics Data System (ADS)

    Logue, Michael D.; Kushner, Mark J.

    2012-10-01

    In many applications requiring energetic ion bombardment, such as plasma etching, gas mixtures containing several ion species are used. In cases where two ions have significantly different masses, it may be feasible to selectively control the ion energy distributions (IEDs) by preferentially extracting the lighter ion mass with a controllable energy. In this work, we investigate the possibility of using a pulsed DC substrate bias in an inductively coupled plasma (ICP) to obtain this control. Pulsing of the substrate bias in the afterglow of a pulsed ICP plasma should allow for shifting of the IED peak energy by an amount approximately equal to the applied bias. If short enough pulses are used it may be possible to obtain a higher flux at high energy of the lower mass ion compared to the higher mass ion. A computational investigation of IEDs in low pressure (a few to 100 mTorr) ICPs sustained in gas mixtures such as Ar/H2 or Xe/H2 (having large mass differences) was conducted as a proof of principle. The model is the Hybrid Plasma Equipment Model with which electron energy distributions (EEDs) and IEDs as a function of position and time are obtained using Monte Carlo simulations. We have found a selective ability to mass and energy discriminate ion fluxes when using sufficiently short bias pulses. Results from the model for plasmas densities, electron temperatures, EEDs and IEDs will be discussed.

  8. Unbalance magnetron plasma source for ion mass-separator

    NASA Astrophysics Data System (ADS)

    Paperny, V. L.; Krasov, V. I.; Astrakchantsev, N. V.; Lebedev, N. V.

    2014-11-01

    The report presents the results of the preliminary studies characteristics of an unbalanced magnetron plasma source supplied with the transport system based on a curved magnetic field. The aim of these studies was to recognize if the system is suitable, in principle, for mass-separation of a multi-component plasma flow. The magnetron source has 50 mm diameter cathode manufactured of an alloy composed of Cu (64%), Pb (22.5%) and admixtures, about of 14% (Al, Zn, C). By means of an immersion time-of-flight spectrometer, a spatial distribution of ions of the cathode material was measured through the system output cross-section. Distribution of atom of these elements was measured here by the X-ray fluorescence spectrometry as well. Both methods showed that the ions of the lighter element (Cu) were concentrated in the inner part of the plasma flow deflected by the magnetic field while the distribution of the heavy element (Pb) was shifted toward the outer area of the flow. The similar effect was observed for each couple of the elements. Such a system is promising for use in plasma technology of reprocessing spent nuclear fuel, namely for separation heavy radioactive fission product from nuclear waste.

  9. Relative Sensitivity Factors for Submicron Secondary Ion Mass Spectrometry with Gallium Primary Ion Beam

    NASA Astrophysics Data System (ADS)

    Satoh, Hitomi; Owari, Masanori; Nihei, Yoshimasa

    1993-08-01

    Relative sensitivity factors (RSFs) of thirteen elements in the oxide glass matrix in secondary ion mass spectrometry (SIMS) excited by a gallium focused ion beam were determined. RSFs were obtained by analyzing powder particles of standard glass samples. Whole volumes of each particles were analyzed in the “shave-off” mode in order to avoid topographic effects. Reproducibility of RSFs was good, and sample-to-sample scattering of values was relatively small. Dependence of RSFs on the first ionization potential was shown to be reasonable. In order to check the validity of the RSFs, coal fly ash particles were analyzed. The results were in reasonable agreement with the data obtained through the bulk chemical analysis.

  10. Ion mobility mass spectrometry of peptide, protein, and protein complex ions using a radio-frequency confining drift cell.

    PubMed

    Allen, Samuel J; Giles, Kevin; Gilbert, Tony; Bush, Matthew F

    2016-02-01

    Ion mobility mass spectrometry experiments enable the characterization of mass, assembly, and shape of biological molecules and assemblies. Here, a new radio-frequency confining drift cell is characterized and used to measure the mobilities of peptide, protein, and protein complex ions. The new drift cell replaced the traveling-wave ion mobility cell in a Waters Synapt G2 HDMS. Methods for operating the drift cell and determining collision cross section values using this experimental set up are presented within the context of the original instrument control software. Collision cross sections for 349 cations and anions are reported, 155 of which are for ions that have not been characterized previously using ion mobility. The values for the remaining ions are similar to those determined using a previous radio-frequency confining drift cell and drift tubes without radial confinement. Using this device under 2 Torr of helium gas and an optimized drift voltage, denatured and native-like ions exhibited average apparent resolving powers of 14.2 and 16.5, respectively. For ions with high mobility, which are also low in mass, the apparent resolving power is limited by contributions from ion gating. In contrast, the arrival-time distributions of low-mobility, native-like ions are not well explained using only contributions from ion gating and diffusion. For those species, the widths of arrival-time distributions are most consistent with the presence of multiple structures in the gas phase. PMID:26739109

  11. Ion mobility mass spectrometry of proteins in a modified commercial mass spectrometer

    NASA Astrophysics Data System (ADS)

    Thalassinos, K.; Slade, S. E.; Jennings, K. R.; Scrivens, J. H.; Giles, K.; Wildgoose, J.; Hoyes, J.; Bateman, R. H.; Bowers, M. T.

    2004-08-01

    Ion mobility has emerged as an important technique for determining biopolymer conformations in solvent free environments. These experiments have been nearly exclusively performed on home built systems. In this paper we describe modifications to a commercial high performance mass spectrometer, the Waters UK "Ultima" Q-Tof, that allows high sensitivity measurement of peptide and protein cross sections. Arrival time distributions are obtained for a series of peptides (bradykinin, LHRH, substance P, bombesin) and proteins (bovine and equine cytochrome c, myoglobin, [alpha]-lactalbumin) with good agreement found with literature cross sections where available. In complex ATD's, mass spectra can be obtained for each feature confirming assignments. The increased sensitivity of the commercial instrument is retained along with the convenience of the data system, crucial features for analysis of protein misfolding systems.

  12. Carbohydrate Structure Characterization by Tandem Ion Mobility Mass Spectrometry (IMMS)2

    PubMed Central

    Li, Hongli; Bendiak, Brad; Siems, William F.; Gang, David R.; Hill, Herbert H.

    2013-01-01

    A high resolution ion mobility spectrometer was interfaced to a Synapt G2 high definition mass spectrometer (HDMS) to produce IMMS-IMMS analysis. The hybrid instrument contained an electro-spray ionization source, two ion gates, an ambient pressure linear ion mobility drift tube, a quadrupole mass filter, a traveling wave ion mobility spectrometer (TWIMS) and a time of flight mass spectrometer. The dual gate drift tube ion mobility spectrometer (DTIMS) could be used to acquire traditional IMS spectra, but also could selectively transfer specific mobility selected precursor ions to the Synapt G2 HDMS for mass filtration (quadrupole). The mobility and mass selected ions could then be introduced into a collision cell for fragmentation followed by mobility separation of the fragment ions with the traveling wave ion mobility spectrometer. These mobility separated fragment ions are finally mass analyzed using a time-of-flight mass spectrometer. This results in an IMMS-IMMS analysis and provides a method to evaluate the isomeric heterogeneity of precursor ions by both DTIMS and TWIMS, to acquire a mobility-selected and mass-filtered fragmentation pattern and to additionally obtain traveling wave ion mobility spectra of the corresponding product ions. This new IMMS2 instrument enables the structural diversity of carbohydrates to be studied in greater detail. The physical separation of isomeric oligosaccharide mixtures was achieved by both DTIMS and TWIMS, with DTIMS demonstrating higher resolving power (70~80) than TWIMS (30~40). Mobility selected MS/MS spectra were obtained, and TWIMS evaluation of product ions showed that isomeric forms of fragment ions existed for identical m/z values. PMID:23330948

  13. Carbohydrate structure characterization by tandem ion mobility mass spectrometry (IMMS)2.

    PubMed

    Li, Hongli; Bendiak, Brad; Siems, William F; Gang, David R; Hill, Herbert H

    2013-03-01

    A high resolution ion mobility spectrometer was interfaced to a Synapt G2 high definition mass spectrometer (HDMS) to produce IMMS-IMMS analysis. The hybrid instrument contained an electrospray ionization source, two ion gates, an ambient pressure linear ion mobility drift tube, a quadrupole mass filter, a traveling wave ion mobility spectrometer (TWIMS), and a time-of-flight mass spectrometer. The dual gate drift tube ion mobility spectrometer (DTIMS) could be used to acquire traditional IMS spectra but also could selectively transfer specific mobility selected precursor ions to the Synapt G2 HDMS for mass filtration (quadrupole). The mobility and mass selected ions could then be introduced into a collision cell for fragmentation followed by mobility separation of the fragment ions with the traveling wave ion mobility spectrometer. These mobility separated fragment ions are finally mass analyzed using a time-of-flight mass spectrometer. This results in an IMMS-IMMS analysis and provides a method to evaluate the isomeric heterogeneity of precursor ions by both DTIMS and TWIMS to acquire a mobility-selected and mass-filtered fragmentation pattern and to additionally obtain traveling wave ion mobility spectra of the corresponding product ions. This new IMMS(2) instrument enables the structural diversity of carbohydrates to be studied in greater detail. The physical separation of isomeric oligosaccharide mixtures was achieved by both DTIMS and TWIMS, with DTIMS demonstrating higher resolving power (70-80) than TWIMS (30-40). Mobility selected MS/MS spectra were obtained, and TWIMS evaluation of product ions showed that isomeric forms of fragment ions existed for identical m/z values. PMID:23330948

  14. Ion Sponge: A 3-Dimentional Array of Quadrupole Ion Traps for Trapping and Mass-Selectively Processing Ions in Gas Phase

    PubMed Central

    2015-01-01

    In this study, the concept of ion sponge has been explored for developing 3D arrays of large numbers of ion traps but with simple configurations. An ion sponge device with 484 trapping units in a volume of 10 × 10 × 3.2 cm has been constructed by simply stacking 9 meshes together. A single rf was used for trapping ions and mass-selective ion processing. The ion sponge provides a large trapping capacity and is highly transparent for transfer of ions, neutrals, and photons for gas phase ion processing. Multiple layers of quadrupole ion traps, with 121 trapping units in each layer, can operate as a single device for MS or MS/MS analysis, or as a series of mass-selective trapping devices with interlayer ion transfers facilitated by AC and DC voltages. Automatic sorting of ions to different trapping layers based on their mass-to-charge (m/z) ratios was achieved with traps of different sizes. Tandem-in-space MS/MS has also been demonstrated with precursor ions and fragment ions trapped in separate locations. PMID:24758328

  15. Ion collision cross section measurements in Fourier transform-based mass analyzers.

    PubMed

    Li, Dayu; Tang, Yang; Xu, Wei

    2016-06-01

    With the increasing demands of molecular structure analysis, several methods have been developed to measure ion collision cross sections within Fourier transform (FT) based mass analyzers. Particularly in the recent three years since 2012, the method of obtaining biomolecule collision cross sections was achieved in Fourier transform ion cyclotron resonance (FT-ICR) cells. Furthermore, similar methods have been realized or proposed for orbitraps and quadrupole ion traps. This technique adds a new ion structure analysis capability to FT-based mass analyzers. By providing complementary ion structure information, it could be used together with tandem mass spectrometry and ion mobility spectroscopy techniques. Although many questions and challenges remain, this technique potentially would greatly enhance the ion structure analysis capability of a mass spectrometer, and provide a new tool for chemists and biochemists. PMID:26788551

  16. Development of C{sub 60} plasma ion source for time-of-flight secondary ion mass spectrometry applications

    SciTech Connect

    Ji Qing; Chen Ye; Ji Lili; Hahto, Sami; Leung, Ka-Ngo; Lee, Tae Geol; Moon, Dae Won

    2008-02-15

    Initial data from a multicusp ion source developed for buckminsterfullerene (C{sub 60}) cluster ion production are reported in this article. A C{sub 60}{sup +} beam current of 425 nA and a C{sub 60}{sup -} beam current of 200 nA are obtainable in continuous mode. Compared to prior work using electron impact ionization, the multicusp ion source provides at least two orders of magnitude increase in the extractable C{sub 60}{sup +} beam current. Mass spectra for both positive and negative bismuth cluster ions generated by the multicusp ion source are also included.

  17. Laser Induced-Plasma Ion Mass Spectrometry for Characterization of Lunar and Planetary Surfaces

    NASA Astrophysics Data System (ADS)

    Wiens, R. C.; Blacic, J. D.; Cremers, D. A.; Ritzau, S. M.; Nordholt, J. E.; Funsten, H. O.

    1999-03-01

    LIMS is being developed to perform isotopic and elemental analysis of lunar and planetary surfaces at standoff distances. It uses an advanced ion mass spectrometer to obtain mass and energy spectra from the ionized plume produced by a laser.

  18. Modeling vapor uptake induced mobility shifts in peptide ions observed with transversal modulation ion mobility spectrometry-mass spectrometry.

    PubMed

    Rawat, Vivek K; Vidal-de-Miguel, Guillermo; Hogan, Christopher J

    2015-10-21

    Low field ion mobility spectrometry-mass spectrometry (IMS-MS) techniques exhibit low orthogonality, as inverse mobility often scales with mass to charge ratio. This inadequacy can be mitigated by adding vapor dopants, which may cluster with analyte ions and shift their mobilities by amounts independent of both mass and mobility of the ion. It is therefore important to understand the interactions of vapor dopants with ions, to better quantify the extent of dopant facilitated mobility shifts. Here, we develop predictive models of vapor dopant facilitated mobility shifts, and compare model calculations to measurements of mobility shifts for peptide ions exposed to variable gas phase concentrations of isopropanol. Mobility measurements were made at atmospheric pressure and room temperature using a recently developed transversal modulation ion mobility spectrometer (TMIMS). Results are compared to three separate models, wherein mobility shifts due to vapor dopants are attributed to changes in gas composition and (I) no vapor dopant uptake is assumed, (II) site-specific dopant uptake by the ion is assumed (approximated via a Langmuir adsorption model), and (III) site-unspecific dopant uptake by the ion is assumed (approximated via a classical nucleation model). We find that mobility shifts in peptide ions are in excellent agreement with model II, site-specific binding predictions. Conversely, mobility shifts of tetraalkylammonium ions from previous measurements were compared with these models and best agreement was found with model III predictions, i.e. site-unspecific dopant uptake. PMID:26051323

  19. Structurally selective imaging mass spectrometry by imaging ion mobility-mass spectrometry.

    PubMed

    McLean, John A; Fenn, Larissa S; Enders, Jeffrey R

    2010-01-01

    This chapter describes the utility of structurally based separations combined with imaging mass spectrometry (MS) by ion mobility-MS (IM-MS) approaches. The unique capabilities of combining rapid (mus-ms) IM separations with imaging MS are detailed for an audience ranging from new to potential practitioners in IM-MS technology. Importantly, imaging IM-MS provides the ability to rapidly separate and elucidate various types of endogenous and exogenous biomolecules (e.g., nucleotides, carbohydrates, peptides, and lipids), including isobaric species. Drift tube and traveling wave IM-MS instrumentation are described and specific protocols are presented for calculating ion-neutral collision cross sections (i.e., apparent ion surface area or structure) from experimentally obtained IM-MS data. Special emphasis is placed on the use of imaging IM-MS for the analysis of samples in life sciences research (e.g., thin tissue sections), including selective imaging for peptide/protein and lipid distributions. Future directions for rapid and multiplexed imaging IM-MS/MS are detailed. PMID:20680602

  20. Protein derivatization and sequential ion/ion reactions to enhance sequence coverage produced by electron transfer dissociation mass spectrometry

    PubMed Central

    Anderson, Lissa C.; English, A. Michelle; Wang, Weihan; Bai, Dina L.; Shabanowitz, Jeffrey; Hunt, Donald F

    2014-01-01

    Previously, we described implementation of a front-end ETD (electron transfer dissociation) source for an Orbitrap instrument (1). This source facilitates multiple fills of the C-trap with product ions from ETD of intact proteins prior to mass analysis. The result is a dramatic enhancement of the observed ion current without the need for time consuming averaging of data from multiple mass measurements. Here we show that ion-ion proton transfer (IIPT) reactions can be used to simplify ETD spectra and to disperse fragment ions over the entire mass range in a controlled manner. We also show that protein derivatization can be employed to selectively enhance the sequence information observed at the N- and C-termini of a protein. PMID:25844056

  1. Infrared Multiphoton Dissociation of Peptide Cations in a Dual Pressure Linear Ion Trap Mass Spectrometer

    PubMed Central

    Gardner, Myles W.; Smith, Suncerae I.; Ledvina, Aaron R.; Madsen, James A.; Coon, Joshua J.; Schwartz, Jae C.; Stafford, George C.; Brodbelt, Jennifer S.

    2009-01-01

    A dual pressure linear ion trap mass spectrometer was modified to permit infrared multiphoton dissociation (IRMPD) in each of the two cells - the first a high pressure cell operated at nominally 5 × 10-3 Torr and the second a low pressure cell operated at nominally 3 × 10-4 Torr. When IRMPD was performed in the high pressure cell, most peptide ions did not undergo significant photodissociation; however, in the low pressure cell peptide cations were efficiently dissociated with less than 25 ms of IR irradiation regardless of charge state. IRMPD of peptide cations allowed the detection of low m/z product ions including the y1 fragments and immonium ions which are not typically observed by ion trap collision induced dissociation (CID). Photodissociation efficiencies of ~100% and MS/MS (tandem mass spectrometry) efficiencies of greater than 60% were observed for both multiply and singly protonated peptides. In general, higher sequence coverage of peptides was obtained using IRMPD over CID. Further, greater than 90% of the product ion current in the IRMPD mass spectra of doubly charged peptide ions was composed of singly charged product ions compared to the CID mass spectra in which the abundances of the multiply and singly charged product ions were equally divided. Highly charged primary product ions also underwent efficient photodissociation to yield singly charged secondary product ions, thus simplifying the IRMPD product ion mass spectra. PMID:19739654

  2. Examining the Influence of Phosphorylation on Peptide Ion Structure by Ion Mobility Spectrometry-Mass Spectrometry.

    PubMed

    Glover, Matthew S; Dilger, Jonathan M; Acton, Matthew D; Arnold, Randy J; Radivojac, Predrag; Clemmer, David E

    2016-05-01

    Ion mobility spectrometry-mass spectrometry (IMS-MS) techniques are used to study the general effects of phosphorylation on peptide structure. Cross sections for a library of 66 singly phosphorylated peptide ions from 33 pairs of positional isomers, and unmodified analogues were measured. Intrinsic size parameters (ISPs) derived from these measurements yield calculated collision cross sections for 85% of these phosphopeptide sequences that are within ±2.5% of experimental values. The average ISP for the phosphoryl group (0.64 ± 0.05) suggests that in general this moiety forms intramolecular interactions with the neighboring residues and peptide backbone, resulting in relatively compact structures. We assess the capability of ion mobility to separate positional isomers (i.e., peptide sequences that differ only in the location of the modification) and find that more than half of the isomeric pairs have >1% difference in collision cross section. Phosphorylation is also found to influence populations of structures that differ in the cis/trans orientation of Xaa-Pro peptide bonds. Several sequences with phosphorylated Ser or Thr residues located N-terminally adjacent to Pro residues show fewer conformations compared to the unmodified sequences. Graphical Abstract ᅟ. PMID:26860087

  3. Examining the Influence of Phosphorylation on Peptide Ion Structure by Ion Mobility Spectrometry-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Glover, Matthew S.; Dilger, Jonathan M.; Acton, Matthew D.; Arnold, Randy J.; Radivojac, Predrag; Clemmer, David E.

    2016-05-01

    Ion mobility spectrometry-mass spectrometry (IMS-MS) techniques are used to study the general effects of phosphorylation on peptide structure. Cross sections for a library of 66 singly phosphorylated peptide ions from 33 pairs of positional isomers, and unmodified analogues were measured. Intrinsic size parameters (ISPs) derived from these measurements yield calculated collision cross sections for 85% of these phosphopeptide sequences that are within ±2.5% of experimental values. The average ISP for the phosphoryl group (0.64 ± 0.05) suggests that in general this moiety forms intramolecular interactions with the neighboring residues and peptide backbone, resulting in relatively compact structures. We assess the capability of ion mobility to separate positional isomers (i.e., peptide sequences that differ only in the location of the modification) and find that more than half of the isomeric pairs have >1% difference in collision cross section. Phosphorylation is also found to influence populations of structures that differ in the cis/ trans orientation of Xaa-Pro peptide bonds. Several sequences with phosphorylated Ser or Thr residues located N-terminally adjacent to Pro residues show fewer conformations compared to the unmodified sequences.

  4. Examining the Influence of Phosphorylation on Peptide Ion Structure by Ion Mobility Spectrometry-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Glover, Matthew S.; Dilger, Jonathan M.; Acton, Matthew D.; Arnold, Randy J.; Radivojac, Predrag; Clemmer, David E.

    2016-02-01

    Ion mobility spectrometry-mass spectrometry (IMS-MS) techniques are used to study the general effects of phosphorylation on peptide structure. Cross sections for a library of 66 singly phosphorylated peptide ions from 33 pairs of positional isomers, and unmodified analogues were measured. Intrinsic size parameters (ISPs) derived from these measurements yield calculated collision cross sections for 85% of these phosphopeptide sequences that are within ±2.5% of experimental values. The average ISP for the phosphoryl group (0.64 ± 0.05) suggests that in general this moiety forms intramolecular interactions with the neighboring residues and peptide backbone, resulting in relatively compact structures. We assess the capability of ion mobility to separate positional isomers (i.e., peptide sequences that differ only in the location of the modification) and find that more than half of the isomeric pairs have >1% difference in collision cross section. Phosphorylation is also found to influence populations of structures that differ in the cis/trans orientation of Xaa-Pro peptide bonds. Several sequences with phosphorylated Ser or Thr residues located N-terminally adjacent to Pro residues show fewer conformations compared to the unmodified sequences.

  5. Determination of Cu Concentrations in CdTe/CdS Devices by High Mass Resolution Secondary Ion Mass Spectrometry

    SciTech Connect

    Asher, S. E.; Reedy, R. C.; Dhere, R.; Gessert, t. A.; Young, M. R.

    2000-01-01

    We have used secondary ion mass spectrometry (SIMS) to quantitatively determine the concentration of Cu in CdTe/CdS devices. Empirical standards were fabricated by ion implantation of Cu into single-crystal and polycrystalline CdTe and single-crystal CdS.

  6. Determination of N-linked glycosylation in viral glycoproteins by negative ion mass spectrometry and ion mobility

    PubMed Central

    Bitto, David; Harvey, David J.; Halldorsson, Steinar; Doores, Katie J.; Pritchard, Laura K.; Huiskonen, Juha T.; Bowden, Thomas A.; Crispin, Max

    2016-01-01

    Summary Glycan analysis of virion-derived glycoproteins is challenging due to the difficulties in glycoprotein isolation and low sample abundance. Here, we describe how ion mobility mass spectrometry can be used to obtain spectra from virion samples. We also describe how negative ion fragmentation of glycans can be used to probe structural features of virion glycans. PMID:26169737

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

    USGS Publications Warehouse

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

    2005-01-01

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

  8. Improving Secondary Ion Mass Spectrometry Image Quality with Image Fusion

    PubMed Central

    Tarolli, Jay G.; Jackson, Lauren M.; Winograd, Nicholas

    2014-01-01

    The spatial resolution of chemical images acquired with cluster secondary ion mass spectrometry (SIMS) is limited not only by the size of the probe utilized to create the images, but also by detection sensitivity. As the probe size is reduced to below 1 µm, for example, a low signal in each pixel limits lateral resolution due to counting statistics considerations. Although it can be useful to implement numerical methods to mitigate this problem, here we investigate the use of image fusion to combine information from scanning electron microscope (SEM) data with chemically resolved SIMS images. The advantage of this approach is that the higher intensity and, hence, spatial resolution of the electron images can help to improve the quality of the SIMS images without sacrificing chemical specificity. Using a pan-sharpening algorithm, the method is illustrated using synthetic data, experimental data acquired from a metallic grid sample, and experimental data acquired from a lawn of algae cells. The results show that up to an order of magnitude increase in spatial resolution is possible to achieve. A cross-correlation metric is utilized for evaluating the reliability of the procedure. PMID:24912432

  9. Laser mass spectrometry of biological molecular ions produced by matrix assisted laser desorption ionization (MALDI)

    NASA Astrophysics Data System (ADS)

    Jia, W. J.; Kosmidis, C.; Ledingham, K. W. D.; Scott, C. T. J.; Singhal, R. P.

    1996-10-01

    A tandem reflectron laser mass spectrometer is used for investigations of the photo fragmentation of molecular ions. The observed fragmentation patterns for 2,5-dihydrobenzoic acid and its fragments ions are analysed. PTH-trytophan and PTH-valine ions, generated by MALDI, are photodissociated and their fragmentation pattern is discussed.

  10. An electrodynamic ion funnel interface for greater sensitivity and higher throughput with linear ion trap mass spectrometers

    NASA Astrophysics Data System (ADS)

    Page, Jason S.; Tang, Keqi; Smith, Richard D.

    2007-09-01

    An electrospray ionization interface incorporating an electrodynamic ion funnel has been designed and implemented on a linear ion trap mass spectrometer (Thermo Electron, LTQ). We found ion transmission to be greatly improved by replacing the standard capillary-skimmer interface with the capillary-ion funnel interface. An infusion study using a serial dilution of a reserpine solution showed that ion injection (accumulation) times to fill the ion trap at a given automatic gain control (AGC) target value were reduced by ~90% which resulted in an ~10-fold increase in peak intensities. In liquid chromatography tandem MS (LC-MS/MS) experiments performed using a global protein digest sample from the bacterium, Shewanella oneidensis, more peptides and proteins were identified when the ion funnel interface was used in place of the standard interface. This improvement was most pronounced at lower sample concentrations, where extended ion accumulation times are required, resulting in an ~2-fold increase in the number of protein identifications. Implementation of the ion funnel interface on a LTQ Fourier transform (FT) mass spectrometer showed a ~25-50% reduction in spectrum acquisition time. The duty cycle improvement in this case was due to the ion accumulation event contributing a larger portion to the total spectrum acquisition time.

  11. An electrodynamic ion funnel interface for greater sensitivity and higher throughput with linear ion trap mass spectrometers

    SciTech Connect

    Page, Jason S.; Tang, Keqi; Smith, Richard D.

    2007-09-01

    An electrospray ionization interface incorporating an electrodynamic ion funnel has been designed and implemented in conjunction with a linear ion trap mass spectrometer (Thermo Electron, LTQ). We found ion transmission to be greatly improved by replacing the standard capillary-skimmer interface with the capillary-ion funnel interface. An infusion study using a serial dilution of a reserpine solution showed that ion injection times to fill the ion trap were reduced by ~90% which resulted in an ~10-fold increase in reported peak intensities. In liquid chromatography (LC)-MS and LC tandem MS (MS/MS) experiments performed using a proteomic sample from the bacterium, Shewanella oneidensis, the ion funnel interface provided an ~7-fold reduction in ion injection (accumulation) times. In a series of LC-MS/MS experiments we found that more dilute S. oneidensis samples provided more peptide and protein identifications when the ion funnel interface was used in place of the standard interface. This improvement was most pronounced at lower sample concentrations, where extended ion accumulation times are required, resulting in an ~2-fold increase in the number of protein identifications. Implementation of the ion funnel interface with a LTQ Fourier transform (FT) MS requiring much greater ion populations resulted in spectrum acquisition times reduced by ~25 to 50%.

  12. Ion-Surface Collisions in Mass Spectrometry: Where Analytical Chemistry Meets Surface Science

    SciTech Connect

    Laskin, Julia

    2015-02-01

    This article presents a personal perspective regarding the development of key concepts in understanding hyperthermal collisions of polyatomic ions with surfaces as a unique tool for mass spectrometry applications. In particular, this article provides a historic overview of studies focused on understanding the phenomena underlying surface-induced dissociation (SID) and mass-selected deposition of complex ions on surfaces. Fast energy transfer in ion-surface collisions makes SID especially advantageous for structural characterization of large complex molecules, such as peptides, proteins, and protein complexes. Soft, dissociative, and reactive landing of mass-selected ions provide the basis for preparatory mass spectrometry. These techniques enable precisely controlled deposition of ions on surfaces for a variety of applications. This perspective article shows how basic concepts developed in the 1920s and 1970s have evolved to advance promising mass-spectrometry-based applications.

  13. Remote mass spectrometric sampling of electrospray- and desorption electrospray-generated ions using an air ejector.

    PubMed

    Dixon, R Brent; Bereman, Michael S; Muddiman, David C; Hawkridge, Adam M

    2007-10-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data are presented. PMID:17716909

  14. Remote Mass Spectrometric Sampling of Electrospray- and Desorption Electrospray-Generated Ions Using an Air Ejector

    PubMed Central

    Dixon, R. Brent; Bereman, Michael S.; Muddiman, David C.; Hawkridge, Adam M.

    2007-01-01

    A commercial air ejector was coupled to an electrospray ionization linear ion trap mass spectrometer (LTQ) to transport remotely generated ions from both electrospray (ESI) and desorption electrospray ionization (DESI) sources. We demonstrate the remote analysis of a series of analyte ions that range from small molecules and polymers to polypeptides using the AE-LTQ interface. The details of the ESI-AE-LTQ and DESI-AE-LTQ experimental configurations are described and preliminary mass spectrometric data is presented. PMID:17716909

  15. Gas phase ion chemistry of an ion mobility spectrometry based explosive trace detector elucidated by tandem mass spectrometry.

    PubMed

    Kozole, Joseph; Levine, Lauren A; Tomlinson-Phillips, Jill; Stairs, Jason R

    2015-08-01

    The gas phase ion chemistry for an ion mobility spectrometer (IMS) based explosive detector has been elucidated using tandem mass spectrometry. The IMS system, which is operated with hexachloroethane and isobutyramide reagent gases and an ion shutter type gating scheme, is connected to the atmospheric pressure interface of a triple quadrupole mass spectrometer (MS/MS). Product ion masses, daughter ion masses, and reduced mobility values for a collection of nitro, nitrate, and peroxide explosives measured with the IMS/MS/MS instrument are reported. The mass and mobility data together with targeted isotopic labeling experiments and information about sample composition and reaction environment are leveraged to propose molecular formulas, structures, and ionization pathways for the various product ions. The major product ions are identified as [DNT-H](-) for DNT, [TNT-H](-) for TNT, [RDX+Cl](-) and [RDX+NO2](-) for RDX, [HMX+Cl](-) and [HMX+NO2](-) for HMX, [NO3](-) for EGDN, [NG+Cl](-) and [NG+NO3](-) for NG, [PETN+Cl](-) and [PETN+NO3](-) for PETN, [HNO3+NO3](-) for NH4NO3, [NO2](-) for DMNB, [HMTD-NC3H6O3+H+Cl](-) and [HMTD+H-CH2O-H2O2](+) for HMTD, and [(CH3)3CO2](+) for TATP. In general, the product ions identified for the IMS system studied here are consistent with the product ions reported previously for an ion trap mobility spectrometer (ITMS) based explosive trace detector, which is operated with dichloromethane and ammonia reagent gases and an ion trap type gating scheme. Differences between the explosive trace detectors include the [NG+Cl](-) and [PETN+Cl](-) product ions being major ions in the IMS system compared to minor ions in the ITMS system as well as the major product ion for TATP being [(CH3)3CO2](+) for the IMS system and [(CH3)2CNH2](+) for the ITMS system. PMID:26048817

  16. Surpassing the mass restriction of buffer gas cooling: Cooling of low mass ions by localized heavier atoms

    NASA Astrophysics Data System (ADS)

    Dutta, Sourav; Sawant, Rahul; Rangwala, S. A.

    2016-05-01

    Cooling of trapped ions has resulted in fascinating science including the realization of some of the most accurate atomic clocks. It has also found widespread application, for example, in mass spectrometry and cold chemistry. Among the different methods for cooling ions, cooling by elastic collisions with ultracold neutral atoms is arguably the most generic. However, in spite of its widespread application, there is confusion with regards the collisional heating/cooling of light ions by heavier neutral atoms. We address the question experimentally and demonstrate, for the first time, cooling of light ions by co-trapped heavy atoms. We show that trapped 39 K+ ions are cooled by localized ultracold neutral 85 Rb atoms. The atom-ion mass ratio (= 2.18) is well beyond any theoretical predictions so far. We further argue that cooling of ions by localized cold atoms is possible for any mass ratio. The result opens up the possibility of reaching the elusive s-wave collision regime in atom-ion collisions. S.D. is supported by DST-INSPIRE Faculty Fellowship, India.

  17. Design and performance of an instrument for electron impact tandem mass spectrometry and action spectroscopy of mass/charge selected macromolecular ions stored in RF ion trap*

    NASA Astrophysics Data System (ADS)

    Ranković, Milos Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

    2016-05-01

    A new apparatus was designed, coupling an electron gun with a linear quadrupole ion trap mass spectrometer, to perform m/z (mass over charge) selected ion activation by electron impact for tandem mass spectrometry and action spectroscopy. We present in detail electron tracing simulations of a 300 eV electron beam inside the ion trap, design of the mechanical parts, electron optics and electronic circuits used in the experiment. We also report examples of electron impact activation tandem mass spectra for Ubiquitin protein, Substance P and Melittin peptides, at incident electron energies in the range from 280 eV to 300 eV. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  18. High charge state ions observed with a thermal ion mass spectrometer at the high-altitude polar ionosphere

    NASA Astrophysics Data System (ADS)

    Sagawa, E.; Watanabe, S.; Watanabe, S.

    The Suprathermal Ion Mass Spectrometer (SMS) on board the AKEBONO satellite has occasionally observed ions with broad mass peak in mass spectrum between amu/q=2 and 3. The SMS is capable to measure a wide range of ion mass (1-64 amu/q) at low energy (E<100 eV) with a good mass resolution (dM/M~0.1). Energy distribution can be measured with RPA section of the instrument below 25 eV, and the energy pass band in this operation mode of instrument is below 100 eV. The events were observed at about 1 Re altitude, and m stly near the polar cuspo region, specifically, collocated with the intense "cusp/mantle" precipitation region (Newell and Meng, 1992) identified with the on-board particle experiment. Following is summary of characteristics of these events; (1) Almost uniform pitch angle distribution. (2) Within the instrument ability, there is no meaningful information about energydistribution. (3) Collocation with the "cusp/mantle" type of ion precipitation (4) The broad mass peak is consistent with high-charge state ions commonly seenin the solar wind such as C +, O7 +, O6 +, and C5 +. However, because the6

  19. An electrodynamic ion funnel for electrospray ionization source based time-of-flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bhushan, K. G.; Rao, K. C.; Sule, U.; Reddy, P.; Rodrigues, S. M.; Gaikwad, D. T.; Mukundhan, R.; Gupta, S. K.

    2016-04-01

    An electrodynamic ion funnel has been developed for improving the sensitivity of electrospray ionization sources widely used in the mass spectrometric study of proteins and other biological macromolecules. The ion funnel consists of 52 electrodes and works under the combined influence of RF and DC voltages in the pressure range of 0.1 to 5 mbar. A novel feature of this ion funnel is the specific shape of the exit electrode that improves transmission of lower mass ions by reducing the depth of effective trapping potentials. In this paper, we report on the optimization of the ion funnel design using ion trajectory simulation software SIMION 8.0 especially in the mass range 500–5000 amu, followed by experimental observations of the ion transmission from the electrospray interface. It is seen that the electrospray-ion funnel combination greatly enhances the transmission when compared with an electrospray-skimmer interface. Ion currents > 1 nA could be obtained at the exit of the ion funnel for dilute Streptomycin Sulphate (~ 1500 amu) solution with the ion funnel operating in the 500–900 kHz frequency range, amplitude of 70 Vp‑p, under a DC gradient of about 20 Volts/cm at a background pressure of 0.3 mbar. Details of the construction of the ion funnel along with the experimental results are presented.

  20. Improvement of biological time-of-flight-secondary ion mass spectrometry imaging with a bismuth cluster ion source.

    PubMed

    Touboul, David; Kollmer, Felix; Niehuis, Ewald; Brunelle, Alain; Laprévote, Olivier

    2005-10-01

    A new liquid metal ion gun (LMIG) filled with bismuth has been fitted to a time-of-flight-secondary ion mass spectrometer (TOF-SIMS). This source provides beams of Bi(n)q+ clusters with n = 1-7 and q = 1 and 2. The appropriate clusters have much better intensities and efficiencies than the Au3+ gold clusters recently used in TOF-SIMS imaging, and allow better lateral and mass resolution. The different beams delivered by this ion source have been tested for biological imaging of rat brain sections. The results show a great improvement of the imaging capabilities in terms of accessible mass range and useful lateral resolution. Secondary ion yields Y, disappearance cross sections sigma, efficiencies E = Y/sigma , and useful lateral resolutions deltaL have been compared using the different bismuth clusters, directly onto the surface of rat brain sections and for several positive and negative secondary ions with m/z ranging from 23 up to more than 750. The efficiency and the imaging capabilities of the different primary ions are compared by taking into account the primary ion current for reasonable acquisition times. The two best primary ions are Bi3+ and Bi5(2+). The Bi3+ ion beam has a current at least five times larger than Au3+ and therefore is an excellent beam for large-area imaging. Bi5(2+) ions exhibit large secondary ions yields and a reasonable intensity making them suitable for small-area images with an excellent sensitivity and a possible useful lateral resolution <400 nm. PMID:16112869

  1. Analysis of megadalton ions using cryodetection MALDI time-of-flight mass spectrometry.

    PubMed

    Wenzel, Ryan J; Matter, Urs; Schultheis, Lothar; Zenobi, Renato

    2005-07-15

    Presented are initial results from the first commercially available matrix-assisted laser desorption/ionization time-of-flight mass spectrometer specifically designed for the sensitive detection of very high mass ions (macromizer, Comet AG). This new instrument utilizes a 16-element superconducting tunnel junction detector coupled with a fully adjustable gimbal-mounted ion source/focusing region that allows unparalleled sensitivity for detection of singly charged high molecular weight ions. Using this new technology, the singly charged ions in the megadalton region are detected from immunoglobulin M and von Willebrand factor proteins. This detector technology also measures the kinetic energy of the particles impacting the detector, which can be correlated to the charge of the particles. Immunoglobulin G and streptavidin were used to demonstrate the ability of the macromizer instrument to detect high-mass ions and to discern the charge state of the ions. PMID:16013843

  2. Fourier transform ion cyclotron resonance (FT ICR) mass spectrometry: Theory and simulations.

    PubMed

    Nikolaev, Eugene N; Kostyukevich, Yury I; Vladimirov, Gleb N

    2016-01-01

    Fourier transform ion cyclotron resonance (FT ICR) mass spectrometer offers highest resolving power and mass accuracy among all types of mass spectrometers. Its unique analytical characteristics made FT ICR important tool for proteomics, metabolomics, petroleomics, and investigation of complex mixtures. Signal acquisition in FT ICR MS takes long time (up to minutes). During this time ion-ion interaction considerably affects ion motion and result in decreasing of the resolving power. Understanding of those effects required complicated theory and supercomputer simulations but culminated in the invention of the ion trap with dynamic harmonization which demonstrated the highest resolving power ever achieved. In this review we summarize latest achievements in theory and simulation of FT ICR mass spectrometers. PMID:24515872

  3. High precision electric gate for time-of-flight ion mass spectrometers

    NASA Technical Reports Server (NTRS)

    Sittler, Edward C. (Inventor)

    2011-01-01

    A time-of-flight mass spectrometer having a chamber with electrodes to generate an electric field in the chamber and electric gating for allowing ions with a predetermined mass and velocity into the electric field. The design uses a row of very thin parallel aligned wires that are pulsed in sequence so the ion can pass through the gap of two parallel plates, which are biased to prevent passage of the ion. This design by itself can provide a high mass resolution capability and a very precise start pulse for an ion mass spectrometer. Furthermore, the ion will only pass through the chamber if it is within a wire diameter of the first wire when it is pulsed and has the right speed so it is near all other wires when they are pulsed.

  4. Advances in ion trap mass spectrometry: Photodissociation as a tool for structural elucidation

    SciTech Connect

    Stephenson, J.L. Jr.; Booth, M.M.; Eyler, J.R.; Yost, R.A.

    1995-12-01

    Photo-induced dissociation (PID) is the next most frequently used method (after collisional activation) for activation of Polyatomic ions in tandem mass spectrometry. The range of internal energies present after the photon absorption process are much narrower than those obtained with collisional energy transfer. Therefore, the usefulness of PID for the study of ion structures is greatly enhanced. The long storage times and instrumental configuration of the ion trap mass spectrometer are ideally suited for photodissociation experiments. This presentation will focus on both the fundamental and analytical applications of CO{sub 2} lasers in conjunction with ion trap mass spectrometry. The first portion of this talk will examine the fundamental issues of wavelength dependence, chemical kinetics, photoabsorption cross section, and collisional effects on photodissociation efficiency. The second half of this presentation will look at novel instrumentation for electrospray/ion trap mass spectrometry, with the concurrent development of photodissociation as a tool for structural elucidation of organic compounds and antibiotics.

  5. Secondary-ion emission from clean and oxidized aluminum as a function of incident ion mass and energy

    NASA Astrophysics Data System (ADS)

    Blauner, Patricia G.; Weller, Robert A.

    1987-02-01

    Measurements of the intensities of low-energy secondary ions emitted from clean and oxidized polycrystalline aluminum surfaces under (15-275)-KeV He+, Ne+, Ar+, Kr+, and Xe+ bombardment are reported. An additional measurement of the secondary-ion mass spectrum obtained from a clean Al surface under 40-MeV Br5+ bombardment is also presented. By varying both the beam energy and mass over such a large range, we have been able to identify three distinct categories of secondary ions. The first category includes the metallic-ion species emitted from the oxide surface. The intensities of these ions are observed to be proportional to the sputtering yield of aluminum, indicating that they are produced by means which are consistent with several of the mechanisms already proposed to explain oxygen-enhanced secondary-ion emission from metals. The second category includes both singly and multiply charged Al ions from the clean surface as well as multiply charged ions from the oxide surface. Under high-energy bombardment, these ions all appear to be produced by the kinetic mechanism which has been proposed to explain multiply charged ion emission from Al under lower-energy bombardment. The third category of secondary ions identified includes only O+ emitted from the oxide surface. This species, although usually a small component of the spectrum, is produced by means wholly unrelated to elastic energy deposition. Its production cannot be explained by any of the proposed models of metallic secondary-ion emission. The possibility that O+ is produced by a mechanism similar to that of electron-stimulated desorption is discussed.

  6. Secondary-ion emission from clean and oxidized aluminum as a function of incident ion mass and energy

    SciTech Connect

    Blauner, P.G.; Weller, R.A.

    1987-02-01

    Measurements of the intensities of low-energy secondary ions emitted from clean and oxidized polycrystalline aluminum surfaces under (15--275)-KeV He/sup +/, Ne/sup +/, Ar/sup +/, Kr/sup +/, and Xe/sup +/ bombardment are reported. An additional measurement of the secondary-ion mass spectrum obtained from a clean Al surface under 40-MeV Br/sup 5+/ bombardment is also presented. By varying both the beam energy and mass over such a large range, we have been able to identify three distinct categories of secondary ions. The first category includes the metallic-ion species emitted from the oxide surface. The intensities of these ions are observed to be proportional to the sputtering yield of aluminum, indicating that they are produced by means which are consistent with several of the mechanisms already proposed to explain oxygen-enhanced secondary-ion emission from metals. The second category includes both singly and multiply charged Al ions from the clean surface as well as multiply charged ions from the oxide surface. Under high-energy bombardment, these ions all appear to be produced by the kinetic mechanism which has been proposed to explain multiply charged ion emission from Al under lower-energy bombardment. The third category of secondary ions identified includes only O/sup +/ emitted from the oxide surface. This species, although usually a small component of the spectrum, is produced by means wholly unrelated to elastic energy deposition. Its production cannot be explained by any of the proposed models of metallic secondary-ion emission. The possibility that O/sup +/ is produced by a mechanism similar to that of electron-stimulated desorption is discussed.

  7. Investigation of Scrambled Ions in Tandem Mass Spectra, Part 2. On the Influence of the Ions on Peptide Identification

    NASA Astrophysics Data System (ADS)

    Dong, Nai-ping; Liang, Yi-zeng; Yi, Lun-zhao; Lu, Hong-mei

    2013-06-01

    A comprehensive investigation was performed to understand the influence of sequence scrambling in peptide ions on peptide identification results. To achieve this, four tandem mass spectrometry datasets with scrambled ions included and with them excluded were analyzed by Crux, X!Tandem, SpectraST, Lutefisk, and PepNovo. While the different algorithms differed in their performance, an increase in the number of correctly identified peptides was generally observed when removing scrambled ions, with the exception of the SpectraST algorithm. However, the variation of the match scores upon removal was unpredictable. Following these investigations, an interpretation was given on how the scrambled ions affect peptide identification. Lastly, a simulated theoretical mass spectral library derived from the NIST peptide Libraries was constructed and searched by SpectraST to study whether scrambled ions in predicted mass spectra could affect peptide identification. Consistent with the peptide library search results, no significant variations for dot product scores as well as peptide identification results were observed when these ions were included in the theoretical MS/MS spectra. From the five adopted algorithms, the SpectraST and Crux provided the most robust results, whereas X!Tandem, PepNovo, and Lutefisk were sensitive to the existence of the scrambled ions, especially the latter two de novo sequencing algorithms.

  8. Stored waveform inverse Fourier transform (SWIFT) ion excitation in trapped-ion mass spectometry: Theory and applications

    NASA Astrophysics Data System (ADS)

    Guan, Shenheng; Marshall, Alan G.

    1996-12-01

    Stored waveform excitation produced by inverse Fourier transformation of a specified magnitude/phase excitation spectrum offers the most general and versatile means for broadband mass-selective excitation and ejection in Penning (FT-ICR) and Paul (quadrupole) ion trap mass spectrometry. Since the last comprehensive review of SWIFT excitation in 1987, the technique has been adopted, modified, and extended widely in both the ICR and quadrupole ion trap communities. Here, we review the principles, variations, algorithms, hardware implementation, and some applications of SWIFT for both ICR and quadrupole ion trap mass spectrometry. We show that the most desirable SWIFT waveform is that optimized to reduce both the time-domain SWIFT maximum amplitude and the amplitude near the start and end of the SWIFT waveform. We examine the "true" magnitude excitation spectrum, obtained by zero-filling and forward Fourier transforming the SWIFT time-domain waveform, in order to evaluate the trade-off between spectral magnitude uniformity and frequency (mass) selectivity. Apodization of the SWIFT waveform is optimally conducted by smoothing the excitation magnitude spectrum prior to generation of the SWIFT waveform by inverse FT. When (as for broadband ejection in a quadrupole ion trap) it is important that ions be excited near-simultaneously over a wide mass range, the phase spectrum (before inverse FT to generate the SWIFT waveform) may be overmodulated or randomly modulated ("filtered noise field"), with the recognition that very substantial non-uniformity in the "true" excitation magnitude spectrum will result.

  9. Fourier Analysis Method for Analyzing Highly Congested Mass Spectra of Ion Populations with Repeated Subunits.

    PubMed

    Cleary, Sean P; Thompson, Avery M; Prell, James S

    2016-06-21

    Highly heterogeneous samples that are difficult to resolve chromatographically arise in many contexts, including hetero-oligomeric protein assemblies, chaperone-target and protein-lipid assemblies, and long-chain polymers. Native mass spectrometry has emerged as a powerful tool to probe the stoichiometry and structure of biomolecular ion complexes, including megadalton-sized assemblies and assemblies with dozens of subunits. However, mass spectra of these ions are often highly congested, obfuscating determination of charge state, total mass, or subunit mass with conventional analysis methods. Here, we present a fast Fourier transform-based algorithm that can be used to deconvolve highly congested mass spectra for heterogeneous ion populations with repeated subunits. The method is parameter-free and requires no initial guesses of charge states, total mass, or subunit mass. To demonstrate a range of applications, the method is applied to ubiquitin with multiple adductions of sodium and potassium, single and mixed polymers, and self-assembled native protein-lipid complexes (Nanodiscs). The algorithm facilitates identification of the charge states, subunit mass, and charge-state specific total mass distribution present in the ion population. Results from application of the algorithm to these analytes include the first reported mass spectra and lipid stoichiometries of intact Nanodiscs containing lipid-raft associated sphingomyelin. Advantages to using this method with ion assemblies that have undergone minimal gas-phase collisional "clean-up" to retain native-like stoichiometries are discussed. PMID:27213759

  10. Bennett ion mass spectrometers on the Pioneer Venus Bus and Orbiter

    NASA Technical Reports Server (NTRS)

    Taylor, H. A., Jr.; Brinton, H. C.; Wagner, T. C. G.; Blackwell, B. H.; Cordier, G. R.

    1980-01-01

    Identical Bennett radio-frequency ion mass spectrometer instruments on the Pioneer Venus Bus and Orbiter have provided the first in-situ measurements of the detailed composition of the planet's ionosphere. The sensitivity, resolution, and dynamic range are sufficient to provide measurements of the solar-wind-induced bow-shock, the ionopause, and highly structured distributions of up to 16 thermal ion species within the ionosphere. The use of adaptive scan and detection circuits and servo-controlled logic for ion mass and energy analysis permits detection of ion concentrations as low as 5 ions/cu cm and ion flow velocities as large as 9 km/sec for O(+). A variety of commandable modes provides ion sampling rates ranging from 0.1 to 1.6 sec between measurements of a single constituent. A lightweight sensor and electronics housing are features of a compact instrument package.

  11. On the structural denaturation of biological analytes in trapped ion mobility spectrometry - mass spectrometry.

    PubMed

    Liu, Fanny C; Kirk, Samuel R; Bleiholder, Christian

    2016-06-01

    Key to native ion mobility/mass spectrometry is to prevent the structural denaturation of biological molecules in the gas phase. Here, we systematically assess structural changes induced in the protein ubiquitin during a trapped ion mobility spectrometry (TIMS) experiment. Our analysis shows that the extent of structural denaturation induced in ubiquitin ions is largely proportional to the amount of translational kinetic energy an ion gains from the applied electric field between two collisions with buffer gas particles. We then minimize the efficiency of the structural denaturation of ubiquitin ions in the gas phase during a TIMS experiment. The resulting "soft" TIMS spectra of ubiquitin are found largely identical to those observed on "soft" elevated-pressure ion mobility drift tubes and the corresponding calibrated cross sections are consistent with structures reported from NMR experiments for the native and A-state of ubiquitin. Thus, our analysis reveals that TIMS is useful for native ion mobility/mass spectrometry analysis. PMID:26998732

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

    PubMed

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

    2015-03-01

    A compact time-of-flight mass spectrometer with overall dimension of about 413 × 250 × 414 mm based on orthogonal injection and angle reflection has been developed for ion source characterization. Configuration and principle of the time-of-flight mass spectrometer are introduced in this paper. The mass resolution is optimized to be about 1690 (FWHM), and the ion energy detection range is tested to be between about 3 and 163 eV with the help of electron impact ion source. High mass resolution and compact configuration make this spectrometer useful to provide a valuable diagnostic for ion spectra fundamental research and study the mass to charge composition of plasma with wide range of parameters. PMID:25832275

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

    SciTech Connect

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

    2015-03-15

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

  14. Enhancing Secondary Ion Yields in Time of Flight-Secondary Ion Mass Spectrometry Using Water Cluster Primary Beams

    PubMed Central

    2013-01-01

    Low secondary ion yields from organic and biological molecules are the principal limitation on the future exploitation of time of flight-secondary ion mass spectrometry (TOF-SIMS) as a surface and materials analysis technique. On the basis of the hypothesis that increasing the density of water related fragments in the ion impact zone would enhance proton mediated reactions, a prototype water cluster ion beam has been developed using supersonic jet expansion methodologies that enable ion yields using a 10 keV (H2O)1000+ beam to be compared with those obtained using a 10 keV Ar1000+ beam. The ion yields from four standard compounds, arginine, haloperidol, DPPC, and angiotensin II, have been measured under static+ and high ion dose conditions. Ion yield enhancements relative to the argon beam on the order of 10 or more have been observed for all the compounds such that the molecular ion yield per a 1 μm pixel can be as high as 20, relative to 0.05 under an argon beam. The water beam has also been shown to partially lift the matrix effect in a 1:10 mixture of haloperidol and dipalmitoylphosphatidylcholine (DPPC) that suppresses the haloperidol signal. These results provide encouragement that further developments of the water cluster beam to higher energies and larger cluster sizes will provide the ion yield enhancements necessary for the future development of TOF-SIMS. PMID:23718847

  15. Composition measurements of the topside ionosphere using a magnetic mass spectrometer, ion mass spectrometer on ISIS-2 spacecraft

    NASA Technical Reports Server (NTRS)

    Hoffman, J. H.

    1975-01-01

    The ion mass spectrometer (IMS) on the ISIS-II satellite is described; it measures the composition and distribution of positive ions in the earth's ionosphere in the mass range of 1 to 64 atomic mass units. Significant data were received which show a wide variation in ion composition at night near the equator and in the daytime poleward of the plasmapause. It was found that these data enable further study of the polar wind and that the experiment produced timely data during the August, 1972 magnetic storm to show the development of a unique ionosphere above the plasmapause during the period of the storm. The scientific objectives and results of the experiment, the technical description of the instrument, a bibliography with sample papers attached, and a summary of recommendations for further study are presented.

  16. DeconMSn: A Software Tool for accurate parent ion monoisotopic mass determination for tandem mass spectra

    SciTech Connect

    Mayampurath, Anoop M.; Jaitly, Navdeep; Purvine, Samuel O.; Monroe, Matthew E.; Auberry, Kenneth J.; Adkins, Joshua N.; Smith, Richard D.

    2008-04-01

    We present a new software tool for tandem MS analyses that: • accurately calculates the monoisotopic mass and charge of high–resolution parent ions • accurately operates regardless of the mass selected for fragmentation • performs independent of instrument settings • enables optimal selection of search mass tolerance for high mass accuracy experiments • is open source and thus can be tailored to individual needs • incorporates a SVM-based charge detection algorithm for analyzing low resolution tandem MS spectra • creates multiple output data formats (.dta, .MGF) • handles .RAW files and .mzXML formats • compatible with SEQUEST, MASCOT, X!Tandem

  17. Ion chromatography/mass spectrometry for the determination of organic ammonium and sulfate compounds

    SciTech Connect

    Conboy, J.J.; Henion, J.D. ); Martin, M.W.; Zweigenbaum, J.A. )

    1990-04-15

    The ion spray liquid chromatography/mass spectrometry (LC/MS) interface is coupled via a postsuppressor split with an ion chromatography (IC) system. The micromembrane suppressor selectively removes over 99.9% of the ion-pair agents required for ion chromatography from the eluent. The resulting solution consists of analyte, organic modifier, and water, which is compatible with ion evaporation mass spectrometry. A flow rate of 0.8 or 1.0 mL/min from the column was split after suppression such that approximately 10-20 {mu}L/min was directed to the ion spray LC/MS interface, which was coupled to an atmospheric pressure ionization (API) mass spectrometer. This system provided a convenient way to effect isocratic and gradient separations of organic ions under chromatographic conditions incompatible with most forms of mass spectrometric ionization. This work describes the separation and positive ion detection of quaternary ammonium drugs and tetraalkylammonium compounds of industrial importance using both single and tandem mass spectrometric detection (e.g., IC/MS and IC/MS/MS).

  18. High-resolution accurate mass measurements of biomolecules using a new electrospray ionization ion cyclotron resonance mass spectrometer.

    PubMed

    Winger, B E; Hofstadler, S A; Bruce, J E; Udseth, H R; Smith, R D

    1993-07-01

    A novel electrospray ionization/Fourier transform ion cyclotron resonance mass spectrometer based on a 7-T superconducting magnet was developed for high-resolution accurate mass measurements of large biomolecules. Ions formed at atmospheric pressure using electrospray ionization (ESI) were transmitted (through six differential pumping stages) to the trapped ion cell maintained below 10(-9) torr. The increased pumping speed attainable with cryopumping (> 10(5) L/s) allowed brief pressure excursions to above 10(-4) torr, with greatly enhanced trapping efficiencies and subsequent short pumpdown times, facilitating high-resolution mass measurements. A set of electromechanical shutters were also used to minimize the effect of the directed molecular beam produced by the ES1 source and were open only during ion injection. Coupled with the use of the pulsed-valve gas inlet, the trapped ion cell was generally filled to the space charge limit within 100 ms. The use of 10-25 ms ion injection times allowed mass spectra to be obtained from 4 fmol of bovine insulin (Mr 5734) and ubiquitin (Mr 8565, with resolution sufficient to easily resolve the isotopic envelopes and determine the charge states. The microheterogeneity of the glycoprotein ribonuclease B was examined, giving a measured mass of 14,898.74 Da for the most abundant peak in the isotopic envelope of the normally glycosylated protein (i.e., with five mannose and two N-acetylglucosamine residues (an error of approximately 2 ppm) and an average error of approximately 1 ppm for the higher glycosylated and various H3PO4 adducted forms of the protein. Time-domain signals lasting in excess of 80 s were obtained for smaller proteins, producing, for example, a mass resolution of more than 700,000 for the 4(+) charge state (m/z 1434) of insulin. PMID:24227643

  19. Mass- and energy-analyses of ions from plasma by means of a miniature Thomson spectrometer

    SciTech Connect

    Sadowski, M. J.; Czaus, K.; Malinowski, K.; Skladnik-Sadowska, E.; Zebrowski, J.

    2009-05-15

    The paper presents an improved version of a miniature mass-spectrometer of the Thomson-type, which has been adopted for ion analysis near the dense plasma region inside a vacuum chamber. Problems connected with the separation of ions from plasma streams are considered. Input diaphragms and pumping systems, needed to ensure good vacuum inside the analyzing region, are described. The application of the miniature Thomson-type analyzer is illustrated by ion parabolas recorded in plasma-focus facility and rod plasma injector experiment. A quantitative analysis of the recorded ion parabolas is presented. Factors influencing accuracy of the ion analysis are discussed and methods of the spectrometer calibration are described.

  20. Mass- and energy-analyses of ions from plasma by means of a miniature Thomson spectrometer

    NASA Astrophysics Data System (ADS)

    Sadowski, M. J.; Czaus, K.; Malinowski, K.; Skladnik-Sadowska, E.; Zebrowski, J.

    2009-05-01

    The paper presents an improved version of a miniature mass-spectrometer of the Thomson-type, which has been adopted for ion analysis near the dense plasma region inside a vacuum chamber. Problems connected with the separation of ions from plasma streams are considered. Input diaphragms and pumping systems, needed to ensure good vacuum inside the analyzing region, are described. The application of the miniature Thomson-type analyzer is illustrated by ion parabolas recorded in plasma-focus facility and rod plasma injector experiment. A quantitative analysis of the recorded ion parabolas is presented. Factors influencing accuracy of the ion analysis are discussed and methods of the spectrometer calibration are described.

  1. Nuclear point mass effects in the interaction of energetic ion with carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Ping; Yan, Long; Zhu, Zhi-Yong; Ma, Guo-Liang

    2016-03-01

    We have calculated deposited energies of various energetic ions in carbon nanotubes, to study nuclear point mass effects, with the help of a static Monte Carlo (MC) simulation program. As a result of nuclear point mass effects, we show that at the same incident energy, the ion-deposited energy maximizes, while its mass has intermediate mass values, such as 11B, 12C and 14N ion masses, under hundreds keV 4He, 11B, 12C, 14N, 20Ne, 28Si and 40Ar ion irradiations of a thin-walled carbon nanotube. We also show that at the same incident energy, the coordination defect number maximizes, while its mass has an intermediate mass (20Ne) value, under hundreds keV 4He, 20Ne and 40Ar ion irradiations of the thin-walled nanotube. We derive an ion-deposited energy formula to analyze these maximum phenomena, and compare the MC simulation results with the MD (molecular dynamics) ones.

  2. Comet Encke: Meteor metallic ion identification by mass spectrometer

    NASA Technical Reports Server (NTRS)

    Goldberg, R. A.; Aikin, A. C.

    1972-01-01

    Metal ions including Na-40(+), Mg-24(+), Si-28(+), K-39(+), Ca-40(+), Sc-45(+), Cr-52(+), Fe-56(+), and Ni-58(+) were detected in the upper atmosphere during the beta Taurids meteor shower. Abundances of these ions relative to Si(+) show agreement in most instances with chondrites. A notable exception is 45(+), which is Sc(+), is 100 times more abundant than neutral scandium found in chondrites.

  3. Comet encke: meteor metallic ion identification by mass spectrometer.

    PubMed

    Goldberg, R A; Aikin, A C

    1973-04-20

    Metal ions including 23(+) (Na(+)), 24(+) (Mg(+)) 28(+) (Si(+)), 39(+) (K(+)), 40(+) (Ca(+)), 45(+) (Sc(+)), 52(+) Cr(+)). 56(+) (Fe(+)), and 58(+) (Ni(+)) have been detected in the upper atmosphere during the period of the Beta Taurids meteor shower. The abundances of these ions relative to Si(+) show, agreement in most instances with abundances in chondrites. A notable exception is 45(+), which, if it is Sc(+), is 100 times more abundant than neutral scandium found in chondrites. PMID:17816288

  4. Fast ion mass spectrometry and charged particle spectrography investigations of transverse ion acceleration and beam-plasma interactions

    NASA Technical Reports Server (NTRS)

    Gibson, W. C.; Tomlinson, W. M.; Marshall, J. A.

    1987-01-01

    Ion acceleration transverse to the magnetic field in the topside ionosphere was investigated. Transverse acceleration is believed to be responsible for the upward-moving conical ion distributions commonly observed along auroral field lines at altitudes from several hundred to several thousand kilometers. Of primary concern in this investigation is the extent of these conic events in space and time. Theoretical predictions indicate very rapid initial heating rates, depending on the ion species. These same theories predict that the events will occur within a narrow vertical region of only a few hundred kilometers. Thus an instrument with very high spatial and temporal resolution was required; further, since different heating rates were predicted for different ions, it was necessary to obtain composition as well as velocity space distributions. The fast ion mass spectrometer (FIMS) was designed to meet these criteria. This instrument and its operation is discussed.

  5. Development and Evaluation of a Variable-Temperature Quadrupole Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Derkits, David; Wiseman, Alex; Snead, Russell F.; Dows, Martina; Harge, Jasmine; Lamp, Jared A.; Gronert, Scott

    2016-02-01

    A new, variable-temperature mass spectrometer system is described. By applying polyimide heating tape to the end-cap electrodes of a Bruker (Bremen, Germany) Esquire ion trap, it is possible to vary the effective temperature of the system between 40 and 100°C. The modification does not impact the operation of the ion trap and the heater can be used for extended periods without degradation of the system. The accuracy of the ion trap temperatures was assessed by examining two gas-phase equilibrium processes with known thermochemistry. In each case, the variable-temperature ion trap provided data that were in good accord with literature data, indicating the effective temperature in the ion trap environment was being successfully modulated by the changes in the set-point temperatures on the end-cap electrodes. The new design offers a convenient and effective way to convert commercial ion trap mass spectrometers into variable-temperature instruments.

  6. Development and Evaluation of a Variable-Temperature Quadrupole Ion Trap Mass Spectrometer.

    PubMed

    Derkits, David; Wiseman, Alex; Snead, Russell F; Dows, Martina; Harge, Jasmine; Lamp, Jared A; Gronert, Scott

    2016-02-01

    A new, variable-temperature mass spectrometer system is described. By applying polyimide heating tape to the end-cap electrodes of a Bruker (Bremen, Germany) Esquire ion trap, it is possible to vary the effective temperature of the system between 40 and 100°C. The modification does not impact the operation of the ion trap and the heater can be used for extended periods without degradation of the system. The accuracy of the ion trap temperatures was assessed by examining two gas-phase equilibrium processes with known thermochemistry. In each case, the variable-temperature ion trap provided data that were in good accord with literature data, indicating the effective temperature in the ion trap environment was being successfully modulated by the changes in the set-point temperatures on the end-cap electrodes. The new design offers a convenient and effective way to convert commercial ion trap mass spectrometers into variable-temperature instruments. PMID:26483183

  7. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers

    NASA Astrophysics Data System (ADS)

    Snyder, Dalton T.; Pulliam, Christopher J.; Wiley, Joshua S.; Duncan, Jason; Cooks, R. Graham

    2016-07-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection.

  8. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers

    NASA Astrophysics Data System (ADS)

    Snyder, Dalton T.; Pulliam, Christopher J.; Wiley, Joshua S.; Duncan, Jason; Cooks, R. Graham

    2016-03-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection.

  9. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers.

    PubMed

    Snyder, Dalton T; Pulliam, Christopher J; Wiley, Joshua S; Duncan, Jason; Cooks, R Graham

    2016-07-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. Graphical Abstract ᅟ. PMID:27032650

  10. DETERMINATION OF ELEMENTAL COMPOSITIONS FROM MASS PEAK PROFILES OF THE MOLECULAR ION (M) AND THE M + 1 AND M + 2 IONS

    EPA Science Inventory

    The relative abundances of M + 1 and M + 2 ions help to identify the elemental composition of the molecular ion (M). But scan speed, snesitiity, and resolution limitations of mass spectrometers have impeded determination of these abundances. Mass peak profiling from selected ion ...

  11. Mobility-Resolved Ion Selection in Uniform Drift Field Ion Mobility Spectrometry/Mass Spectrometry; Dynamic Switching in Structures for Lossless Ion Manipulations

    SciTech Connect

    Webb, Ian K.; Garimella, Venkata BS; Tolmachev, Aleksey V.; Chen, Tsung-Chi; Zhang, Xinyu; Cox, Jonathan T.; Norheim, Randolph V.; Prost, Spencer A.; Lamarche, Brian L.; Anderson, Gordon A.; Ibrahim, Yehia M.; Smith, Richard D.

    2014-10-07

    A Structures for Lossless Ion Manipulations (SLIM) module that allows ion mobility separations and the switching of ions between alternative drift paths is described. The SLIM switch component has a “Tee” configuration and allows switching of ions between a linear path and a 90-degree bend. By controlling switching times, ions can be deflected to an alternative channel as a function of their mobilities. In the initial evaluation the switch is used in a static mode and shown compatible with high performance ion mobility separations at 4 torr. In the “dynamic mode” we show that mobility-selected ions can be switched into the alternative channel, and that various ion species can be independently selected based on their mobilities for time-of-flight mass spectrometer (TOF MS) IMS detection and mass analysis. This development also provides the basis for e.g. the selection of specific mobilities for storage and accumulation, and key modules for the assembly of SLIM devices enabling much more complex sequences of ion manipulations.

  12. Solution-phase secondary-ion mass spectrometry of protonated amino acids.

    PubMed

    Pettit, G R; Cragg, G M; Holzapfel, C W; Tuinman, A A; Gieschen, D P

    1987-04-01

    Although sulfolane proved unexpectedly to be a poor solvent for solution-phase secondary-ion mass spectrometry of underivatized amino acids in the presence of thallium(I) salts, glycerol was somewhat more effective. Also, the addition of trifluoromethanesulfonic acid proved more effective than addition of the metal in generating molecular ion complexes. A convenient and reliable method for rapidly determining amino acid molecular ions is based on these observations. PMID:3037939

  13. Cluster ion distributions and correlation with fragment valence in laser-induced mass spectra of oxides

    SciTech Connect

    Michiels, E.; Bijbels, R.

    1984-06-01

    Laser microprobe mass analysis (LAMMA) spectra are described for binary oxides belonging to different groups in the periodic table. The positive and negative cluster ion distributions show a strong correlation with the valence electron configuration of the metal in the oxide. The bond dissociation energy of the MO/sup +/ ion also affects the intensity distributions. 20 references, 10 figures.

  14. COLLISIONAL ACTIVATION MASS SPECTRA OF M-. IONS OF AZO DYES CONTAINING 2-NAPHTHOL

    EPA Science Inventory

    Collisionally activated decomposition mass spectra of M- ions of azo dyes are presented. he compounds are of general structure Ar(l)-N=N-Ar(2), where Ar(l) is substituted phenyl and Ar(2) is 2-naphthol. Characteristic fragment ions observed include m/z 157, which corresponds to t...

  15. Submicron mass spectrometry imaging of single cells by combined use of mega electron volt time-of-flight secondary ion mass spectrometry and scanning transmission ion microscopy

    SciTech Connect

    Siketić, Zdravko; Bogdanović Radović, Ivančica; Jakšić, Milko; Popović Hadžija, Marijana; Hadžija, Mirko

    2015-08-31

    In order to better understand biochemical processes inside an individual cell, it is important to measure the molecular composition at the submicron level. One of the promising mass spectrometry imaging techniques that may be used to accomplish this is Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS), using MeV energy heavy ions for excitation. MeV ions have the ability to desorb large intact molecules with a yield that is several orders of magnitude higher than conventional SIMS using keV ions. In order to increase the spatial resolution of the MeV TOF-SIMS system, we propose an independent TOF trigger using a STIM (scanning transmission ion microscopy) detector that is placed just behind the thin transmission target. This arrangement is suitable for biological samples in which the STIM detector simultaneously measures the mass distribution in scanned samples. The capability of the MeV TOF-SIMS setup was demonstrated by imaging the chemical composition of CaCo-2 cells.

  16. Enhancement of low-mass dileptons in heavy ion collisions

    SciTech Connect

    Li, G.Q.; Ko, C.M.; Brown, G.E. |

    1995-11-27

    Using a relativistic transport model for the expansion stage of S+Au collisions at 200 GeV/nucleon, we show that the recently observed enhancement of low-mass dileptons by the CERES Collaboration can be explained by the decrease of vector meson masses in hot and dense hadronic matter. {copyright} {ital 1995} {ital The} {ital American} {ital Physical} {ital Society}.

  17. Mass Spectrometric Collisional Activation and Product Ion Mobility of Human Serum Neutral Lipid Extracts

    PubMed Central

    Hankin, Joseph A.; Barkley, Robert M.; Zemski-Berry, Karin; Deng, Yiming; Murphy, Robert C.

    2016-01-01

    A novel method for lipid analysis called CTS (collisional activation and traveling wave mass spectrometry) involving tandem mass spectrometry of all precursor ions with ion mobility determinations of all product ions was applied to a sample of human serum. The resulting four dimensional data set (precursor ion, product ion, ion mobility values, and intensity) was found to be useful for characterization of lipids as classes as well as identification of specific species. Utilization of ion mobility measurements of the product ions is a novel approach for lipid analysis. The trends and patterns of product mobility values when visually displayed yield information on lipid classes and specific species independent of mass determination. The collection of a comprehensive set of data that incorporates all precursor-product relationships combined with ion mobility measurements of all products enables data analysis where different molecular properties can be juxtaposed and analyzed to assist with class and species identification. Overall, CTS is powerful, specific, and comprehensive method for lipid analysis. PMID:27213895

  18. A quadrupole ion trap with cylindrical geometry operated in the mass-selective instability mode.

    PubMed

    Wells, J M; Badman, E R; Cooks, R G

    1998-02-01

    A cylindrical geometry ion trap is used to record mass spectra in the mass-selective instability mode. The geometry of the cylindrical ion trap has been optimized to maximize the quadrupole field component relative to the higher-order field content through field calculations using the Poisson/Superfish code and through experimental variation of the electrode structure. The results correspond well with predictions of the calculations. The trap has been used to record mass spectra with better than unit mass resolution, high sensitivity, and a mass/charge range of ∼600 Th. Multistage (MS(3)) experiments have been performed, and the Mathieu stability region has been experimentally mapped. The performance of this device compares satisfactorily with that of the hyperbolic ion trap. PMID:21644742

  19. 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer: A National Resource for Ultrahigh Resolution Mass Analysis.

    PubMed

    Hendrickson, Christopher L; Quinn, John P; Kaiser, Nathan K; Smith, Donald F; Blakney, Greg T; Chen, Tong; Marshall, Alan G; Weisbrod, Chad R; Beu, Steven C

    2015-09-01

    We describe the design and initial performance of the first 21 tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The 21 tesla magnet is the highest field superconducting magnet ever used for FT-ICR and features high spatial homogeneity, high temporal stability, and negligible liquid helium consumption. The instrument includes a commercial dual linear quadrupole trap front end that features high sensitivity, precise control of trapped ion number, and collisional and electron transfer dissociation. A third linear quadrupole trap offers high ion capacity and ejection efficiency, and rf quadrupole ion injection optics deliver ions to a novel dynamically harmonized ICR cell. Mass resolving power of 150,000 (m/Δm(50%)) is achieved for bovine serum albumin (66 kDa) for a 0.38 s detection period, and greater than 2,000,000 resolving power is achieved for a 12 s detection period. Externally calibrated broadband mass measurement accuracy is typically less than 150 ppb rms, with resolving power greater than 300,000 at m/z 400 for a 0.76 s detection period. Combined analysis of electron transfer and collisional dissociation spectra results in 68% sequence coverage for carbonic anhydrase. The instrument is part of the NSF High-Field FT-ICR User Facility and is available free of charge to qualified users. PMID:26091892

  20. 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometer: A National Resource for Ultrahigh Resolution Mass Analysis

    NASA Astrophysics Data System (ADS)

    Hendrickson, Christopher L.; Quinn, John P.; Kaiser, Nathan K.; Smith, Donald F.; Blakney, Greg T.; Chen, Tong; Marshall, Alan G.; Weisbrod, Chad R.; Beu, Steven C.

    2015-09-01

    We describe the design and initial performance of the first 21 tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The 21 tesla magnet is the highest field superconducting magnet ever used for FT-ICR and features high spatial homogeneity, high temporal stability, and negligible liquid helium consumption. The instrument includes a commercial dual linear quadrupole trap front end that features high sensitivity, precise control of trapped ion number, and collisional and electron transfer dissociation. A third linear quadrupole trap offers high ion capacity and ejection efficiency, and rf quadrupole ion injection optics deliver ions to a novel dynamically harmonized ICR cell. Mass resolving power of 150,000 ( m/Δm 50% ) is achieved for bovine serum albumin (66 kDa) for a 0.38 s detection period, and greater than 2,000,000 resolving power is achieved for a 12 s detection period. Externally calibrated broadband mass measurement accuracy is typically less than 150 ppb rms, with resolving power greater than 300,000 at m/z 400 for a 0.76 s detection period. Combined analysis of electron transfer and collisional dissociation spectra results in 68% sequence coverage for carbonic anhydrase. The instrument is part of the NSF High-Field FT-ICR User Facility and is available free of charge to qualified users.

  1. 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

  2. Tracing the atomic mass unit to the kilogram by ion accumulation

    NASA Astrophysics Data System (ADS)

    Gläser, Michael

    2003-12-01

    An experimental approach for linking the atomic mass unit to the kilogram with an uncertainty sufficiently small for a future re-definition of the kilogram is described. The concept consists of accumulation of ions from an ion beam up to a weighable mass and measurable total charge. The main problems and influencing factors connected with ion beam technology, weighing and current measurement together with the corresponding experimental solutions are discussed in detail. The first experiments with consistent results, but still large uncertainty, are described.

  3. Experimental investigations of trimer ion contributions in the low resolution mass spectrometry of hydrogen isotope mixtures.

    PubMed

    Bidica, Nicolae

    2012-01-01

    This paper reports on some preliminary experimental results of a work in progress regarding a problem involving the quantitative analysis of hydrogen isotopes by mass spectrometry of low resolution: the triatomic (trimer) ions interferences with the isotopic hydrogen species having the same mass/charge. These results indicate that, in complex mixtures of hydrogen isotopes, trimer ions are strongly affected by the presence of other species, and a new approach that takes into account the destruction mechanism of trimer ions is necessary for a proper determination of their contributions. PMID:23149602

  4. Secondary ion counting for surface-sensitive chemical analysis of organic compounds using time-of-flight secondary ion mass spectroscopy with cluster ion impact ionization

    SciTech Connect

    Hirata, K.; Saitoh, Y.; Chiba, A.; Yamada, K.; Takahashi, Y.; Narumi, K.

    2011-03-15

    We report suitable secondary ion (SI) counting for surface-sensitive chemical analysis of organic compounds using time-of-flight (TOF) SI mass spectroscopy, based on considerably higher emission yields of SIs induced by cluster ion impact ionization. A SI counting system for a TOF SI mass spectrometer was developed using a fast digital storage oscilloscope, which allows us to perform various types of analysis as all the signal pulses constituting TOF SI mass spectra can be recorded digitally in the system. Effects of the SI counting strategy on SI mass spectra were investigated for C{sub 8} and C{sub 60} cluster ion impacts on an organically contaminated silicon wafer and on polytetrafluoroethylene targets by comparing TOF SI mass spectra obtained from the same recorded signals with different SI counting procedures. Our results show that the use of a counting system, which can cope with high SI yields, is necessary for quantitative analysis of SI mass spectra obtained under high SI yield per impact conditions, including the case of cluster ion impacts on organic compounds.

  5. Rocket-borne Ion Mass Spectrometer for the Mesosphere That is Pumped by Rocket Aerodynamics

    NASA Astrophysics Data System (ADS)

    Sternovsky, Zoltan; Smith, Steven; Robertson, Scott

    The mesospheric region close to the mesopause is populated by electrons, ions and aerosol particles. The number density of aerosol particles may exceed that of the background plasma creating conditions where the free electron density is reduced. Understanding the full charge balance of the region requires the simultaneous detection of electrons, charged aerosol particles and ions. Rocket borne instruments for the measurement of electrons and aerosols are readily available. Mass spectrometers for ions have been flown that were evacuated by cryogenic vacuum pumps with liquid helium or neon. There have not been flights since 1993 because these instruments required expensive deliveries of cryogens and frequent refilling. Advances in (1) aerodynamic modeling, (2) mass spectrometer design, and (3) ion detection technology make possible a new approach to mass spectrometry in the mesosphere in which the spectrometer is pumped by the flow around the rocket. A miniature Rotating Field Mass Analyzer (RFMS) is presented that is suitable for the measurement of ions in from 70 km upward. RFMS has a 2 x 2 x 20 mm3 velocity selection cell and utilizes and advanced ion detector that is capable of single ions operation mode at these altitudes. The instrument is pumped by the aerodynamic effect of the supersonic payload. A prototype version of RFMS is under laboratory testing.

  6. ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS BY ION TRAP TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to...

  7. Ion-retarding lens improves the abundance sensitivity of tandem mass spectrometers

    NASA Technical Reports Server (NTRS)

    Kaiser, K. A.; Stevens, C. M.

    1969-01-01

    Ion-retarding lens which increases the abundance sensitivity of tandem magnetic-analyzer mass spectrometers measures isotopes of low abundance in mass positions adjacent to isotopes of high abundance. The lens increases the abundance sensitivity for isotopes lying farther from high abundance isotopes than the energy cutoff of the lens.

  8. INFLUENCE OF EXPERIMENTAL CONDITIONS ON THE LIQUID SECONDARY ION MASS SPECTRA OF SULFONATED AZO DYES

    EPA Science Inventory

    Two monosulfonated and eight disulfonated azo dyes of varying relative molecular mass were examined by liquid secondary ion mass spectrometry (LSIMS). he effects of matrix, concentration, primary beam energy, and mode of operation were addressed in order to optimize sample ioniza...

  9. MASS MEASUREMENTS BY AN ACCURATE AND SENSITIVE SELECTED ION RECORDING TECHNIQUE

    EPA Science Inventory

    Trace-level components of mixtures were successfully identified or confirmed by mass spectrometric accurate mass measurements, made at high resolution with selected ion recording, using GC and LC sample introduction. Measurements were made at 20 000 or 10 000 resolution, respecti...

  10. Angular emission of ions and mass deposition from femtosecond and nanosecond laser-produced plasmas

    SciTech Connect

    Verhoff, B.; Harilal, S. S.; Hassanein, A.

    2012-06-15

    We investigated the angular distribution of ions and atoms emanating from femto- and nanosecond laser-produced metal plasmas under similar laser fluence conditions. For producing plasmas, aluminum targets are ablated in vacuum employing pulses from a Ti:Sapphire ultrafast laser (40 fs, 800 nm) and an Nd:YAG laser (6 ns, 1064 nm). The angular distribution of ion emission as well as the kinetic energy distribution is characterized by a Faraday cup, while a quartz microbalance is used for evaluating deposited mass. The ion and deposited mass features showed that fs laser ablated plasmas produced higher kinetic energy and more mass per pulse than ns plumes over all angles. The ion flux and kinetic energy studies show fs laser plasmas produce narrower angular distribution while ns laser plasmas provide narrower energy distribution.

  11. Vacuum Ultraviolet Photodissociation and Fourier Transform-Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry: Revisited.

    PubMed

    Shaw, Jared B; Robinson, Errol W; Paša-Tolić, Ljiljana

    2016-03-15

    We revisited the implementation of 193 nm ultraviolet photodissociation (UVPD) within the ion cyclotron resonance (ICR) cell of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. UVPD performance characteristics were examined in the context of recent developments in the understanding of UVPD and in-cell tandem mass spectrometry. Efficient UVPD and photo-ECD of a model peptide and proteins within the ICR cell of a FT-ICR mass spectrometer are accomplished through appropriate modulation of laser pulse timing, relative to ion magnetron motion and the potential applied to an ion optical element upon which photons impinge. It is shown that UVPD yields efficient and extensive fragmentation, resulting in excellent sequence coverage for model peptide and protein cations. PMID:26882021

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

    SciTech Connect

    Whitten, W.B.

    2002-12-18

    This report covers the three main projects that collectively comprised the Advanced Ion Trap Mass Spectrometry Program. Chapter 1 describes the direct interrogation of individual particles by laser desorption within the ion trap mass spectrometer analyzer. The goals were (1) to develop an ''intelligent trigger'' capable of distinguishing particles of biological origin from those of nonbiological origin in the background and interferent particles and (2) to explore the capability for individual particle identification. Direct interrogation of particles by laser ablation and ion trap mass spectrometry was shown to have good promise for discriminating between particles of biological origin and those of nonbiological origin, although detailed protocols and operating conditions were not worked out. A library of more than 20,000 spectra of various types of biological particles has been assembled. Methods based on multivariate analysis and on neural networks were used to discriminate between particles of biological origin and those of nonbiological origin. It was possible to discriminate between at least some species of bacteria if mass spectra of several hundred similar particles were obtained. Chapter 2 addresses the development of a new ion trap mass analyzer geometry that offers the potential for a significant increase in ion storage capacity for a given set of analyzer operating conditions. This geometry may lead to the development of smaller, lower-power field-portable ion trap mass spectrometers while retaining laboratory-scale analytical performance. A novel ion trap mass spectrometer based on toroidal ion storage geometry has been developed. The analyzer geometry is based on the edge rotation of a quadrupolar ion trap cross section into the shape of a torus. Initial performance of this device was poor, however, due to the significant contribution of nonlinear fields introduced by the rotation of the symmetric ion-trapping geometry. These nonlinear resonances

  13. Multidimensional Separation of Natural Products Using Liquid Chromatography Coupled to Hadamard Transform Ion Mobility Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Wenjie; Zhang, Xing; Knochenmuss, Richard; Siems, William F.; Hill, Herbert H.

    2016-05-01

    A high performance liquid chromatograph (HPLC)was interfaced to an atmospheric drift tube ion mobility time of flight mass spectrometry. The power of multidimensional separation was demonstrated using chili pepper extracts. The ambient pressure drift tube ion mobility provided high resolving powers up to 166 for the HPLC eluent. With implementation of Hadamard transform (HT), the duty cycle for the ion mobility drift tube was increased from less than 1% to 50%, and the ion transmission efficiency was improved by over 200 times compared with pulsed mode, improving signal to noise ratio 10 times. HT ion mobility and TOF mass spectrometry provide an additional dimension of separation for complex samples without increasing the analysis time compared with conventional HPLC.

  14. Multidimensional Separation of Natural Products Using Liquid Chromatography Coupled to Hadamard Transform Ion Mobility Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Wenjie; Zhang, Xing; Knochenmuss, Richard; Siems, William F.; Hill, Herbert H.

    2016-02-01

    A high performance liquid chromatograph (HPLC)was interfaced to an atmospheric drift tube ion mobility time of flight mass spectrometry. The power of multidimensional separation was demonstrated using chili pepper extracts. The ambient pressure drift tube ion mobility provided high resolving powers up to 166 for the HPLC eluent. With implementation of Hadamard transform (HT), the duty cycle for the ion mobility drift tube was increased from less than 1% to 50%, and the ion transmission efficiency was improved by over 200 times compared with pulsed mode, improving signal to noise ratio 10 times. HT ion mobility and TOF mass spectrometry provide an additional dimension of separation for complex samples without increasing the analysis time compared with conventional HPLC.

  15. Ion mobility tandem mass spectrometry enhances performance of bottom-up proteomics.

    PubMed

    Helm, Dominic; Vissers, Johannes P C; Hughes, Christopher J; Hahne, Hannes; Ruprecht, Benjamin; Pachl, Fiona; Grzyb, Arkadiusz; Richardson, Keith; Wildgoose, Jason; Maier, Stefan K; Marx, Harald; Wilhelm, Mathias; Becher, Isabelle; Lemeer, Simone; Bantscheff, Marcus; Langridge, James I; Kuster, Bernhard

    2014-12-01

    One of the limiting factors in determining the sensitivity of tandem mass spectrometry using hybrid quadrupole orthogonal acceleration time-of-flight instruments is the duty cycle of the orthogonal ion injection system. As a consequence, only a fraction of the generated fragment ion beam is collected by the time-of-flight analyzer. Here we describe a method utilizing postfragmentation ion mobility spectrometry of peptide fragment ions in conjunction with mobility time synchronized orthogonal ion injection leading to a substantially improved duty cycle and a concomitant improvement in sensitivity of up to 10-fold for bottom-up proteomic experiments. This enabled the identification of 7500 human proteins within 1 day and 8600 phosphorylation sites within 5 h of LC-MS/MS time. The method also proved powerful for multiplexed quantification experiments using tandem mass tags exemplified by the chemoproteomic interaction analysis of histone deacetylases with Trichostatin A. PMID:25106551

  16. Ion Mobility Tandem Mass Spectrometry Enhances Performance of Bottom-up Proteomics

    PubMed Central

    Helm, Dominic; Vissers, Johannes P. C.; Hughes, Christopher J.; Hahne, Hannes; Ruprecht, Benjamin; Pachl, Fiona; Grzyb, Arkadiusz; Richardson, Keith; Wildgoose, Jason; Maier, Stefan K.; Marx, Harald; Wilhelm, Mathias; Becher, Isabelle; Lemeer, Simone; Bantscheff, Marcus; Langridge, James I.; Kuster, Bernhard

    2014-01-01

    One of the limiting factors in determining the sensitivity of tandem mass spectrometry using hybrid quadrupole orthogonal acceleration time-of-flight instruments is the duty cycle of the orthogonal ion injection system. As a consequence, only a fraction of the generated fragment ion beam is collected by the time-of-flight analyzer. Here we describe a method utilizing postfragmentation ion mobility spectrometry of peptide fragment ions in conjunction with mobility time synchronized orthogonal ion injection leading to a substantially improved duty cycle and a concomitant improvement in sensitivity of up to 10-fold for bottom-up proteomic experiments. This enabled the identification of 7500 human proteins within 1 day and 8600 phosphorylation sites within 5 h of LC-MS/MS time. The method also proved powerful for multiplexed quantification experiments using tandem mass tags exemplified by the chemoproteomic interaction analysis of histone deacetylases with Trichostatin A. PMID:25106551

  17. Multidimensional Separation of Natural Products Using Liquid Chromatography Coupled to Hadamard Transform Ion Mobility Mass Spectrometry.

    PubMed

    Liu, Wenjie; Zhang, Xing; Knochenmuss, Richard; Siems, William F; Hill, Herbert H

    2016-05-01

    A high performance liquid chromatograph (HPLC)was interfaced to an atmospheric drift tube ion mobility time of flight mass spectrometry. The power of multidimensional separation was demonstrated using chili pepper extracts. The ambient pressure drift tube ion mobility provided high resolving powers up to 166 for the HPLC eluent. With implementation of Hadamard transform (HT), the duty cycle for the ion mobility drift tube was increased from less than 1% to 50%, and the ion transmission efficiency was improved by over 200 times compared with pulsed mode, improving signal to noise ratio 10 times. HT ion mobility and TOF mass spectrometry provide an additional dimension of separation for complex samples without increasing the analysis time compared with conventional HPLC. Graphical Abstract ᅟ. PMID:26914233

  18. GlycoMob: an ion mobility-mass spectrometry collision cross section database for glycomics.

    PubMed

    Struwe, Weston B; Pagel, Kevin; Benesch, Justin L P; Harvey, David J; Campbell, Matthew P

    2016-06-01

    Ion mobility mass spectrometry (IM-MS) is a promising analytical technique for glycomics that separates glycan ions based on their collision cross section (CCS) and provides glycan precursor and fragment masses. It has been shown that isomeric oligosaccharide species can be separated by IM and identified on basis of their CCS and fragmentation. These results indicate that adding CCSs information for glycans and glycan fragments to searchable databases and analysis pipelines will increase identification confidence and accuracy. We have developed a freely accessible database, GlycoMob ( http://www.glycomob.org ), containing over 900 CCSs values of glycans, oligosaccharide standards and their fragments that will be continually updated. We have measured the absolute CCSs of calibration standards, biologically derived and synthetic N-glycans ionized with various adducts in positive and negative mode or as protonated (positive ion) and deprotonated (negative ion) ions. PMID:26314736

  19. Searching For A Suitable Gas Ion Source For 14C Accelerator Mass Spectrometry

    SciTech Connect

    Reden, Karl von; Roberts, Mark; Han, Baoxi; Schneider, Robert; Wills, John

    2007-08-10

    This paper describes the challenges facing 14C Accelerator Mass Spectrometry (AMS) in the effort to directly analyze the combusted effluent of a chromatograph (or any other continuous source of sample material). An efficient, low-memory negative gas ion source would greatly simplify the task to make this a reality. We discuss our tests of a microwave ion source charge exchange canal combination, present an improved design, and hope to generate more interest in the negative ion source community to develop a direct-extraction negative carbon gas ion source for AMS.

  20. Broad spectrum drug screening using liquid chromatography-hybrid triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Stone, Judy

    2010-01-01

    Centrifuged urine, internal standard (promazine), and ammonium formate buffer are mixed in an autosampler vial to achieve a 10-fold dilution of the specimen. Without additional pretreatment, 10 microL of the sample is injected onto a C18 reverse phase column for gradient analysis with ammonium formate/acetonitrile mobile phases. Drugs in the column eluent become charged in the ion source using positive electrospray atmospheric pressure ionization. Pseudomolecular drug ions are analyzed by a hybrid triple quadrupole linear ion trap mass spectrometer operated with a 264-drug selected ion monitoring (SRM) acquisition method that includes an information-dependant acquisition (IDA) algorithm. PMID:20077072

  1. A feasibility study of ion implantation techniques for mass spectrometer calibration

    NASA Technical Reports Server (NTRS)

    Koslin, M. E.; Krycuk, G. A.; Schatz, J. G., Jr.; White, F. A.; Wood, G. M.

    1978-01-01

    An experimental study was undertaken to examine the feasibility of using ion-implanted filaments doped with either an alkali metal or noble gas for in situ recalibration of onboard mass spectrometers during extended space missions. Implants of rubidium and krypton in rhenium ribbon filaments were subsequently tested in a bakeable 60 deg sector mass spectrometer operating in the static mode. Surface ionization and electron impact ion sources were both used, each yielding satisfactory results. The metallic implant with subsequent ionization provided a means of mass scale calibration and determination of system operating parameters, whereas the noble gas thermally desorbed into the system was more suited for partial pressure and sensitivity determinations.

  2. Mass spectrometry on the nanoscale with ion sputtering based techniques: What is feasible

    NASA Astrophysics Data System (ADS)

    Veryovkin, Igor V.; Calaway, Wallis F.; Tripa, C. Emil; Pellin, Michael J.

    2007-08-01

    The potential of ion sputtering based mass spectrometry applied to materials characterization on the nanometer scale is discussed. Analytical approaches and required instrumental capabilities are outlined, and the current state-of-the-art is summarized. A new generation of analytical instruments specifically optimized for laser post-ionization secondary neutral mass spectrometry has been developed at Argonne National Laboratory (ANL). Experimentally verified (or anticipated after near-future upgrades) analytical capabilities of these instruments, capable of quantitative analysis at the nanometer-scale, are reported and compared to secondary ion mass spectrometry.

  3. Design and performance of an atmospheric pressure inlet system for lithium ion attachment mass spectrometry.

    PubMed

    Selvin, P Christopher; Iwase, Keiichiro; Fujii, Toshihiro

    2002-05-01

    We designed a simple and efficient inlet system to act as an interface between samples at atmospheric pressure and the high vacuum inside a mass spectrometer. The newly designed stainless steel orifice leak sample inlet system is simple and rugged and fulfills all the basic requirements. With this inlet system coupled with a lithium ion attachment mass spectrometer, it is possible to detect any chemical species at atmospheric pressure, including radical intermediates, on a real-time basis. For illustrative purposes, the sampling efficiency of the inlet probe coupled with a lithium ion attachment mass spectrometer is discussed for laboratory air and polyethylene pyrolysis. PMID:12033306

  4. Hybrid BEEQ tandem mass spectrometer for the study of ion/surface collision processes

    NASA Astrophysics Data System (ADS)

    Winger, B. E.; Laue, H.-J.; Horning, S. R.; Julian, R. K., Jr.; Lammert, S. A.; Riederer, D. E., Jr.; Cooks, R. G.

    1992-12-01

    A hybrid mass spectrometer consisting of a magnetic sector, two electric sectors, and a quadrupole mass filter (BEEQ) has been built for the study of polyatomic ion/surface collision phenomena over the energy range of a few electron volts to several keV. Primary ions are generated by electron ionization or by chemical ionization, and the first two sectors are used to deliver a monoenergetic beam of ions, of a selected mass-to-charge m/z ratio, to a decelerator which sets the desired collision energy. The target, which can be introduced into the system without breaking vacuum, is mounted on a goniometer and situated in an electrically shielded region in the center of a large scattering chamber which contains an electric sector and a quadrupole mass analyzer used for kinetic energy and mass measurements on the ejected ions. These analyzers rotate around the scattering center to allow selection of the scattering angle of ions leaving the surface. Ultimate pressures attainable in the main scattering chamber are below 10-9 Torr allowing molecular targets, such as self-assembled monolayers of alkyl thiols on gold, to be examined without surface contamination. Low-energy (20-100 eV) collisions of polyatomic ions are reported, and examples are given of the effects of collision energy and scattering angle on surface induced dissociation mass spectra. The kinetic energy of the inelastically scattered ions is also measured, and in some cases, the internal energy can be estimated, the two measurements together providing information on energy partitioning associated with surface collisions. For example, it is shown that n-butylbenzene molecular ions of 25 eV colliding with ferrocenyl-terminated self-assembled monolayer surfaces, rebound with 10 eV of recoil energy and 3 eV of internal energy. The remainder of the energy goes into the surface. The capability of the BEEQ instrument to provide data on ion/surface reactive collisions is also illustrated with reactions such as alkyl

  5. Imaging mass-spectrometer of ions for studying near-planetary plasma

    NASA Astrophysics Data System (ADS)

    Vaisberg, O. L.; Leibov, A. V.; Smirnov, V. N.; Avanov, L. A.; Bertelier, J.-J.; Torcar, K.; Leblan, F.; Babkin, V. F.; Grishin, V. A.; Baumjohann, V.; Escoubet, F.

    2006-05-01

    A numerical model of an ion mass-spectrometer is developed based on the new type of charged-particle analyzer CAMERA suggested previously [1 3]. The spectrometer provides for complete instantaneous imaging of the flux distribution of various ions in a hemisphere. Such a type of the mass-spectrometer is chosen, which allows one to analyze a conelike beam of ions at the exit of the CAMERA. The mathematical model of the CAMERA with this time-of-flight mass-analyzer ensures sufficiently high mass resolution (M/ΔM > 100) at conserved imaging capabilities of the CAMERA. Such an instrument can find a wide application both in magnetospheric studies and in studying various objects of the solar system.

  6. Electronics of an ion trap with integrated time-of-flight mass spectrometer

    NASA Astrophysics Data System (ADS)

    Schneider, Christian; Schowalter, Steven J.; Yu, Peter; Hudson, Eric R.

    2016-01-01

    Recently, we reported an ion trap experiment with an integrated time-of-flight mass spectrometer (TOFMS) [Phys. Rev. Appl. 2, 034013 (2014)] focussing on the improvement of mass resolution and detection limit due to sample preparation at millikelvin temperatures. The system utilizes a radio-frequency (RF) ion trap with asymmetric drive for storing and manipulating laser-cooled ions and features radial extraction into a compact $275$ mm long TOF drift tube. The mass resolution exceeds $m / \\Delta m = 500$, which provides isotopic resolution over the whole mass range of interest in current experiments and constitutes an improvement of almost an order of magnitude over other implementations. In this manuscript, we discuss the experimental implementation in detail, which is comprised of newly developed drive electronics for generating the required voltages to operate RF trap and TOFMS, as well as control electronics for regulating RF outputs and synchronizing the TOFMS extraction.

  7. 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

  8. Mass sensor for in situ monitoring of focused ion and electron beam induced processes

    SciTech Connect

    Friedli, Vinzenz; Santschi, Christian; Michler, Johann; Hoffmann, Patrik; Utke, Ivo

    2007-01-29

    A cantilever-based mass sensor for in situ monitoring of deposition and milling using focused ion and electron beams is presented. Carefully designed experiments allowed for mass measurements with a noise level of {+-}10 fg by tracking the resonance frequency of a temperature stabilized piezoresistive cantilever using phase locking. The authors report on measurements of precursor surface coverage, residence time, mass deposition rates, yields, and deposit density using the (CH{sub 3}){sub 3}PtCpCH{sub 3} precursor.

  9. Ion-stimulated mass transport in nanoscale morphology evolution

    NASA Astrophysics Data System (ADS)

    George, Henry Bola

    We observe temporal evolution of two distinct lateral length scales in surface topography following low energy, E, argon ion (Ar+) irradiation of Si(001). From real-space AFM topographs, we observe that the short-wavelength, lambda (high-wavenumber, q) evolve as nearly isotropic dots while the longer-lambda (low- q) features appear as isotropic "rings" at normal incidence and as anisotropic ripples at off-normal incidence with their wavevector orthogonal to the ion beam. We explain our results in terms of an interplay between smoothening by ion-enhanced viscous flow and roughening driven by ion sputtering (for high-q features) or elastic strain energy relief (for low- q features). Our proposed mechanisms also explain the weak temperature and flux dependence of both wavelengths. We also observe stable flat surfaces following irradiation at incidence angles greater than 20° from normal, E > 500 eV and temperature > 300°C. To explain non-diverging wavelengths as the smoothening boundary is approached, we present evidence that non-local terms are needed in the height evolution equation. We report the influence of pre-patterned boundaries in guiding ripples appearing during uniform irradiation at high temperatures. Compared to untemplated samples, we observe that the long-range order of the guided ripples is significantly enhanced. We develop a scalar figure of merit to characterize the degree of order of the patterns. We observe that templating is most efficient when the boundaries are separated by an integer multiple of the spontaneously arising wavelength. We report new observations following ion sculpting of nanopores. Among these are: (1) The formation of nanopores is not limited to insulators: we successfully close pores in other materials including silicon dioxide, amorphous silicon (semiconductor) and palladium silicide (metallic glass). (2) Pores retain "memory" of their initial radius: at the same instantaneous radius, pores that started off smaller require

  10. Optimization of an ion-to-photon detector for large molecules in mass spectrometry.

    PubMed

    Dubois; Knochenmuss; Zenobi

    1999-10-15

    Ion packets can be detected in time-of-flight mass spectrometry by collecting the photons that are produced during the impact of the packets with a scintillator. The photon yield is a function of the ion energy. It was found that post-acceleration of the particles in front of the scintillator was an efficient way of increasing signal intensities. For the same total ion energy, the intensities were larger with post-acceleration than when only increasing the initial ion kinetic energy. A venetian blind dynode, converting the primary ion beam into electrons/secondary ions, was also introduced. Positive or negative secondary particles produced on the dynode surface could be accelerated to the scintillator. Electrons were found to give the highest signals. Intensities similar to those measured with microchannel plates were found. The linearity and onset of saturation of the microchannel plates and the ion-to-photon detector were compared. At optimum operating conditions, the ion-to-photon detector gave around 10 times higher signals than the microchannel plates for heavy ions (150 kDa), with similar mass resolution. Copyright 1999 John Wiley & Sons, Ltd. PMID:10487943

  11. Imaging and Rapid-Scanning Ion Mass Spectrometer (IRM) for the CASSIOPE e-POP Mission

    NASA Astrophysics Data System (ADS)

    Yau, Andrew W.; Howarth, Andrew; White, Andrew; Enno, Greg; Amerl, Peter

    2015-06-01

    The imaging and rapid-scanning ion mass spectrometer (IRM) is part of the Enhanced Polar Outflow Probe (e-POP) instrument suite on the Canadian CASSIOPE small satellite. Designed to measure the composition and detailed velocity distributions of ions in the ˜1-100 eV/q range on a non-spinning spacecraft, the IRM sensor consists of a planar entrance aperture, a pair of electrostatic deflectors, a time-of-flight (TOF) gate, a hemispherical electrostatic analyzer, and a micro-channel plate (MCP) detector. The TOF gate measures the transit time of each detected ion inside the sensor. The hemispherical analyzer disperses incident ions by their energy-per-charge and azimuth in the aperture plane onto the detector. The two electrostatic deflectors may be optionally programmed to step through a sequence of deflector voltages, to deflect ions of different incident elevation out of the aperture plane and energy-per-charge into the sensor aperture for sampling. The position and time of arrival of each detected ion at the detector are measured, to produce an image of 2-dimensional (2D), mass-resolved ion velocity distribution up to 100 times per second, or to construct a composite 3D velocity distribution by combining successive images in a deflector voltage sequence. The measured distributions are then used to investigate ion composition, density, drift velocity and temperature in polar ion outflows and related acceleration and transport processes in the topside ionosphere.

  12. Hydrogen Attachment/Abstraction Dissociation (HAD) of Gas-Phase Peptide Ions for Tandem Mass Spectrometry.

    PubMed

    Takahashi, Hidenori; Sekiya, Sadanori; Nishikaze, Takashi; Kodera, Kei; Iwamoto, Shinichi; Wada, Motoi; Tanaka, Koichi

    2016-04-01

    Dissociation of gas-phase peptide ions through interaction with low-energy hydrogen (H) radical (∼0.15 eV) was observed with a quadrupole ion trap mass spectrometry. The H radical generated by thermal dissociation of H2 molecules passing through a heated tungsten capillary (∼2000 °C) was injected into the ion trap containing target peptide ions. The fragmentation spectrum showed abundant c-/z- and a-/x-type ions, attributable to H attachment/abstraction to/from peptide ion. Because the low-energy neutral H radical initiated the fragmentation, the charge state of the precursor ion was maintained during the dissociation. As a result, precursor ions of any charge state, including singly charged positive and negative ions, could be analyzed for amino acid sequence. The sequence coverage exceeding 90% was obtained for both singly protonated and singly deprotonated substance P peptide. This mass spectrometry also preserved labile post-translational modification bonds. The modification sites of triply phosphorylated peptide (kinase domain of insulin receptor) were identified with the sequence coverage exceeding 80%. PMID:27002918

  13. Incorporation of a Flared Inlet Capillary Tube on a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer.

    SciTech Connect

    Wu, Si; Zhang, Kai; Kaiser, Nathan K.; Bruce, James E.; Prior, David C.; Anderson, Gordon A.

    2006-04-17

    Atmospheric pressure ion sources such as electrospray ionization (ESI) and atmospheric pressure matrix assisted laser desorption ionization (AP-MALDI) are widely used with mass spectrometry for proteomics studies. Other newly developed atmospheric ion sources include desorption electrospray ionization (DESI). For these ionization methods, analyte ions created at atmospheric pressure are transferred to the high vacuum region for mass analysis after several stages of differential pumping. It has been reported that overall charge transmission between the ion source and the first vacuum stage is primarily dependent upon the proximity of the emitter and gas conductance of the interface inlet. We therefore developed an atmospheric pressure interface using flared inlet tubes. This report highlights our results obtained by coupling the customized flared inlet tubes with a Fourier transfer ion cyclotron resonance mass spectrometer (FT-ICRMS). We have also investigated the new interface with different types of atmospheric pressure ionization methods. For most of the ionization methods we investigated, such as ESI and DESI, increased ion current transmitted from the atmospheric pressure ion source to the first stage vacuum system was observed with the use of our enhanced ion inlet designs. The ion intensity that was detected with the flared inlet tube on a FT-ICRMS was also observed to increase {approx} 2-5 fold using ESI or DESI with the flared tube inlet. Moreover, increased spray tip positional tolerance was observed with implementation of the flared inlet tube. We also include our preliminary results obtained by coupling APMALDI with flared inlet tube in this paper. For AP-MALDI, the measured ion current transferred through the flared inlet tube was about 3 times larger than the ion current through the control non-flared inlet tube.

  14. Ion separation in imperfect fields of the quadrupole mass analyzer Part I. Ion beam dynamics in the phase-space

    NASA Astrophysics Data System (ADS)

    Titov, Vladimir V.

    1995-01-01

    The theoretical aspects of ion separation in imperfect fields of the quadrupole mass analyzer are discussed by applying analysis of the beam dynamics in a phase-space. The analytical method which uses an approximate solution of the Hill equation with a small heterogeneous part which indicates that the trap mechanism of ion separation is conditioned by the properties of characteristic solutions is improved. These solutions are reduced to an approximate solution in the form of a general solution of a homogeneous Mathieu equation with combined factors taking into account a small heterogeneous part which defines the region of beam capture (acceptance) in a phase-space. The estimation criterion of simulation accuracy is the relative deviation of an operating point on the Mathieu diagram from the top of a stability triangle. The infringement of independence principle of ion oscillations about each of the positional axes caused by distortions increases the cross-sectional area of the beam. The beam is cut out by the mass analyzer aperture. This causes transmission losses which depend on phase. Therefore, the ion current at the mass analyzer exit is amplitude modulated by the frequency of the alternate component of field. The maximum current is at zero phase. The modulation depth is proportional to the relative value of the distortions.

  15. The mass multiplet in Penning trap ion cyclotron resonance mass spectroscopy

    NASA Astrophysics Data System (ADS)

    Barlow, S. E.

    2007-01-01

    A model for the behavior of closely spaced masses—the "mass multiplet"—in a Penning trap mass spectrometer is developed. The model shows how these species separate from each other (or not) following resonant excitation, and gives quantitative criteria for mass separation. More surprisingly, the model shows the species tend to drift to different mean cyclotron radii. This latter effect undoubtedly plays a role in the problem of abundance determinations in Penning trap mass spectrometers.

  16. Probing effective nucleon masses with heavy-ion collisions

    NASA Astrophysics Data System (ADS)

    Coupland, D. D. S.; Youngs, M.; Chajecki, Z.; Lynch, W. G.; Tsang, M. B.; Zhang, Y. X.; Famiano, M. A.; Ghosh, T. K.; Giacherio, B.; Kilburn, M. A.; Lee, Jenny; Liu, H.; Lu, F.; Morfouace, P.; Russotto, P.; Sanetullaev, A.; Showalter, R. H.; Verde, G.; Winkelbauer, J.

    2016-07-01

    It has been generally accepted that momentum-dependent potentials for neutrons and protons at energies well away from the Fermi surface cause both to behave as if their inertial masses are effectively 70% of the vacuum values. This similarity in effective masses may no longer hold in dense neutron-rich regions within neutron stars, core-collapse supernovas, and nuclear collisions. There differences in the momentum-dependent symmetry potentials may cause neutron and proton effective masses to differ significantly. We investigate this effect by measuring the energy spectra of neutrons, protons, and charged particles emitted in 112Sn+112Sn and 124Sn+124Sn collisions at Ebeam/A =50 and 120 MeV with precision sufficient to distinguish, in principle, between effective interactions with very different values of the neutron and proton effective masses. These data and model comparisons point the way towards future advances in our capabilities to understand the density and momentum dependence of the nuclear symmetry energy.

  17. Double focusing ion mass spectrometer of cylindrical symmetry

    NASA Technical Reports Server (NTRS)

    Coplan, M. A.; Moore, J. H.; Hoffman, R. A.

    1984-01-01

    A mass spectrometer consisting of an electric sector followed by a magnetic sector is described. The geometry is a cylindrically symmetric generalization of the Mattauch-Herzog spectrometer (1934). With its large annular entrance aperture and a position-sensitive detector, the instrument provides a large geometric factor and 100-percent duty factor, making it appropriate for spacecraft experiments.

  18. Design of a Laser Ablation Ion Source for High-Precision Penning Trap Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Hunt, Curtis; Ratnayake, Ishara; Hawks, Paul; Bryce, Richard; Redshaw, Matthew

    2014-05-01

    High-precision atomic mass measurements provide important data for a wide range of fields including atomic, nuclear and neutrino physics, determination of fundamental constants, and metrology. At Central Michigan University we are building a Penning trap system that will utilize ions produced by external ion sources to allow access to a wide range of isotopes, including long-lived radioactive isotopes and isotopes with low natural abundances. The ions will be transported to a ``capture'' trap, before being transferred to double precision-measurement trap structure. In this poster we will present the design of a laser ablation ion source and the ion extraction and transport optics. We will report on the current status of the construction and operation of the ion source and the CMU Penning trap. This work supported in part by NSF award no. 1307233.

  19. False sugar sequence ions in electrospray tandem mass spectrometry of underivatized sialyl-Lewis-type oligosaccharides

    NASA Astrophysics Data System (ADS)

    Ernst, Beat; Müller, Dieter R.; Richter, Wilhelm J.

    1997-01-01

    Formation of "false" sugar sequence ions from branched tetrasaccharides of the sialyl-Lewis-type by migration of fucose towards sialic acid residues is shown to occur in [M + H]+ and [M + NH4]+ ions produced by electrospray ionization and subjected to low energy collision induced dissociation (CID). For the verification of their composition and sequence, such irregular ions were produced in the orifice region of the ion source, mass selected in Q1, and subjected to a second CID step in Q2 of a triple quadrupole analyser. When produced and analysed in the same "double CID" fashion, the branched B3 ions still containing all four sugar subunits show such migration to only a minor extent. The analysis of Bn fragment ions with high numbers for n may thus have advantages over the analysis of M-like species

  20. Heavy residues from very mass asymmetric heavy ion reactions

    SciTech Connect

    Hanold, K.A.

    1994-08-01

    The isotopic production cross sections and momenta of all residues with nuclear charge (Z) greater than 39 from the reaction of 26, 40, and 50 MeV/nucleon {sup 129}Xe + Be, C, and Al were measured. The isotopic cross sections, the momentum distribution for each isotope, and the cross section as a function of nuclear charge and momentum are presented here. The new cross sections are consistent with previous measurements of the cross sections from similar reaction systems. The shape of the cross section distribution, when considered as a function of Z and velocity, was found to be qualitatively consistent with that expected from an incomplete fusion reaction mechanism. An incomplete fusion model coupled to a statistical decay model is able to reproduce many features of these reactions: the shapes of the elemental cross section distributions, the emission velocity distributions for the intermediate mass fragments, and the Z versus velocity distributions. This model gives a less satisfactory prediction of the momentum distribution for each isotope. A very different model based on the Boltzman-Nordheim-Vlasov equation and which was also coupled to a statistical decay model reproduces many features of these reactions: the shapes of the elemental cross section distributions, the intermediate mass fragment emission velocity distributions, and the Z versus momentum distributions. Both model calculations over-estimate the average mass for each element by two mass units and underestimate the isotopic and isobaric widths of the experimental distributions. It is shown that the predicted average mass for each element can be brought into agreement with the data by small, but systematic, variation of the particle emission barriers used in the statistical model. The predicted isotopic and isobaric widths of the cross section distributions can not be brought into agreement with the experimental data using reasonable parameters for the statistical model.

  1. On the Benefits of Acquiring Peptide Fragment Ions at High Measured Mass Accuracy

    PubMed Central

    Scherl, Alexander; Shaffer, Scott A.; Taylor, Gregory K.; Hernandez, Patricia; Appel, Ron D.; Binz, Pierre-Alain; Goodlett, David R.

    2008-01-01

    The advantages and disadvantages of acquiring tandem mass spectra by collision-induced dissociation (CID) of peptides in linear ion trap – Fourier-transform hybrid instruments are described. These instruments offer the possibility to transfer fragment ions from the linear ion trap to the FT-based analyzer for analysis with both high resolution and high mass accuracy. In addition, performing CID during the transfer of ions from the linear ion trap (LTQ) to the FT analyzer is also possible in instruments containing an additional collision cell (i.e., the “C-trap” in the LTQ-Orbitrap), resulting in tandem mass spectra over the full m/z range and not limited by the ejection q value of the LTQ. Our results show that these scan modes have lower duty cycles than tandem mass spectra acquired in the LTQ with nominal mass resolution, and typically result in fewer peptide identifications during data-dependent analysis of complex samples. However, the higher measured mass accuracy and resolution provides more specificity and hence provides a lower false positive ratio for the same number of true positives during database search of peptide tandem mass spectra. In addition, the search for modified and unexpected peptides is greatly facilitated with this data acquisition mode. It is therefore concluded that acquisition of tandem mass spectral data with high measured mass accuracy and resolution is a competitive alternative to “classical” data acquisition strategies, especially in situations of complex searches from large databases, searches for modified peptides, or for peptides resulting from unspecific cleavages. PMID:18417358

  2. Application of mass-separated focused ion beams in nano-technology

    NASA Astrophysics Data System (ADS)

    Bischoff, L.

    2008-04-01

    FIB applications like writing ion implantation, ion beam mixing or ion beam synthesis in the μm- or nm range often require ion species other than gallium. Therefore alloy liquid metal ion sources (LMIS) have to be developed and applied in FIB tools. The energy distribution of ions emitted from an alloy LMIS is one of the crucial parameters for the performance of a FIB column. Different source materials like AuGe, AuSi, AuGeSi, CoNd, ErNi, ErFeNiCr, MnGe, GaBi, GaBiLi, SnPb, … were investigated with respect to the energy spread of the different ion species as a function of emission current, ion mass and emitter temperature. Different alloy LMIS's have been developed and used in the FZD - FIB system especially for writing implantation to fabricate sub-μm pattern without any lithographic steps. Co and various other ion species were applied to generate CoSi2 nano-structures, like dots and wires by ion beam synthesis or to manipulate the properties of magnetic films. Additionally, the possibility of varying the flux in the FIB by changing the pixel dwell-time can be used for the investigation of the radiation damage and dynamic annealing in Si, Ge and SiC at elevated implantation temperatures. Furthermore, a broad spectrum of ions was employed to study in a fast manner the sputtering process depending on temperature, angle of incidence and ion mass on a couple of target materials. These studies are important for the 3D-fabrication of various kinds of micro-tools by FIB milling.

  3. MAVEN Observations of Escaping Planetary Ions from the Martian Atmosphere: Mass, Velocity, and Spatial Distributions

    NASA Astrophysics Data System (ADS)

    Dong, Yaxue; Fang, Xiaohua; Brain, D. A.; McFadden, James P.; Halekas, Jasper; Connerney, Jack

    2015-04-01

    The Mars-solar wind interaction accelerates and transports planetary ions away from the Martian atmosphere through a number of processes, including ‘pick-up’ by electromagnetic fields. The MAVEN spacecraft has made routine observations of escaping planetary ions since its arrival at Mars in September 2014. The SupraThermal And Thermal Ion Composition (STATIC) instrument measures the ion energy, mass, and angular spectra. It has detected energetic planetary ions during most of the spacecraft orbits, which are attributed to the pick-up process. We found significant variations in the escaping ion mass and velocity distributions from the STATIC data, which can be explained by factors such as varying solar wind conditions, contributions of particles from different source locations and different phases during the pick-up process. We also study the spatial distributions of different planetary ion species, which can provide insight into the physics of ion escaping process and enhance our understanding of atmospheric erosion by the solar wind. Our results will be further interpreted within the context of the upstream solar wind conditions measured by the MAVEN Solar Wind Ion Analyzer (SWIA) instrument and the magnetic field environment measured by the Magnetometer (MAG) instrument. Our study shows that the ion spatial distribution in the Mars-Sun-Electric-Field (MSE) coordinate system and the velocity space distribution with respect to the local magnetic field line can be used to distinguish the ions escaping through the polar plume and those through the tail region. The contribution of the polar plume ion escape to the total escape rate will also be discussed.

  4. Reduced matrix effects for anionic compounds with paired ion electrospray ionization mass spectrometry.

    PubMed

    Guo, Hongyue; Breitbach, Zachary S; Armstrong, Daniel W

    2016-03-17

    It is well-known that matrix effects in high performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC-ESI-MS) can seriously compromise quantitative analysis and affect method reproducibility. Paired ion electrospray ionization (PIESI) mass spectrometry is an approach for analyzing ultra-low levels of anions in the positive ion mode. This approach uses a structurally optimized ion pairing reagent to post-column associate with the anionic analyte, subsequently forming positively charged complexes. These newly formed complex ions are often more surface-active as compared to either the native anion or the ion pairing reagent. No studies have examined whether or not the PIESI approach mitigates matrix effects. Consequently, a controlled study was done using five analytes in highly controlled and reproducible synthetic groundwater and urine matrices. In addition, two different mass spectrometers (linear ion trap and triple quadrupole) were used. Compared to the negative ion mode, the PIESI-MS approach was less susceptible to matrix effects when performed on two different MS platforms. Using PIESI-MS, less dilution of the sample is needed to eliminate ionization suppression which, in turn, permits lower limits of detection and quantitation. PMID:26920775

  5. Detections of lunar exospheric ions by the LADEE neutral mass spectrometer

    NASA Astrophysics Data System (ADS)

    Halekas, J. S.; Benna, M.; Mahaffy, P. R.; Elphic, R. C.; Poppe, A. R.; Delory, G. T.

    2015-07-01

    The Lunar Atmosphere and Dust Environment Explorer (LADEE) Neutral Mass Spectrometer (NMS), operating in ion mode, provides sensitive detections of ions from the lunar exosphere. By analyzing ion-mode data from the entire mission, utilizing Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon's Interaction with the Sun (ARTEMIS) plasma and magnetic field measurements to organize NMS data and eliminate background sources, we identify highly significant detections of lunar ions at mass per charge of 2, 4, 12, 20, 28, 39, and 40, moderately significant detections at 14 and 23, and weak detections at 24, 25, and 36. Unlike many previous observations of Moon-derived ions, an outward pointing viewing geometry ensures that these ions originate from the exosphere, rather than directly from the surface. For species with known neutral distributions, inferred ion production rates appear consistent with expectations for both magnitude and spatial distribution, assuming photoionization as the predominant source mechanism. Unexpected signals at mass per charge 12 and 28 suggest the presence of a significant exospheric population of carbon-bearing molecules.

  6. Evaluation of Ion Mobility-Mass Spectrometry for Comparative Analysis of Monoclonal Antibodies.

    PubMed

    Ferguson, Carly N; Gucinski-Ruth, Ashley C

    2016-05-01

    Analytical techniques capable of detecting changes in structure are necessary to monitor the quality of monoclonal antibody drug products. Ion mobility mass spectrometry offers an advanced mode of characterization of protein higher order structure. In this work, we evaluated the reproducibility of ion mobility mass spectrometry measurements and mobiligrams, as well as the suitability of this approach to differentiate between and/or characterize different monoclonal antibody drug products. Four mobiligram-derived metrics were identified to be reproducible across a multi-day window of analysis. These metrics were further applied to comparative studies of monoclonal antibody drug products representing different IgG subclasses, manufacturers, and lots. These comparisons resulted in some differences, based on the four metrics derived from ion mobility mass spectrometry mobiligrams. The use of collision-induced unfolding resulted in more observed differences. Use of summed charge state datasets and the analysis of metrics beyond drift time allowed for a more comprehensive comparative study between different monoclonal antibody drug products. Ion mobility mass spectrometry enabled detection of differences between monoclonal antibodies with the same target protein but different production techniques, as well as products with different targets. These differences were not always detectable by traditional collision cross section studies. Ion mobility mass spectrometry, and the added separation capability of collision-induced unfolding, was highly reproducible and remains a promising technique for advanced analytical characterization of protein therapeutics. Graphical Abstract ᅟ. PMID:26988372

  7. Evaluation of Ion Mobility-Mass Spectrometry for Comparative Analysis of Monoclonal Antibodies

    NASA Astrophysics Data System (ADS)

    Ferguson, Carly N.; Gucinski-Ruth, Ashley C.

    2016-05-01

    Analytical techniques capable of detecting changes in structure are necessary to monitor the quality of monoclonal antibody drug products. Ion mobility mass spectrometry offers an advanced mode of characterization of protein higher order structure. In this work, we evaluated the reproducibility of ion mobility mass spectrometry measurements and mobiligrams, as well as the suitability of this approach to differentiate between and/or characterize different monoclonal antibody drug products. Four mobiligram-derived metrics were identified to be reproducible across a multi-day window of analysis. These metrics were further applied to comparative studies of monoclonal antibody drug products representing different IgG subclasses, manufacturers, and lots. These comparisons resulted in some differences, based on the four metrics derived from ion mobility mass spectrometry mobiligrams. The use of collision-induced unfolding resulted in more observed differences. Use of summed charge state datasets and the analysis of metrics beyond drift time allowed for a more comprehensive comparative study between different monoclonal antibody drug products. Ion mobility mass spectrometry enabled detection of differences between monoclonal antibodies with the same target protein but different production techniques, as well as products with different targets. These differences were not always detectable by traditional collision cross section studies. Ion mobility mass spectrometry, and the added separation capability of collision-induced unfolding, was highly reproducible and remains a promising technique for advanced analytical characterization of protein therapeutics.

  8. Matrix-enhanced secondary ion mass spectrometry: The Alchemist's solution?

    NASA Astrophysics Data System (ADS)

    Delcorte, Arnaud

    2006-07-01

    Because of the requirements of large molecule characterization and high-lateral resolution SIMS imaging, the possibility of improving molecular ion yields by the use of specific sample preparation procedures has recently generated a renewed interest in the static SIMS community. In comparison with polyatomic projectiles, however, signal enhancement by a matrix might appear to some as the alchemist's versus the scientist's solution to the current problems of organic SIMS. In this contribution, I would like to discuss critically the pros and cons of matrix-enhanced SIMS procedures, in the new framework that includes polyatomic ion bombardment. This discussion is based on a short review of the experimental and theoretical developments achieved in the last decade with respect to the three following approaches: (i) blending the analyte with a low-molecular weight organic matrix (MALDI-type preparation procedure); (ii) mixing alkali/noble metal salts with the analyte; (iii) evaporating a noble metal layer on the analyte sample surface (organic molecules, polymers).

  9. Analysis of high-altitude planetary ion velocity space distributions detected by the Ion Mass Analyzer aboard Mars Express

    NASA Astrophysics Data System (ADS)

    Johnson, B. C.; Liemohn, M. W.; Fraenz, M.; Curry, S.; Mitchell, D. L.

    2012-12-01

    We present observations of planetary ion velocity space distributions from the Ion Mass Analyzer (IMA) onboard Mars Express (MEX). The magnetometer data from Mars Global Surveyor is used to obtain a rough estimate of the interplanetary magnetic field (IMF) orientation. Characteristic features of the velocity space distributions will be examined and discussed for orbits aligned with the convective electric field and those in the Mars terminator plane. This study will focus on the high (keV) energy ions, as well as the relative importance of a high-altitude magnetosheath source of escaping planetary ions. Furthermore, this paper will examine various methods for converting the IMA detector counts to species-specific fluxes. After mimicking the methods previously used by researchers, we apply each of these methods of species extraction to data collected during the same time intervals. We discuss the implications for planetary ion motion around Mars, using the details of the velocity space observations to better understand the solar wind interaction with Mars. Comparisons to virtual detections using a test particle simulation will also provide insight into ion origins and trajectories.

  10. Evaluation of Pulse Counting for the Mars Organic Mass Analyzer (MOMA) Ion Trap Detection Scheme

    NASA Technical Reports Server (NTRS)

    Van Amerom, Friso H.; Short, Tim; Brinckerhoff, William; Mahaffy, Paul; Kleyner, Igor; Cotter, Robert J.; Pinnick, Veronica; Hoffman, Lars; Danell, Ryan M.; Lyness, Eric I.

    2011-01-01

    The Mars Organic Mass Analyzer is being developed at Goddard Space Flight Center to identify organics and possible biological compounds on Mars. In the process of characterizing mass spectrometer size, weight, and power consumption, the use of pulse counting was considered for ion detection. Pulse counting has advantages over analog-mode amplification of the electron multiplier signal. Some advantages are reduced size of electronic components, low power consumption, ability to remotely characterize detector performance, and avoidance of analog circuit noise. The use of pulse counting as a detection method with ion trap instruments is relatively rare. However, with the recent development of high performance electrical components, this detection method is quite suitable and can demonstrate significant advantages over analog methods. Methods A prototype quadrupole ion trap mass spectrometer with an internal electron ionization source was used as a test setup to develop and evaluate the pulse-counting method. The anode signal from the electron multiplier was preamplified. The an1plified signal was fed into a fast comparator for pulse-level discrimination. The output of the comparator was fed directly into a Xilinx FPGA development board. Verilog HDL software was written to bin the counts at user-selectable intervals. This system was able to count pulses at rates in the GHz range. The stored ion count nun1ber per bin was transferred to custom ion trap control software. Pulse-counting mass spectra were compared with mass spectra obtained using the standard analog-mode ion detection. Prelin1inary Data Preliminary mass spectra have been obtained for both analog mode and pulse-counting mode under several sets of instrument operating conditions. Comparison of the spectra revealed better peak shapes for pulse-counting mode. Noise levels are as good as, or better than, analog-mode detection noise levels. To artificially force ion pile-up conditions, the ion trap was overfilled

  11. Lunar and Asteroid Composition Using a Remote Secondary Ion Mass Spectrometer

    NASA Technical Reports Server (NTRS)

    Elphic, R. C.; Funsten, H. O.; Barraclough, B. L.; Mccomas, D. J.; Nordholt, J. E.

    1992-01-01

    Laboratory experiments simulating solar wind sputtering of lunar surface materials have shown that solar wind protons sputter secondary ions in sufficient numbers to be measured from low-altitude lunar orbit. Secondary ions of Na, Mg, Al, Si, K, Ca, Mn, Ti, and Fe have been observed sputtered from sample simulants of mare and highland soils. While solar wind ions are hundreds of times less efficient than those used in standard secondary ion mass spectrometry, secondary ion fluxes expected at the Moon under normal solar wind conditions range from approximately 10 to greater than 10(exp 4) ions cm(sup -2)s(sup -1), depending on species. These secondary ion fluxes depend both on concentration in the soil and on probability of ionization; yields of easily ionized elements such as K and Na are relatively much greater than those for the more electronegative elements and compounds. Once these ions leave the surface, they are subject to acceleration by local electric and magnetic fields. For typical solar wind conditions, secondary ions can be accelerated to an orbital observing location. The same is true for atmospheric atoms and molecules that are photoionized by solar EUV. The instrument to detect, identify, and map secondary ions sputtered from the lunar surface and photoions arising from the tenuous atmosphere is discussed.

  12. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 1. Peptides to Proteins

    NASA Astrophysics Data System (ADS)

    Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

    2015-04-01

    Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

  13. Laser Ablation Electrodynamic Ion Funnel for In Situ Mass Spectrometry on Mars

    NASA Technical Reports Server (NTRS)

    Johnson, Paul V.; Hodyss, Robert P.; Tang, Keqi; Smith, Richard D.

    2012-01-01

    A front-end instrument, the laser ablation ion funnel, was developed, which would ionize rock and soil samples in the ambient Martian atmosphere, and efficiently transport the product ions into a mass spectrometer for in situ analysis. Laser ablation creates elemental ions from a solid with a high-power pulse within ambient Mars atmospheric conditions. Ions are captured and focused with an ion funnel into a mass spectrometer for analysis. The electrodynamic ion funnel consists of a series of axially concentric ring-shaped electrodes whose inside diameters (IDs) decrease over the length of the funnel. DC potentials are applied to each electrode, producing a smooth potential slope along the axial direction. Two radio-frequency (RF) AC potentials, equal in amplitude and 180 out of phase, are applied alternately to the ring electrodes. This creates an effective potential barrier along the inner surface of the electrode stack. Ions entering the funnel drift axially under the influence of the DC potential while being restricted radially by the effective potential barrier created by the applied RF. The net result is to effectively focus the ions as they traverse the length of the funnel.

  14. EBIT in the Magnetic Trapping Mode: Mass Spectrometry, Atomic Lifetime Measurements, and Charge Transfer Reactions of Highly Charged Atomic Ions

    SciTech Connect

    Schweikhard, L; Beiersdorfer, P; Trabert, E

    2001-07-10

    Although it may sound like a contradiction in terms, the electron beam ion trap (EBIT) works as an ion trap even when the electron beam is switched off. We present various experiments that exploit the ''magnetic trapping mode'' for investigations of ion confinement, charge exchange processes, atomic lifetime and ion mass measurements.

  15. Design of An Improved Miniature Ion Neutral Mass Spectrometer for NASA Applications

    NASA Technical Reports Server (NTRS)

    Swaminathan, Viji K.; Alig, Roger C.

    1997-01-01

    The ion optics of NASA's Ion Neutral Mass Spectrometer (INMS) sensor was simulated with three dimensional models of the open source, the quadrupole deflector, the exit lens system and the quadrupole mass analyzer to design more compact models with lower weight. Comparison of calculated transmission with experimental results shows good agreement. Transmission analyses with varying geometrical parameters and voltages throw light on possible ways of reducing the size of the sensor. Trajectories of ions of mass 1-99 amu were simulated to analyze and optimize transmission. Analysis of open source transmission with varying angle of attack shows that the angular acceptance can be considerably increased by programming the voltages on the ion trap/ collimator. Analysis of transmission sensitivity to voltages and misalignments of the quadrupole deflector rods indicate that increased transmission is possible with a geometrically asymmetrical deflector and a deflector can be designed with much lower sensitivities of transmission. Bringing the disks closer together can decrease the size of the quadrupole deflector and also increase transmission. The exit lens system can be redesigned to be smaller by eliminating at least one electrode entirely without loss of transmission. Ceramic materials were investigated to find suitable candidates for use in the construction of lighter weight mass spectrometer. A high-sensitivity, high-resolution portable gas chromatograph mass spectrometer with a mass range of 2-700 amu has been built and will be commercialized in Phase 3.

  16. Soft Supercharging of Biomolecular Ions in Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chingin, Konstantin; Xu, Ning; Chen, Huanwen

    2014-06-01

    The charge states of biomolecular ions in ESI-MS can be significantly increased by the addition of low-vapor supercharging (SC) reagents into the spraying solution. Despite the considerable interest from the community, the mechanistic aspects of SC are not well understood and are hotly debated. Arguments that denaturation accounts for the increased charging observed in proteins sprayed from aqueous solutions containing SC reagent have been published widely, but often with incomplete or ambiguous supporting data. In this work, we explored ESI MS charging and SC behavior of several biopolymers including proteins and DNA oligonucleotides. Analytes were ionized from 100 mM ammonium acetate (NH4Ac) aqueous buffer in both positive (ESI+) and negative (ESI-) ion modes. SC was induced either with m-NBA or by the elevated temperature of ESI capillary. For all the analytes studied we, found striking differences in the ESI MS response to these two modes of activation. The data suggest that activation with m-NBA results in more extensive analyte charging with lower degree of denaturation. When working solution with m-NBA was analyzed at elevated temperatures, the SC effect from m-NBA was neutralized. Instead, the net SC effect was similar to the SC effect achieved by thermal activation only. Overall, our observations indicate that SC reagents enhance ESI charging of biomolecules via distinctly different mechanism compared with the traditional approaches based on analyte denaturation. Instead, the data support the hypothesis that the SC phenomenon involves a direct interaction between a biopolymer and SC reagent occurring in evaporating ESI droplets.

  17. Developments of multiplexed and miniature two-dimensional quadrupole ion trap mass spectrometers

    NASA Astrophysics Data System (ADS)

    Smith, Scott A.

    Quadrupole ion trap mass spectrometry (QIT MS) is a powerful and commonly-employed method for the specific analysis of mass, composition, and structure of gas-phase ionic chemical species. Useful for a wide variety of tasks, applications of ion traps include environmental monitoring, surface analysis (including depth profiling and imaging), ion thermochemical property elucidation, protein and DNA sequencing, and high-resolution chemical separations (through ion soft-landing). Though the principles of QIT MS have been known for over half a century, innovations in instrumentation and applications continue. As new needs for specific and sensitive chemical analysis arise, so also do new and more efficient analytical devices and methods of analysis. Such a trend is exemplified through the construction of a dual-source QIT mass spectrometer (described herein) capable of multi-source chemical analyses for the purposes of enhanced proteomic sequence coverage and for the strictly-controlled comparison of the structural differences in ion populations generated by different ionization techniques. Furthermore, as mass spectrometry becomes increasingly commonplace outside the bounds of the analytical laboratory, demand for capable researcher equipment is also increasing. Advances in instrument performance, such as can be had through enhanced power efficiency and the enabling of chemical analysis of high mass-to-charge ratio (m/z) species (e.g., proteins), will open new doors to in situ chemical analysis hand-portable mass spectrometers. Hence, research into new mass analyzer designs and methods of fabrication using stereolithography apparatus (SLA) for the purpose of creating enhanced-performance mass spectrometers are accordingly described in the text of this dissertation.

  18. Rapid profiling and identification of anthocyanins in fruits with Hadamard transform ion mobility mass spectrometry.

    PubMed

    Liu, Wenjie; Zhang, Xing; Siems, William F; Hill, Herbert H; Yin, Dulin

    2015-06-15

    The use of Hadamard transform ion mobility mass spectrometry (HT-IMMS) in the profiling of anthocyanins from different fruits is presented. Samples extracted with acidic methanol and purified with solid phase extraction were analyzed with direct IMMS infusion. The separation of various anthocyanins was achieved within 30s with resolving powers up to 110. The ion mobility drift times correlated with their mass-to-charge ratios with a correlation coefficient of 0.979 to produce a trend line that was characteristic for anthocyanins. Isomers with the same anthocyanidin but different hexoses were differentiated by ion mobility spectrometry. Furthermore, mobility separated ions underwent collision induced dissociation at the IMMS interface to provide MS/MS spectra. These fragmentation spectra aided in the identification of anthocyanidins via the loss of the saccharide groups. IMMS appears to be a rapid and efficient approach for profiling and identifying anthocyanins. PMID:25660880

  19. Fragmentation of HCN in optically selected mass spectrometry: Nonthermal ion cooling in helium nanodroplets

    SciTech Connect

    Lewis, William K.; Bemish, Raymond J.; Miller, Roger E.

    2005-10-08

    A technique that combines infrared laser spectroscopy and helium nanodroplet mass spectrometry, which we refer to as optically selected mass spectrometry, is used to study the efficiency of ion cooling in helium. Electron-impact ionization is used to form He{sup +} ions within the droplets, which go on to transfer their charge to the HCN dopant molecules. Depending upon the droplet size, the newly formed ion either fragments or is cooled by the helium before fragmentation can occur. Comparisons with gas-phase fragmentation data suggest that the cooling provided by the helium is highly nonthermal. An 'explosive' model is proposed for the cooling process, given that the initially hot ion is embedded in such a cold solvent.

  20. Global structural changes of an ion channel during its gating are followed by ion mobility mass spectrometry

    PubMed Central

    Konijnenberg, Albert; Yilmaz, Duygu; Ingólfsson, Helgi I.; Dimitrova, Anna; Marrink, Siewert J.; Li, Zhuolun; Vénien-Bryan, Catherine; Sobott, Frank; Koçer, Armağan

    2014-01-01

    Mechanosensitive ion channels are sensors probing membrane tension in all species; despite their importance and vital role in many cell functions, their gating mechanism remains to be elucidated. Here, we determined the conditions for releasing intact mechanosensitive channel of large conductance (MscL) proteins from their detergents in the gas phase using native ion mobility–mass spectrometry (IM-MS). By using IM-MS, we could detect the native mass of MscL from Escherichia coli, determine various global structural changes during its gating by measuring the rotationally averaged collision cross-sections, and show that it can function in the absence of a lipid bilayer. We could detect global conformational changes during MscL gating as small as 3%. Our findings will allow studying native structure of many other membrane proteins. PMID:25404294

  1. Selected Ion Flow-Drift Tube Mass Spectrometry: Quantification of Volatile Compounds in Air and Breath.

    PubMed

    Spesyvyi, Anatolii; Smith, David; Španěl, Patrik

    2015-12-15

    A selected ion flow-drift tube mass spectrometric analytical technique, SIFDT-MS, is described that extends the established selected ion flow tube mass spectrometry, SIFT-MS, by the inclusion of a static but variable E-field along the axis of the flow tube reactor in which the analytical ion-molecule chemistry occurs. The ion axial speed is increased in proportion to the reduced field strength E/N (N is the carrier gas number density), and the residence/reaction time, t, which is measured by Hadamard transform multiplexing, is correspondingly reduced. To ensure a proper understanding of the physics and ion chemistry underlying SIFDT-MS, ion diffusive loss to the walls of the flow-drift tube and the mobility of injected H3O(+) ions have been studied as a function of E/N. It is seen that the derived diffusion coefficient and mobility of H3O(+) ions are consistent with those previously reported. The rate coefficient has been determined at elevated E/N for the association reaction of the H3O(+) reagent ions with H2O molecules, which is the first step in the production of H3O(+)(H2O)1,2,3 reagent hydrate ions. The production of hydrated analyte ion was also experimentally investigated. The analytical performance of SIFDT-MS is demonstrated by the quantification of acetone and isoprene in exhaled breath. Finally, the essential features of SIFDT-MS and SIFT-MS are compared, notably pointing out that a much lower speed of the flow-drive pump is required for SIFDT-MS, which facilitates the development of smaller cost-effective analytical instruments for real time breath and fluid headspace analyses. PMID:26583448

  2. Time-of-flight secondary neutral & ion mass spectrometry using swift heavy ions

    NASA Astrophysics Data System (ADS)

    Breuer, L.; Meinerzhagen, F.; Bender, M.; Severin, D.; Wucher, A.

    2015-12-01

    We report on a new time-of-flight (TOF) spectrometer designed to investigate sputtering phenomena induced by swift heavy ions in the electronic stopping regime. In this experiment, particular emphasis is put on the detection of secondary ions along with their emitted neutral counterparts in order to examine the ionization efficiency of the sputtered material. For the detection of neutral species, the system is equipped with a pulsed VUV laser for post-ionization of sputtered neutral atoms and molecules via single photon ionization at a wavelength of 157 nm (corresponding to 7.9 eV photon energy). For alignment purposes and in order to facilitate comparison to nuclear sputtering conditions, the system also includes a 5 keV Ar+ ion beam directed to the same sample area. The instrument has been added to the M1-branch beam line at the German accelerator facility in Darmstadt (GSI) and was tested with 4.8 MeV/u Au26+ ions impinging onto various samples including metals, salts and organic films. It is found that secondary ion and neutral spectra obtained under both bombardment conditions can be acquired in an interleaved manner throughout a single accelerator pulse cycle, thus making efficient use of valuable beam time. In addition, the keV ion beam can be intermittently switched to dc mode between subsequent data acquisition windows and accelerator pulses in order to ensure reproducible surface conditions. For the case of a dynamically sputter cleaned metal surface, comparison of secondary ion and neutral signals obtained under otherwise identical instrumental conditions reveals a nearly identical ionization probability of atoms emitted under electronic and nuclear sputtering conditions.

  3. DtaRefinery: a software tool for elimination of systematic errors from parent ion mass measurements in tandem mass spectra datasets

    SciTech Connect

    Petyuk, Vladislav A.; Mayampurath, Anoop M.; Monroe, Matthew E.; Polpitiya, Ashoka D.; Purvine, Samuel O.; Anderson, Gordon A.; Camp, David G.; Smith, Richard D.

    2009-12-16

    Hybrid two-stage mass spectrometers capable of both highly accurate mass measurement and MS/MS fragmentation have become widely available in recent years and have allowed for sig-nificantly better discrimination between true and false MS/MS pep-tide identifications by applying relatively narrow windows for maxi-mum allowable deviations for parent ion mass measurements. To fully gain the advantage of highly accurate parent ion mass meas-urements, it is important to limit systematic mass measurement errors. The DtaRefinery software tool can correct systematic errors in parent ion masses by reading a set of fragmentation spectra, searching for MS/MS peptide identifications, then fitting a model that can estimate systematic errors, and removing them. This results in a new fragmentation spectrum file with updated parent ion masses.

  4. Determination of electron affinity of carbonyl radicals by means of negative ion mass spectrometry.

    PubMed

    Muftakhov; Vasil'ev; Mazunov

    1999-06-01

    Appearance energies of [M-H](-) ions from carbonyl compounds R-CO-R' (R,R' = H, CH(3), NH(2), OH) have been measured by means of negative ion mass spectrometry in resonant electron capture mode. Values of electron affinity of the corresponding radicals, CH(2)&dbond;C(X)O, NH&dbond;C(X)O and O&dbond;C(X)O, have been determined. Copyright 1999 John Wiley & Sons, Ltd. PMID:10407285

  5. Research for optimizing the performance of an LEF-TOF ion energy mass analyzer

    SciTech Connect

    Tanaka, T.; Saito, Y.

    2009-06-16

    There are few in-situ heavy ion observations from lunar soil or tenuous alkali atmosphere. It is commonly thought that the heavy ions around the Moon are produced by ion-induced desorption (sputtering) or photon-stimulated desorption from the lunar surface and by photoionization from the atmosphere. These ions are picked up and transported by the solar wind. IMA (Ion Mass Analyzer) on board the SELENE satellite will measure these picked-up ions around the Moon. IMA adopts foil-based LEF (Linear Electric Field) TOF (Time Of Flight) technique for mass analysis in order to discriminate heavy ions up to mass number 60. MgO-coated metal plate is installed at the upper part of the mass analyzer to generate TOF stop electrons efficiently. Though we empirically knew that stop electron generations were enhanced by MgO-coated metal plate, quantitative analyses for the efficiency were insufficient. We compared the efficiency of electron emitter plates with different substrate materials: CuBe and Al and with different MgO thickness: 20 nm, 500 nm and 1000 nm. We also changed the surface roughness of these base plates. Our experimental results showed there are notable differences in the electron emission efficiency between MgO-coated plates and non-coated plates. We also found that the thicker MgO emits secondary electrons more efficiently. The efficient electron emission was mainly caused by the enhancement of the secondary electron yields of a single ion impact because the pulse height distribution of the stop signals generated by MgO coated plates was higher than that of non-coated plates.

  6. Using metal complex ion-molecule reactions in a miniature rectilinear ion trap mass spectrometer to detect chemical warfare agents.

    PubMed

    Graichen, Adam M; Vachet, Richard W

    2013-06-01

    The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n](y+) complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n](2+) complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations. PMID:23532782

  7. Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Graichen, Adam M.; Vachet, Richard W.

    2013-06-01

    The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

  8. T-wave Ion Mobility-mass Spectrometry: Basic Experimental Procedures for Protein Complex Analysis

    PubMed Central

    Michaelevski, Izhak; Kirshenbaum, Noam; Sharon, Michal

    2010-01-01

    Ion mobility (IM) is a method that measures the time taken for an ion to travel through a pressurized cell under the influence of a weak electric field. The speed by which the ions traverse the drift region depends on their size: large ions will experience a greater number of collisions with the background inert gas (usually N2) and thus travel more slowly through the IM device than those ions that comprise a smaller cross-section. In general, the time it takes for the ions to migrate though the dense gas phase separates them, according to their collision cross-section (Ω). Recently, IM spectrometry was coupled with mass spectrometry and a traveling-wave (T-wave) Synapt ion mobility mass spectrometer (IM-MS) was released. Integrating mass spectrometry with ion mobility enables an extra dimension of sample separation and definition, yielding a three-dimensional spectrum (mass to charge, intensity, and drift time). This separation technique allows the spectral overlap to decrease, and enables resolution of heterogeneous complexes with very similar mass, or mass-to-charge ratios, but different drift times. Moreover, the drift time measurements provide an important layer of structural information, as Ω is related to the overall shape and topology of the ion. The correlation between the measured drift time values and Ω is calculated using a calibration curve generated from calibrant proteins with defined cross-sections1. The power of the IM-MS approach lies in its ability to define the subunit packing and overall shape of protein assemblies at micromolar concentrations, and near-physiological conditions1. Several recent IM studies of both individual proteins2,3 and non-covalent protein complexes4-9, successfully demonstrated that protein quaternary structure is maintained in the gas phase, and highlighted the potential of this approach in the study of protein assemblies of unknown geometry. Here, we provide a detailed description of IMS-MS analysis of protein

  9. Tailored Noise Waveform/ Collision-Induced Dissociation of Ions Stored in a Linear Ion Trap Combined with Liquid Chromatography/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    SciTech Connect

    Vilkov, Andrey N.; Bogdanov, Bogdan; Pasa-Tolic, Liljiana; Prior, David C.; Anderson, Gordon A.; Masselon, Christophe D.; Moore, Ronald J.; Smith, Richard D.

    2004-11-01

    A new collision-induced dissociation (CID) technique based on broadband tailored noise waveform (TNW) excitation of ions stored in a linear ion trap has been developed. In comparison with the conventional sustained off-resonance irradiation (SORI) CID method commonly used in Fourier transform ion cyclotron resonance mass spectrometry, this MS/MS technique increases throughput by eliminating the long pump-down delay associated with gas introduction into the high vacuum ICR cell region. In addition, the TNW-CID method speeds spectrum acquisition since it does not require Fourier transformation, calculation of resonant frequencies and generation of the excitation waveforms. We demonstrate TNW-CID coupled with on-line capillary reverse phase liquid chromatography separations for identification of peptides. The experimental results are compared with data obtained using conventional quadrupole ion trap MS/MS and SORI-CID MS/MS in an ICR cell.

  10. Traveling Wave Ion Mobility Mass Spectrometry and Ab Initio Calculations of Phosphoric Acid Clusters

    NASA Astrophysics Data System (ADS)

    Lavanant, Hélène; Tognetti, Vincent; Afonso, Carlos

    2014-04-01

    Positive and negative ion electrospray mass spectra obtained from 50 mM phosphoric acid solutions presented a large number of phosphoric acid clusters: [(H3PO4)n + zH] z+ or [(H3PO4)n - zH] z- , with n up to 200 and z up to 4 for positively charged clusters, and n up to 270 and z up to 7 for negatively charged cluster ions. Ion mobility experiments allowed very explicit separation of the different charge states. Because of the increased pressures involved in ion mobility experiments, dissociation to smaller clusters was observed both in the trap and transfer areas. Voltages along the ion path could be optimized so as to minimize this effect, which can be directly associated with the cleavage of hydrogen bonds. Having excluded the ion mobility times that resulted from dissociated ions, each cluster ion appeared at a single drift time. These drift times showed a linear progression with the number of phosphoric atoms for cluster ions of the same charge state. Cross section calculations were carried out with MOBCAL on DFT optimized geometries with different hydrogen locations and with three types of atomic charges. DFT geometry optimizations yielded roughly spherical structures. Our results for nitrogen gas interaction cross sections showed that values were dependent on the atomic charges definition used in the MOBCAL calculation. This pinpointed the necessity to define a clear theoretical framework before any comparative interpretations can be attempted with uncharacterized compounds.

  11. Evaluation and optimization of electron capture dissociation efficiency in fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    McFarland, Melinda A; Chalmers, Michael J; Quinn, John P; Hendrickson, Christopher L; Marshall, Alan G

    2005-07-01

    Electron capture dissociation (ECD) efficiency has typically been lower than for other dissociation techniques. Here we characterize experimental factors that limit ECD and seek to improve its efficiency. Efficiency of precursor to product ion conversion was measured for a range of peptide (approximately 15% efficiency) and protein (approximately 33% efficiency) ions of differing sizes and charge states. Conversion of precursor ions to products depends on electron irradiation period and maximizes at approximately 5-30 ms. The optimal irradiation period scales inversely with charge state. We demonstrate that reflection of electrons through the ICR cell is more efficient and robust than a single pass, because electrons can cool to the optimal energy for capture, which allows for a wide range of initial electron energy. Further, efficient ECD with reflected electrons requires only a short (approximately 500 micros) irradiation period followed by an appropriate delay for cooling and interaction. Reflection of the electron beam results in electrons trapped in or near the ICR cell and thus requires a brief (approximately 50 micros) purge for successful mass spectral acquisition. Further electron irradiation of refractory precursor ions did not result in further dissociation. Possibly the ion cloud and electron beam are misaligned radially, or the electron beam diameter may be smaller than that of the ion cloud such that remaining precursor ions do not overlap with the electron beam. Several ion manipulation techniques and use of a large, movable dispenser cathode reduce the possibility that misalignment of the ion and electron beams limits ECD efficiency. PMID:15914017

  12. Focusing of intense and divergent ion beams in a magnetic mass analyzer

    SciTech Connect

    Jianlin, Ke; Changgeng, Zhou; Rui, Qiu; Yonghong, Hu

    2014-07-15

    A magnetic mass analyzer is used to determine the beam composition of a vacuum arc ion source. In the analyzer, we used the concentric multi-ring electrodes to focus the intense and divergent ion beams. We describe the principle, design, and the test results of the focusing device. The diameter of the beam profile is less than 20 mm when the accelerating voltage is 30 kV and the focusing voltage is about 2.0 kV. The focusing device has been successfully used in the magnetic mass analyzer to separate Ti{sup +}, Ti{sup 2+}, and Ti{sup 3+}.

  13. Instrument manual for the retarding ion mass spectrometer on Dynamics Explorer-1

    NASA Technical Reports Server (NTRS)

    Fields, S. A.; Baugher, C. R.; Chappell, C. R.; Reasoner, D. L.; Hammack, H. D.; Wright, W. W.; Hoffman, J. H.

    1982-01-01

    The retarding ion mass spectrometer (RIMS) for Dynamics Explorer-1 is an instrument designed to measure the details of the thermal plasma distribution. It combines the ion temperature determining capability of the retarding potential analyzer with the compositional capabilities of the mass spectrometer and adds multiple sensor heads to sample all directions relative to the spacecraft ram direction. This manual provides a functional description of the RIMS, the instrument calibration, and a description of the commands which can be stored in the instrument logic to control its operation.

  14. Novel sampling methods for use with thermal desorption ion trap mass spectrometry

    SciTech Connect

    Barshick, S.A.; Buchanan, M.V.

    1994-12-31

    Novel sampling approaches have been investigated to improve the analytical utility of thermal desorption Direct Sampling Ion Trap Mass Spectrometry (DSITMS). Because DSITMS involves the direct introduction of samples into an ion trap mass spectrometer, problems with detection capabilities (sensitivity and selectivity) can often occur when performing trace analysis in complex matrices. Various sampling approaches have been evaluated to improve thermal desorption detection capabilities and to extend the utilities of DSITMS methodologies without significantly increasing analysis times or the cost-effectiveness of DSITMS methods. Three sampling approaches have been investigated including solid phase microextraction (SPME), solid phase extraction columns (SPEC), and purge and trap.

  15. Multiphoton dissociation of electrosprayed megadalton-sized DNA ions in a charge-detection mass spectrometer.

    PubMed

    Doussineau, Tristan; Paletto, Pierre; Dugourd, Philippe; Antoine, Rodolphe

    2015-01-01

    Charge detection mass spectrometry in combination with a linear electrostatic ion trap coupled to a continuous wavelength infrared CO2 laser has been used to study the multiphoton dissociation of DNA macromolecular ions. Samples, with masses ranging from 2.23 to 31.5 MDa, include single strand circular M13mp18, double strand circular M13mp18, and double strand linear LambdaPhage DNA fragments. Their activation energies for unimolecular dissociation were determined. Activation energy values slightly increase as a function of the molecular weight. The most important result is the difference between the fragmentations observed for hybridized double-strands and dimers of single strands. PMID:25348472

  16. Liquid Beam Ion Desorption Mass Spectrometry for Evaluating CASSINI Data

    NASA Astrophysics Data System (ADS)

    Stolz, Ferdinand; Reviol, Rene; Srama, Ralf; Trieloff, Mario; Postberg, Frank; Abel, Bernd

    2013-04-01

    Saturn's moon Enceladus emits plumes of ice particles from an area near its south pole which are detected and chemically analyzed by the Cosmic Dust Analyzer (CDA) on board the CASSINI spacecraft. Studying these ice particles provides unique insights into Enceladus geological properties. Technically the CDA is a time-of-flight mass spectrometer which delivers mass spectra of the particles and their fragments. Since interpretation of the available CDA data is particularly challenging we employ a laboratory experiment to imitate experimental conditions in space. Key part of our experimental setup is a micron-sized water beam in high vacuum. This beam is rapidly heated up by an infrared laser pulse, which is tuned to excite the OH-stretch vibration of water molecules. This causes the water beam to dissipate into small droplets, some of which carry a net charge even though the laser energy is well below the molecular ionisation energy. The charged droplets are then analyzed in a time-of-flight mass spectrometer. With this experimental setup we successfully simulated the space born ice particles measured at Enceladus. By varying the laser intensity in our experiments, we can vary the amount of energy deposited in the liquid beam, and thus model different particle velocities. Also, variation of solute concentration in the water beam provides valuable information about ice particle composition. Some examples for anorganic solutes studied so far are sodium chloride, ammonia and hydrogen sulfite. A special feature of our experimental technique is that desorption of particles from the liquid beam is particularly soft. This is explained by the fact that all laser energy is absorbed by the water molecules. In this way molecular bonds of solutes stay intact and molecular solutes are transferred into the droplet phase without getting destroyed. This is particularly interesting in the context of analyzing organic compounds - some of which have been detected at Enceladus. Using

  17. Geochemical mass-balance relationships for selected ions in precipitation and stream water, Catoctin Mountains, Maryland.

    USGS Publications Warehouse

    Katz, B.G.; Bricker, O.P.; Kennedy, M.M.

    1985-01-01

    Results of a study of input/output mass balances for major ions based on the chemical composition of precipitation and stream-water, geochemical reactions with different loading rates of hydrogen ion, and watershed processes influencing the chemical character of stream-waters in two small watershed areas are reported with a view to predicting the effect of additions of acidic rain to the watershed systems. Geochemical weathering processes account for the observed changes in the chemistry of stream flow. Although present in bedrock in extremely small quantities, calcite plays an important role in neutralization of the total hydrogen-ion input.-M.S.

  18. Operational Parameters, Considerations, and Design Decisions for Resource-Constrained Ion Trap Mass Spectrometers

    NASA Technical Reports Server (NTRS)

    Danell, Ryan M.; VanAmerom, Friso H. W.; Pinnick, Veronica; Cotter, Robert J.; Brickerhoff, William; Mahaffy, Paul

    2011-01-01

    Mass spectrometers are increasingly finding applications in new and unique areas, often in situations where key operational resources (i.e. power, weight and size) are limited. One such example is the Mars Organic Molecule Analyzer (MOMA). This instrument is a joint venture between NASA and the European Space Agency (ESA) to develop an ion trap mass spectrometer for chemical analysis on Mars. The constraints on such an instrument are significant as are the performance requirements. While the ideal operating parameters for an ion trap are generally well characterized, methods to maintain analytical performance with limited power and system weight need to be investigated and tested. Methods Experiments have been performed on two custom ion trap mass spectrometers developed as prototypes for the MOMA instrument. This hardware consists of quadrupole ion trap electrodes that are 70% the size of common commercial instrumentation. The trapping RF voltage is created with a custom tank circuit that can be tuned over a range of RF frequencies and is driven using laboratory supplies and amplifiers. The entire instrument is controlled with custom Lab VIEW software that allows a high degree of flexibility in the definition of the scan function defining the ion trap experiment. Ions are typically generated via an internal electron ionization source, however, a laser desorption source is also in development for analysis of larger intact molecules. Preliminary Data The main goals in this work have been to reduce the power required to generate the radio frequency trapping field used in an ion trap mass spectrometer. Generally minimizing the power will also reduce the volume and mass of the electronics to support the instrument. In order to achieve optimum performance, commercial instruments typically utilize RF frequencies in the 1 MHz range. Without much concern for power usage, they simply generate the voltage required to access the mass range of interest. In order to reduce the

  19. Low-energy ion implantation: Large mass fractionation of argon

    NASA Technical Reports Server (NTRS)

    Ponganis, K. V.; Graf, TH.; Marti, K.

    1993-01-01

    The isotropic signatures of noble gases in the atmospheres of the Earth and other planets are considerably evolved when compared to signatures observed in the solar wind. The mechanisms driving the evolution of planetary volatiles from original compositions in the solar accretion disk are currently poorly understood. Modeling of noble-gas compositional histories requires knowledge of fractionating processes that may have operated through the evolutionary stages. Since these gases are chemically inert, information on noble-gas fractionation processes can be used as probes. The importance of understanding these processes extends well beyond 'noble-gas planetology.' Trapped argon acquired by low-energy implantation (approximately less than 100 eV) into solids is strongly mass fractionated (approximately greater than or equal to 3 percent/amu). This has potential implications for the origin and evolution of terrestrial planet atmospheres.

  20. Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime

    NASA Astrophysics Data System (ADS)

    Nikolić, Dragan; Madzunkov, Stojan M.; Darrach, Murray R.

    2015-12-01

    We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra.

  1. Reactions of vinyl chloride and methanol in a quadrupole ion trap mass spectrometer during VOC analysis

    SciTech Connect

    Bian, L.; Alley, E.G.; Lynn, B.C. Jr.

    1999-05-01

    A reaction between vinyl chloride and the solvent (methanol) was observed during volatile organic compound (VOC) analysis on a gas chromatograph/quadrupole ion trap mass spectrometer (GC/MS). A chromatographic peak at a retention time consistent with vinyl chloride produced a mass spectrum without the characteristic chlorine isotope ions m/z 62 and 64 but instead contained an apparent molecular ion, m/z 58. The m/z 58 ion is not found in the reference spectrum of vinyl chloride. This spectrum was observed when methanol was used as solvent in internal standard, surrogate standard, or analyte solutions. Subsequent VOC standard analysis indicated that the abundance of the m/z 58 ion was directly proportional to the amount of vinyl chloride in the water samples. The correct spectrum for vinyl chloride was observed when no methanol was added. From these experiments, the authors concluded that a reaction was occurring between the vinyl chloride and methanol in the ion trap producing a new species with a molecular ion at m/z 58. When ethanol was used as the solvent for the internal standard solution or surrogate standard, a correct spectrum of vinyl chloride was obtained.

  2. Broadscale resolving power performance of a high precision uniform field ion mobility-mass spectrometer.

    PubMed

    May, Jody C; Dodds, James N; Kurulugama, Ruwan T; Stafford, George C; Fjeldsted, John C; McLean, John A

    2015-10-21

    An extensive study of two current ion mobility resolving power theories ("conditional" and "semi-empirical") was undertaken using a recently developed drift tube ion mobility-mass spectrometer. The current study investigates the quantitative agreement between experiment and theory at reduced pressure (4 Torr) for a wide range of initial ion gate widths (100 to 500 μs), and ion mobility values (K0 from 0.50 to 3.0 cm(2) V(-1) s(-1)) representing measurements obtained in helium, nitrogen, and carbon dioxide drift gas. Results suggest that the conditional resolving power theory deviates from experimental results for low mobility ions (e.g., high mass analytes) and for initial ion gate widths beyond 200 μs. A semi-empirical resolving power theory provided close-correlation of predicted resolving powers to experimental results across the full range of mobilities and gate widths investigated. Interpreting the results from the semi-empirical theory, the performance of the current instrumentation was found to be highly linear for a wide range of analytes, with optimal resolving powers being accessible for a narrow range of drift fields between 14 and 17 V cm(-1). While developed using singly-charged ion mobility data, preliminary results suggest that the semi-empirical theory has broader applicability to higher-charge state systems. PMID:26191544

  3. 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

  4. Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime.

    PubMed

    Nikolić, Dragan; Madzunkov, Stojan M; Darrach, Murray R

    2015-12-01

    We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra. Graphical Abstract ᅟ. PMID:26286456

  5. Loss of 45 Da from a2 Ions and Preferential Loss of 48 Da from a2 Ions Containing Methionine in Peptide Ion Tandem Mass Spectra

    NASA Astrophysics Data System (ADS)

    Simón-Manso, Yamil; Neta, Pedatsur; Yang, Xiaoyu; Stein, Stephen E.

    2011-02-01

    While analyzing tandem mass spectra of tryptic tripeptides, intense unassigned peaks were observed, corresponding to neutral loss of 45 Da from a2 ions. This process was confirmed by MS3 experiments. Based on exact mass analysis, the loss was ascribed to (NH3 + CO) or formamide. The proposed mechanism involves a cyclic form of the a2 ions. The structure of the a2 - 45 ions was confirmed by their fragmentation in MS3 experiments. Loss of (NH3 + CO) from the a2 ions occurs in competition with other paths, such as the loss of H2O or the formation of immonium ions. However, if the a2 ion contains methionine, a neutral loss of 48 Da (ascribed to CH3SH) predominates, and is followed by the loss of (NH3 + CO). These processes were confirmed by MS3 experiments. The intensity of the a2 - 48 peak formed from XaaMet has a maximum value of 42% (of the total intensity of all ions) for Xaa=Gly, varies between 15% and 40% for most other Xaa residues, is lower for residues that can undergo loss of water or ammonia, and is very low for Lys or Arg. When the order of the residues is reversed to MetXaa, the loss of 48 Da is much smaller. This effect can be used to determine the sequence of b2 ions containing Met in proteomic studies. Considerable loss of CH3SH is observed from doubly protonated tryptic tripeptides with N-terminal Met, but the loss is much less when they are singly protonated or when Met is in the center position.

  6. Development and Deployment of Retrofit PolarisQ Ion Trap Mass Spectrometer for Isotope Ratio Measurements

    SciTech Connect

    Thompson, Cyril V.; Whitten, William B.

    2015-11-01

    This report describes Oak Ridge National Laboratory’s (ORNL) FY15 progress in support of National Nuclear Security Administration’s (NNSA) Portable Mass Spectrometer project. A retrofit PolarisQ ion trap mass spectrometer (RPMS) has been assembled from components of two PolarisQ ion trap mass spectrometers used in previous isotope ratio programs. The retrofit mass spectrometer includes a custom Hastelloy vacuum chamber which is about ¼ the size of the standard aluminum vacuum chamber and reduces the instrument weight from the original by nine pounds. In addition, the new vacuum chamber can be independently heated to reduce impurities such as water, which reacts with UF6 to produce HF in the vacuum chamber. The analyzer and all components requiring service are mounted on the chamber lid, facilitating quick and easy replacement of consumable components such as the filament and electron multiplier.

  7. DtaRefinery, a Software Tool for Elimination of Systematic Errors from Parent Ion Mass Measurements in Tandem Mass Spectra Data Sets*

    PubMed Central

    Petyuk, Vladislav A.; Mayampurath, Anoop M.; Monroe, Matthew E.; Polpitiya, Ashoka D.; Purvine, Samuel O.; Anderson, Gordon A.; Camp, David G.; Smith, Richard D.

    2010-01-01

    Hybrid two-stage mass spectrometers capable of both highly accurate mass measurement and high throughput MS/MS fragmentation have become widely available in recent years, allowing for significantly better discrimination between true and false MS/MS peptide identifications by the application of a relatively narrow window for maximum allowable deviations of measured parent ion masses. To fully gain the advantage of highly accurate parent ion mass measurements, it is important to limit systematic mass measurement errors. Based on our previous studies of systematic biases in mass measurement errors, here, we have designed an algorithm and software tool that eliminates the systematic errors from the peptide ion masses in MS/MS data. We demonstrate that the elimination of the systematic mass measurement errors allows for the use of tighter criteria on the deviation of measured mass from theoretical monoisotopic peptide mass, resulting in a reduction of both false discovery and false negative rates of peptide identification. A software implementation of this algorithm called DtaRefinery reads a set of fragmentation spectra, searches for MS/MS peptide identifications using a FASTA file containing expected protein sequences, fits a regression model that can estimate systematic errors, and then corrects the parent ion mass entries by removing the estimated systematic error components. The output is a new file with fragmentation spectra with updated parent ion masses. The software is freely available. PMID:20019053

  8. Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry

    PubMed Central

    Prokai, Laszlo; Stevens, Stanley M.

    2016-01-01

    Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae. PMID:26784186

  9. Direct Analysis in Real Time (DART) of an Organothiophosphate at Ultrahigh Resolution by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry.

    PubMed

    Prokai, Laszlo; Stevens, Stanley M

    2016-01-01

    Direct analysis in real time (DART) is a recently developed ambient ionization technique for mass spectrometry to enable rapid and sensitive analyses with little or no sample preparation. After swab-based field sampling, the organothiophosphate malathion was analyzed using DART-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) and tandem mass spectrometry (MS/MS). Mass resolution was documented to be over 800,000 in full-scan MS mode and over 1,000,000 for an MS/MS product ion produced by collision-induced dissociation of the protonated analyte. Mass measurement accuracy below 1 ppm was obtained for all DART-generated ions that belonged to the test compound in the mass spectra acquired using only external mass calibration. This high mass measurement accuracy, achievable at present only through FTMS, was required for unequivocal identification of the corresponding molecular formulae. PMID:26784186

  10. Development of analytically capable time-of-flight mass spectrometer with continuous ion introduction

    NASA Astrophysics Data System (ADS)

    Hárs, György; Dobos, Gábor

    2010-03-01

    The present article describes the results and findings explored in the course of the development of the analytically capable prototype of continuous time-of-flight (CTOF) mass spectrometer. Currently marketed pulsed TOF (PTOF) instruments use ion introduction with a 10 ns or so pulse width, followed by a waiting period roughly 100 μs. Accordingly, the sample is under excitation in 10-4 part of the total measuring time. This very low duty cycle severely limits the sensitivity of the PTOF method. A possible approach to deal with this problem is to use linear sinusoidal dual modulation technique (CTOF) as described in this article. This way the sensitivity of the method is increased, due to the 50% duty cycle of the excitation. All other types of TOF spectrometer use secondary electron multiplier (SEM) for detection, which unfortunately discriminates in amplification in favor of the lighter ions. This discrimination effect is especially undesirable in a mass spectrometric method, which targets high mass range. In CTOF method, SEM is replaced with Faraday cup detector, thus eliminating the mass discrimination effect. Omitting SEM is made possible by the high ion intensity and the very slow ion detection with some hundred hertz detection bandwidth. The electrometer electronics of the Faraday cup detector operates with amplification 1010 V/A. The primary ion beam is highly monoenergetic due to the construction of the ion gun, which made possible to omit any electrostatic mirror configuration for bunching the ions. The measurement is controlled by a personal computer and the intelligent signal generator Type Tabor WW 2571, which uses the direct digital synthesis technique for making arbitrary wave forms. The data are collected by a Labjack interface board, and the fast Fourier transformation is performed by the software. Noble gas mixture has been used to test the analytical capabilities of the prototype setup. Measurement presented proves the results of the mathematical

  11. Development of analytically capable time-of-flight mass spectrometer with continuous ion introduction

    SciTech Connect

    Hars, Gyoergy; Dobos, Gabor

    2010-03-15

    The present article describes the results and findings explored in the course of the development of the analytically capable prototype of continuous time-of-flight (CTOF) mass spectrometer. Currently marketed pulsed TOF (PTOF) instruments use ion introduction with a 10 ns or so pulse width, followed by a waiting period roughly 100 {mu}s. Accordingly, the sample is under excitation in 10{sup -4} part of the total measuring time. This very low duty cycle severely limits the sensitivity of the PTOF method. A possible approach to deal with this problem is to use linear sinusoidal dual modulation technique (CTOF) as described in this article. This way the sensitivity of the method is increased, due to the 50% duty cycle of the excitation. All other types of TOF spectrometer use secondary electron multiplier (SEM) for detection, which unfortunately discriminates in amplification in favor of the lighter ions. This discrimination effect is especially undesirable in a mass spectrometric method, which targets high mass range. In CTOF method, SEM is replaced with Faraday cup detector, thus eliminating the mass discrimination effect. Omitting SEM is made possible by the high ion intensity and the very slow ion detection with some hundred hertz detection bandwidth. The electrometer electronics of the Faraday cup detector operates with amplification 10{sup 10} V/A. The primary ion beam is highly monoenergetic due to the construction of the ion gun, which made possible to omit any electrostatic mirror configuration for bunching the ions. The measurement is controlled by a personal computer and the intelligent signal generator Type Tabor WW 2571, which uses the direct digital synthesis technique for making arbitrary wave forms. The data are collected by a Labjack interface board, and the fast Fourier transformation is performed by the software. Noble gas mixture has been used to test the analytical capabilities of the prototype setup. Measurement presented proves the results of

  12. Ion Composition of Comet 19P/Borrelly as Measured by the PEPE Ion Mass Spectrometer on DS1

    NASA Astrophysics Data System (ADS)

    Nordholt, J. E.; Reisenfeld, D. B.; Wiens, R. C.; Gary, P.

    2002-12-01

    Cometary compositions are of great interest because they hold important clues to the formation of the outer solar system, and to the sources of volatiles in the solar system, including the terrestrial planets. In order to understand the primordial compositions of cometary nuclei, it is important to also understand their evolution, as many of the comets most accessible to spacecraft are highly evolved. It is also important to understand the ion and neutral chemistry that occurs in the coma surrounding the nucleus if the coma ion composition is to be used to determine the original composition of the nucleus. Deep Space One (DS1) was only the second spacecraft, after Giotto, to use an ion mass-resolving instrument to explore cometary coma compositions in-situ, which it did during the flyby of Comet Borrelly on September 22, 2001. Borrelly is significantly more evolved than Halley. In addition, the encounter occurred at a significantly greater distance from the sun (1.36 AU vs 0.9 AU for Giotto at Halley). The Plasma Experiment for Planetary Exploration (PEPE) on board DS1 was capable of resolving electron and ion energy, angle of incidence, and ion mass composition. The PEPE ion data from the seven minutes surrounding closest approach (2171 km) have been extensively analyzed. The instrument response was modeled using SIMION and TRIM codes for all of the major species through 20 AMU plus CO (at its operating voltage PEPE was very insensitive to heavier molecules). Chi-squared minimization analysis is being carried out to determine the best fit and the uncertainties. Preliminary results for the predominant heavy ions are OH+ at (72 +/- 9)% of the total water-group ion density, H2O+ at (25 +/- 7)%, CH3+ at (5 +/- 3)%, and O+ at (4 +/- 5)%. Uncertainties are quoted at the 90% confidence level. Comparison with reported Halley compositions from Giotto shows that Borrelly clearly has a lower H3O+ abundance (< 9%), consistent with a more evolved comet. The presence of

  13. Application of Ion Mobility-Mass Spectrometry to the Study of Ionic Clusters: Investigation of Cluster Ions with Stable Sizes and Compositions

    PubMed Central

    Ohshimo, Keijiro; Komukai, Tatsuya; Takahashi, Tohru; Norimasa, Naoya; Wu, Jenna Wen Ju; Moriyama, Ryoichi; Koyasu, Kiichirou; Misaizu, Fuminori

    2014-01-01

    Stable cluster sizes and compositions have been investigated for cations and anions of ionic bond clusters such as alkali halides and transition metal oxides by ion mobility-mass spectrometry (IM-MS). Usually structural information of ions can be obtained from collision cross sections determined in IM-MS. In addition, we have found that stable ion sizes or compositions were predominantly produced in a total ion mass spectrum, which was constructed from the IM-MS measurement. These stable species were produced as a result of collision induced dissociations of the ions in a drift cell. We have confirmed this result in the sodium fluoride cluster ions, in which cuboid magic number cluster ions were predominantly observed. Next the stable compositions, which were obtained for the oxide systems of the first row transition metals, Ti, Fe, and Co, are characteristic for each of the metal oxide cluster ions. PMID:26819887

  14. Precursor-ion mass re-estimation improves peptide identification on hybrid instruments.

    PubMed

    Luethy, Roland; Kessner, Darren E; Katz, Jonathan E; Maclean, Brendan; Grothe, Robert; Kani, Kian; Faça, Vitor; Pitteri, Sharon; Hanash, Samir; Agus, David B; Mallick, Parag

    2008-09-01

    Mass spectrometry-based proteomics experiments have become an important tool for studying biological systems. Identifying the proteins in complex mixtures by assigning peptide fragmentation spectra to peptide sequences is an important step in the proteomics process. The 1-2 ppm mass-accuracy of hybrid instruments, like the LTQ-FT, has been cited as a key factor in their ability to identify a larger number of peptides with greater confidence than competing instruments. However, in replicate experiments of an 18-protein mixture, we note parent masses deviate 171 ppm, on average, for ion-trap data directed identifications and 8 ppm, on average, for preview Fourier transform (FT) data directed identifications. These deviations are neither caused by poor calibration nor by excessive ion-loading and are most likely due to errors in parent mass estimation. To improve these deviations, we introduce msPrefix, a program to re-estimate a peptide's parent mass from an associated high-accuracy full-scan survey spectrum. In 18-protein mixture experiments, msPrefix parent mass estimates deviate only 1 ppm, on average, from the identified peptides. In a cell lysate experiment searched with a tolerance of 50 ppm, 2295 peptides were confidently identified using native data and 4560 using msPrefixed data. Likewise, in a plasma experiment searched with a tolerance of 50 ppm, 326 peptides were identified using native data and 1216 using msPrefixed data. msPrefix is also able to determine which MS/MS spectra were possibly derived from multiple precursor ions. In complex mixture experiments, we demonstrate that more than 50% of triggered MS/MS may have had multiple precursor ions and note that spectra with multiple candidate ions are less likely to result in an identification using TANDEM. These results demonstrate integration of msPrefix into traditional shotgun proteomics workflows significantly improves identification results. PMID:18707148

  15. Towards analytically useful two-dimensional Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    van Agthoven, Maria A; Delsuc, Marc-André; Bodenhausen, Geoffrey; Rolando, Christian

    2013-01-01

    Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) achieves high resolution and mass accuracy, allowing the identification of the raw chemical formulae of ions in complex samples. Using ion isolation and fragmentation (MS/MS), we can obtain more structural information, but MS/MS is time- and sample-consuming because each ion must be isolated before fragmentation. In 1987, Pfändler et al. proposed an experiment for 2D FT-ICR MS in order to fragment ions without isolating them and to visualize the fragmentations of complex samples in a single 2D mass spectrum, like 2D NMR spectroscopy. Because of limitations of electronics and computers, few studies have been conducted with this technique. The improvement of modern computers and the use of digital electronics for FT-ICR hardware now make it possible to acquire 2D mass spectra over a broad mass range. The original experiments used in-cell collision-induced dissociation, which caused a loss of resolution. Gas-free fragmentation modes such as infrared multiphoton dissociation and electron capture dissociation allow one to measure high-resolution 2D mass spectra. Consequently, there is renewed interest to develop 2D FT-ICR MS into an efficient analytical method. Improvements introduced in 2D NMR spectroscopy can also be transposed to 2D FT-ICR MS. We describe the history of 2D FT-ICR MS, introduce recent improvements, and present analytical applications to map the fragmentation of peptides. Finally, we provide a glossary which defines a few keywords for the 2D FT-ICR MS field. PMID:23076397

  16. Investigating ion-surface collisions with a niobium superconducting tunnel junction detector in a time-of-flight mass spectrometer

    PubMed

    Westmacott; Zhong; Frank; Friedrich; Labov; Benner

    2000-01-01

    The performance of an energy sensitive, niobium superconducting tunnel junction (STJ) detector is investigated by measuring the pulse height produced by impacting molecular and atomic ions at different kinetic energies. Ions are produced by laser desorption and matrix-assisted laser desorption in a time-of-flight mass spectrometer. Our results show that the STJ detector pulse height decreases for increasing molecular ion mass, passes through a minimum at around 2000 Da, and then increases with increasing mass of molecular ions above 2000 Da. The detector does not show a decline in sensitivity for high mass ions as is observed with microchannel plate ion detectors. These detector plus height measurements are discussed in terms of several physical mechanisms involved in an ion-surface collision. PMID:10775095

  17. Investigating ion-surface collisions with a niobium superconducting tunnel junction detector in a time-of-flight mass spectrometer

    SciTech Connect

    Westmacott, G.; Zhong, F.; Frank, M.; Friedrich, S.; Labov, S.; Benner, W.H.

    1999-12-01

    The performance of an energy sensitive, niobium superconducting tunnel junction detector is investigated by measuring the pulse height produced by impacting molecular and atomic ions at different kinetic energies. Ions are produced by laser resorption and matrix-assisted laser desorption in a time-of-flight mass spectrometer. Results show that the STJ detector pulse height decreases for increasing molecular ion mass, passes through a minimum at around 2000 Da, and the increases with increasing mass of molecular ions above 2000Da. The detector does not show a decline in sensitivity for high mass ions as is observed with microchannel plate ion detectors. These detector plus height measurements are discussed in terms of several physical mechanisms involved in an ion-surface collision.

  18. The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

    NASA Astrophysics Data System (ADS)

    Oganessian, Yu. Ts.; Shchepunov, V. A.; Dmitriev, S. N.; Itkis, M. G.; Gulbekyan, G. G.; Khabarov, M. V.; Bekhterev, V. V.; Bogomolov, S. L.; Efremov, A. A.; Pashenko, S. V.; Stepantsov, S. V.; Yeremin, A. V.; Yavor, M. I.; Kalimov, A. G.

    2003-05-01

    A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 -3. The set up can work in the wide mass range from A≈20 to A≈500, its mass acceptance is as large as ±2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90° electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considered. Description of its elements and subsystems is given.

  19. Mass Measurement of Single Intact Nanoparticles in a Cylindrical Ion Trap.

    PubMed

    Zhang, Ning; Zhu, Kai; Xiong, Caiqiao; Jiang, Yurong; Chang, Huan-Cheng; Nie, Zongxiu

    2016-06-01

    Accurate nanoparticle mass characterization is a challenging task, especially at a single particle level. To solve this problem, a strategy for the mass measurement of single intact nanoparticle was proposed. A microscopy-based ion trap mass spectrometer was built up. To improve the detection sensitivity, a cylindrical ion trap with transparent conductive end-caps was used to increase the transmission of scattered light, and a vacuum ultraviolet lamp was used to increase the charge state of the isolated nanoparticle. By detecting the scattered light of the isolated nanoparticle, a series of secular frequencies were obtained, from which the corresponding mass-to-charge ratio of the nanoparticle was calculated. Finally, a Labview program was used to help deduce the charge state and absolute mass of the individual nanoparticle. Masses of gold nanoparticles with different sizes were accurately examined, which are (5.08 ± 0.44) × 10(7) Da for 20 nm, (3.55 ± 0.34) × 10(8) Da for 40 nm, and (1.22 ± 0.14) × 10(9) Da for 60 nm, respectively. The mass of MOFs with irregular shapes was also determined, which is (6.48 ± 1.08) × 10(9) Da. This method can provide the mass information on nanomaterials, thus opens up new possibility of characterizing nanoparticles at the single particle level. PMID:27167332

  20. Lunar surface composition and solar wind-induced secondary ion mass spectrometry

    SciTech Connect

    Elphic, R.C.; Funsten, H.O. III; Barraclough, B.L.; McComas, D.J.; Paffett, M.T.; Vaniman, D.T.; Heiken, G. )

    1991-11-01

    The Moon has no strong global magnetic field and only a tenuous atmosphere, so solar wind ions ({approximately}95% H{sup +}, 5% He{sup ++}) directly bombard the lunar surface, sputtering atoms and secondary ions from the exposed grains of the regolith. The secondary ions potentially provide surface composition information through secondary ion mass spectrometry (SIMS), a standard laboratory surface composition analysis technique. In this paper the authors report the results of laboratory SIMS experiments on lunar soil simulants using solar wind-like ions. They find that H{sup +} and He{sup ++}, while not efficient sputterers, nevertheless produce significant fluxes of secondary lunar ions, including Na{sup +}, Mg{sup +}, Al{sup +}, Si{sup +}, K{sup +}, Ca{sup +}, Ti{sup +}, Mn{sup +} and Fe{sup +}. They predict that lunar surface secondary-ion fluxes range between {approximately}10 and 10{sup 4} ions cm{sup {minus}2} s{sup {minus}1}, depending on the species.

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

    PubMed

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

    1995-11-01

    Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode. PMID:8633761

  2. Deep Space 1 Encounter With Comet Borrelly: Composition Measurements By The Pepe Ion Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Reisenfeld, D. B.; Nordholt, J. E.; Wiens, R. C.; Gary, S. P.; Steinberg, J. T.; Pepe Ion Mass Spectrometer Team

    On 22 September 2001 Deep Space One (DS1) successfully encountered Comet Bor- relly at a distance of closest approach of 2171 km. DS1 is, after Giotto, the second spacecraft bearing an ion-mass-resolving instrument to explore the plasma environ- ment of a comet. This mass spectrometer, called the Plasma Experiment for Planetary Exploration (PEPE), is capable of resolving the energy, angle of incidence, and mass composition of a wide range of solar system plasmas. Our preliminary analysis indi- cates that the predominant heavy ions observed during the seven minute interval about closest approach included approximately 63% OH+, 25% H2O+, and 8% CH3+. The ions O+, H3O+, and CH+ are likely present, but at abundances below clear detection. Because H3O+ is collisionally produced from H2O+, the relative absence of H3O+ measured by PEPE is consistent with the much lower activity of Borrelly compared with Halley, where H3O+ was the dominant ion at closest approach. Preliminary anal- ysis also shows a surprisingly high nitrogen to carbon ratio in this cometary plasma. Another new PEPE observation at Borrelly was the non-symmetric character of the water-group ion count rate, which varied approximately as r-3 over much of the /2 inbound approach, but scaled as r-1 on the outbound leg.

  3. Analysis of saturated hydrocarbons by redox reaction with negative-ion electrospray Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Zhou, Xibin; Shi, Quan; Zhang, Yahe; Zhao, Suoqi; Zhang, Rui; Chung, Keng H; Xu, Chunming

    2012-04-01

    A novel technique was developed for characterization of saturated hydrocarbons. Linear alkanes were selectively oxidized to ketones by ruthenium ion catalyzed oxidation (RICO). Branched and cyclic alkanes were oxidized to alcohols and ketones. The ketones were then reduced to alcohols by lithium aluminum hydride (LiAlH(4)). The monohydric alcohols (O(1)) in the products obtained from the RICO and RICO-LiAlH(4) reduction reactions were characterized using negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for identification of iso-paraffins, acyclic paraffins and cyclic paraffins. Various model saturated compounds were used to determine the RICO reaction and ionization selectivity. The results from the FTICR MS analysis on the petroleum distillates derived saturated fraction were in agreement with those from field ionization gas chromatography time-of-flight mass spectrometry (FI GC-TOF MS) analysis. The technique was also used to characterize a petroleum vacuum residue (VR) derived saturates. The results showed that the saturated molecules in the VR contained up to 11 cyclic rings, and the maximum carbon number was up to 92. PMID:22424498

  4. Identification of the sulfoxide functionality in protonated analytes via ion/molecule reactions in linear quadrupole ion trap mass spectrometry.

    PubMed

    Sheng, Huaming; Williams, Peggy E; Tang, Weijuan; Zhang, Minli; Kenttämaa, Hilkka I

    2014-09-01

    A mass spectrometric method utilizing gas-phase ion/molecule reactions of 2-methoxypropene (MOP) has been developed for the identification of the sulfoxide functionality in protonated analytes in a LQIT mass spectrometer. Protonated sulfoxide analytes react with MOP to yield an abundant addition product (corresponding to 37-99% of the product ions), which is accompanied by a much slower proton transfer. The total efficiency (percent of gas-phase collisions leading to products) of the reaction is moderate (3-14%). A variety of compounds with different functional groups, including sulfone, hydroxylamino, N-oxide, aniline, phenol, keto, ester, amino and hydroxy, were examined to probe the selectivity of this reaction. Most of the protonated compounds with proton affinities lower than that of MOP react mainly via proton transfer to MOP. The formation of adduct-MeOH ions was found to be characteristic for secondary N-hydroxylamines. N-Oxides formed abundant MOP adducts just like sulfoxides, but sulfoxides can be differentiated from N-oxides based on their high reaction efficiencies. The reaction was tested by using the anti-inflammatory drug sulindac (a sulfoxide) and its metabolite sulindac sulfone. The presence of a sulfoxide functionality in the drug but a sulfone functionality in the metabolite was readily demonstrated. The presence of other functionalities in addition to sulfoxide in the analytes was found not to influence the diagnostic reactivity. PMID:24968187

  5. Shedding light on the mercury mass discrepancy by weighing Hg 52+ ions in a Penning trap

    NASA Astrophysics Data System (ADS)

    Fritioff, T.; Bluhme, H.; Schuch, R.; Bergström, I.; Björkhage, M.

    2003-07-01

    In their nuclear tables Audi and Wapstra have pointed out a serious mass discrepancy between their extrapolated values for the mercury isotopes and those from a direct measurement by the Manitoba group. The values deviate by as much as 85 ppb from each other with claimed uncertainties of about 16 and 7 ppb, respectively. In order to decide which values are correct the masses of the 198Hg and 204Hg isotopes have been measured in the Stockholm Penning trap mass spectrometer SMILETRAP using 52+ ions. This charge state corresponds to a filled Ni electron configuration for which the electron binding energy can be accurately calculated. The mass values obtained are 197.966 768 44(43) u for 198Hg and 203.973 494 10(39) u for 204Hg. These values agree with those measured by the Manitoba group, with a 3 times lower uncertainty. This measurement was made possible through the implementation of a cooling technique of the highly charged mercury ions during charge breeding in the electron beam ion source used for producing the Hg 52+ ions.

  6. DETERMINATION OF BROMATE IN DRINKING WATERS BY ION CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    Bromate is a disinfection by-product in drinking water, formed during the ozonation of source water containing bromide. An inductively coupled plasma mass spectrometer is combined with an ion chromatograph for the analysis of bromate in drinking waters. Three chromatographic colu...

  7. Compensation of the volume charge of ions in a time-of-flight mass analyzer

    NASA Astrophysics Data System (ADS)

    Hashimov, A. M.; Nuruyev, K. Z.; Gurbanov, K. B.; Nurubeyli, Z. K.; Nurubeyli, T. K.

    2007-11-01

    A method of forced compensation of the volume charge of ions leading to considerable deterioration of the dispersion characteristics of a time-of-flight mass analyzer with a sector electrostatic field is described. It is shown that recompensation of the voluem charge also deteriorates the resolution of the instrument.

  8. ION COMPOSITION ELUCIDATION (ICE): A HIGH RESOLUTION MASS SPECTROMETRIC TECHNIQUE FOR IDENTIFYING COMPOUNDS IN COMPLEX MIXTURES

    EPA Science Inventory

    When tentatively identifying compounds in complex mixtures using mass spectral libraries, multiple matches or no plausible matches due to a high level of chemical noise or interferences can occur. Worse yet, most analytes are not in the libraries. In each case, Ion Composition El...

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

    NASA Astrophysics Data System (ADS)

    Smentkowski, Vincent S.; Ostrowski, Sara G.

    2007-07-01

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

  10. Fragmentation of Multiply-Charged Intact Protein Ions Using MALDI TOF-TOF Mass Spectrometry

    PubMed Central

    Liu, Zhaoyang; Schey, Kevin L.

    2008-01-01

    Top down proteomics in a TOF-TOF instrument was further explored by examining the fragmentation of multiply charged precursors ions generated by matrix-assisted laser desorption ionization. Evaluation of sample preparation conditions allowed selection of solvent/matrix conditions and sample deposition methods to produce sufficiently abundant doubly and triply charged precursor ions for subsequent CID experiments. As previously reported, preferential cleavage was observed at sites C-terminal to acidic residues and N-terminal to proline residues for all ions examined. An increase in non-preferential fragmentation as well as additional low mass product ions was observed in the spectra from multiply charged precursor ions providing increased sequence coverage. This enhanced fragmentation from multiply charged precursor ions became increasingly important with increasing protein molecular weight and facilitates protein identification using database searching algorithms. The useable mass range for MALDI TOF-TOF analysis of intact proteins has been expanded to 18.2 kDa using this approach. PMID:17693096

  11. Advanced Ion Mass Spectrometer for Giant Planet Ionospheres, Magnetospheres and Moons

    NASA Astrophysics Data System (ADS)

    Sittler, EC; Cooper, JF; Paschalidis, N.; Jones, SL; Rodriguez, M.; Ali, A.; Coplan, MA; Chornay, DJ; Sturner; Bateman, FB; Andre, N.; Fedorov, A.; Wurz, P.

    2015-10-01

    The Advanced Ion Composition Spectrometer (AIMS) has been under development from various NASA sources (NASA LWSID, NASA ASTID, NASA Goddard IRADs) to measure elemental, isotopic, and simple molecular composition abundances of 1 eV/e to 25 keV/e hot ions with wide field-of-view (FOV) in the 1 - 60 amu mass range at mass resolution M/ΔM ≤ 60 over a wide dynamic range of intensities and penetrating radiation background from the inner magnetospheres of Jupiter and Saturn to the outer magnetospheric boundary regions and the upstream solar wind. This instrument will work for both spinning spacecraft and 3-axis stabilized spacecraft with wide field-of-view capability in both cases. It will measure the ion velocity distribution functions (IVDF) for the individual ion species; ion velocity moments of the IVDF will give the fluid parameters (density, flow velocity and temperature) of the individual ion species. Outer planet mission applications are Io Observer, Jupiter Europa Orbiter/Europa Clipper, Enceladus Orbiter, and Uranus Orbiter as described in the decadal survey, but would also be valuable for inclusion on other missions to outer planet destinations such as Saturn- Titan and Neptune-Triton and for future missions to terrestrial planets, Venus and Mars, the Moon, asteroids, and comets, and of course for geospace applications to the Earth.

  12. Dipole moments and orientation polarizabilities of diatomic molecular ions for precision atomic mass measurement

    NASA Astrophysics Data System (ADS)

    Cheng, Michelle; Brown, John M.; Rosmus, Pavel; Linguerri, Roberto; Komiha, Najia; Myers, Edmund G.

    2007-01-01

    In high precision Penning trap mass spectrometry the cyclotron frequency of a polarizable ion is perturbed due to the Stark interaction with the motional electric field. For polar diatomic molecular ions, which have adjacent rotational levels of opposite parity, these shifts can be particularly large—especially for the lowest rotational levels, which are those occupied by ions stored for many hours in cryogenic Penning traps. In order to provide corrections to precision atomic mass measurements, we consider the calculation of orientation polarizabilities of CO+ and the positive ions of the first and second row diatomic hydrides, LiH+ to ArH+ . Dipole moments for these ions have been calculated using the restricted coupled cluster method with perturbative triples and large basis sets. Using these dipoles and an effective Hamiltonian, we have obtained rotational-state dependent polarizabilities of the open-shell diatomic ions CO+ , NH+ , OH+ , FH+ , PH+ , SH+ , and ClH+ . Results are given for those rotational levels that are significantly populated at 4.2K , for magnetic fields up to 10T . For the remaining first and second row hydride cations, polarizabilities at the magnetic fields of interest can be obtained from a simple formula valid for closed-shell molecules. Conversely, in cases where the polarizability shifts can be measured, our results enable experimental determination of dipole moments.

  13. Combining ion mobility spectrometry, mass spectrometry, and photoelectron spectroscopy in a high-transmission instrument.

    PubMed

    Vonderach, Matthias; Ehrler, Oli T; Weis, Patrick; Kappes, Manfred M

    2011-02-01

    We have developed a novel instrument that combines ion mobility spectrometry, mass spectro-metry, and photoelectron spectroscopy. The instrument couples an electrospray ion source, a high-transmission ion mobility cell based on ion funnels, a quadrupole mass filter, and a time-of-flight (magnetic bottle) photoelectron spectrometer operated with a pulsed detachment laser. We show that the instrument can resolve highly structured anion arrival time distributions and at the same time provide corresponding photoelectron spectra-using the DNA oligonucleotide ion [dC(6) - 5H](5-) as a test case. For this multianion we find at least four different, noninterconverting isomers (conformers) simultaneously present in the gas phase at room temperature. For each of these we record well-resolved and remarkably different photoelectron spectra at each of three different detachment laser wavelengths. Two-dimensional ion mobility/electron binding energy plots can be acquired with an automated data collection procedure. We expect that this kind of instrument will significantly improve the capabilities for structure determination of (bio)molecular anions in the gas phase. PMID:21214198

  14. Triple quadrupole linear ion trap mass spectrometer for the analysis of small molecules and macromolecules.

    PubMed

    Hopfgartner, Gérard; Varesio, Emmanuel; Tschäppät, Viviane; Grivet, Chantal; Bourgogne, Emmanuel; Leuthold, Luc Alexis

    2004-08-01

    Recently, linear ion traps (LITs) have been combined with quadrupole (Q), time-of-flight (TOF) and Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS). LITs can be used either as ion accumulation devices or as commercially available, stand-alone mass spectrometers with MSn capabilities. The combination of triple quadrupole MS with LIT technology in the form of an instrument of configuration QqLIT, using axial ejection, is particularly interesting, because this instrument retains the classical triple quadrupole scan functions such as selected reaction monitoring (SRM), product ion (PI), neutral loss (NL) and precursor ion (PC) while also providing access to sensitive ion trap experiments. For small molecules, quantitative and qualitative analysis can be performed using the same instrument. In addition, for peptide analysis, the enhanced multiply charged (EMC) scan allows an increase in selectivity, while the time-delayed fragmentation (TDF) scan provides additional structural information. Various methods of operating the hybrid instrument are described for the case of the commercial Q TRAP (AB/MDS Sciex) and applications to drug metabolism analysis, quantitative confirmatory analysis, peptides analysis and automated nanoelectrospray (ESI-chip-MS) analysis are discussed. PMID:15329837

  15. Design and Performance Evaluation of a Linear Ion Trap Mass Analyzer Featuring Half Round Rod Electrodes

    NASA Astrophysics Data System (ADS)

    Li, Xiaoxu; Zhang, Xiaohua; Yao, Rujiao; He, Yang; Zhu, Yongyong; Qian, Jie

    2015-05-01

    A novel linear ion trap mass analyzer featuring half round rod electrodes (HreLIT) has been built. It is mainly composed of two pairs of stainless steel electrodes which have a cross-section of half round rod and a pair of end electrodes. The HreLIT has a simple structure and so it could be assembled by hand with relatively high mechanical accuracy. The external dimension of HreLIT is 50 mm × 29.5 mm × 28 mm (length × width × height) and its internal volume is about 3.8 cm3. A home-made HreLIT mass spectrometer with three-stage vacuum system was built and the performance of HreLIT was characterized using reserpine solution and PPG standard solution. When the scan rate was 254 u/s, mass peak with FWHM of 0.14 u was achieved for ions with m/z 609, which corresponds to a mass resolution of 4350. The HreLIT was also operated at a low q value of 0.28 to extend its mass range. The experiment result showed a mass range of over 2800 u and the amplitude of radio frequency (rf) signal was only 1560 V (0-p). Three-stage tandem mass spectrometry was successfully performed in the HreLIT, and the collision-induced dissociation (CID) efficiencies of MS2 (CID of ions with m/z 609) and MS3 (CID of ions with m/z 448) were 78% and 59%, respectively.

  16. The Bennett ion-mass spectrometer on Atmosphere Explorer-C and -E.

    NASA Technical Reports Server (NTRS)

    Brinton, H. C.; Scott, L. R.; Pharo, M. W., III; Coulson, J. T.

    1973-01-01

    The Bennett spectrometer to be flown on Atmosphere Explorer-C and -E (AE-C and AE-E) is designed to measure, throughout the 120 to 4000-km orbit, the concentrations of all thermal positive ions in the mass range 1 to 72 amu and number density range 5 to 5,000,000 ions per cu cm. To reduce the buildup of ram pressure and facilitate measurements at low altitude, the analyzer is vented, and a multigrid ion-current collector is employed. An extensive command capability permits optimization of instrument parameters for particular measurement objectives; commandable functions include mass-scan range and period, the sensitivity-resolution characteristic of the analyzer, orifice potential, and in-flight calibration.

  17. Tandem time-of-flight mass spectrometer (TOF-TOF) with a quadratic-field ion mirror

    NASA Astrophysics Data System (ADS)

    Giannakopulos, Anastassios E.; Thomas, Benjamin; Colburn, Alex W.; Reynolds, David J.; Raptakis, Emmanuel N.; Makarov, Alexander A.; Derrick, Peter J.

    2002-05-01

    A tandem time-of-flight (TOF-TOF) mass spectrometer comprised of two ion mirrors is described. The first ion mirror, which is a linear-field, single-stage mirror (MS1) with an intermediate collision cell, has been designed to provide the temporal focus necessary for the second, quadratic-field ion mirror (MS2) to function effectively. Due to the wide energy-range focusing capabilities of the quadratic field employed in the second ion mirror all the fragment ions can be collected in one spectrum without the need to step the reflecting working voltage of the MS2. The size of the active area of the microchannel plate detector used in the preliminary experiments was the limiting factor governing the collection efficiently of fragment ions. The use of the first ion mirror to provide temporal focusing of the precursor ion packet at the first focal point of the quadratic mirror used as the MS2 requires no alteration of the focusing conditions for different masses, in contrast to delayed extraction or postsource pulsed focusing. Precursor ions formed by matrix-assisted laser desorption/ionization were mass-selected with an ion gate located before the collision cell and the fragment ions were mass analyzed using the quadratic-field ion mirror. Experimental results demonstrating effective high-energy collision-induced dissociation of polymer and fullerene molecule-ions are presented.

  18. Titan's Topside Ionospheric Composition: Cassini Plasma Spectrometer Ion Mass spectrometer Measurements

    NASA Astrophysics Data System (ADS)

    Sittler, E. C., Jr.; Hartle, R. E.; Ali, A.; Cooper, J. F.; Lipatov, A. S.; Simpson, D. G.; Sarantos, M.; Chornay, D. J.

    2014-12-01

    In [1] the first quantitative evidence of ionospheric outflows (r > 10,000 km) coming from Titan was given using the Cassini Plasma Spectrometer (CAPS) Ion Mass Spectrometer (IMS) data for the T9 flyby. Later in [2] similar outflows were shown for T63 and T75. In [3] evidence for ionospheric outflows for T15 was given and [4] showed evidence of outflows for T41. Normally, the CAPS IMS cannot be used to measure Titan's relatively dense ionosphere because the IMS has high sensitivity to measure the more tenuous plasmas of Saturn's magnetosphere and its detectors will experience count rates beyond their maximum allowed rates, therefore the IMS is configured not to measure the ionospheric plasma. But, whenever there are high altitude Titan wake flybys the ion densities are low enough so the CAPS IMS can measure these ionospheric outflows and their corresponding composition characteristic of the topside ionosphere (i.e., composition freezes in above the exobase) using its unique compositional capabilities. For example, the IMS can distinguish against specific ion types such as hydrocarbon, nitrile and water group ions due fragmentation of molecular ions within the instrument (i.e., incident ions strikes ultra-thin carbon foils at 14.6 kV or higher with exiting fragments such C+,0,-, N+,0, O+,0,-1). The other ionospheric instruments only measure the ion mass-per-charge (M/Q), while the CAPS IMS measures both the ion M/Q and its fragments. Specific attention will be given to such ions as NH4+, N+, O+, CH4+, C2H5+, HCNH+ and C3H7+. These results may impose important constraints upon Titan's ionospheric water group, hydrocarbon and nitrile ion chemistry. Are NH4+ ions present as indicated by INMS at 1100 km altitude and/or water group ions? Our work has concentrated on the T15 flyby. Estimates of the NH4+, N+ and O+ abundances presently have upper values < 20% of the total ion density with actual abundances and their uncertainties to be given. [1] Sittler, E.C. Jr., et al

  19. Evaluation of ion trap mass spectrometry for the determination of ambient nicotine

    SciTech Connect

    Wise, M.B.; Higgins, C.E.; Ilgner, R.H.; Guerin, M.R.

    1989-01-01

    A thermal desorption unit has been interfaced directly with a Finnigan Ion Trap mass spectrometer (ITMS) for the identification and quantification of trace organics in air. No chromatographic separation of the desorbed constituents is performed prior to introduction into the mass spectrometer. Instead, positive identification of a compound is made based on its collision induced dissociation (CID) tandem (MS/MS) mass spectrum. Using this technique, as little as 50 pg of a constituent desorbed from resin trap can be characterized and quantified with a sample turnaround time of only 2--3 minutes. 3 refs.

  20. Effects of anions on the positive ion electrospray ionization mass spectra of peptides and proteins.

    PubMed

    Mirza, U A; Chait, B T

    1994-09-15

    Positive ion electrospray ionization mass spectra of polypeptides are usually obtained from solutions that are acidified and therefore contain relatively high concentrations of anions. The present study describes an investigation of the effects of these ubiquitous anions on the positive ion electrospray ionization mass spectra of peptides and proteins. Certain anionic species in the spray solutions were observed to cause a marked decrease in the net average charge of peptide and protein ions in the mass spectra compared to the average charge measured in the absence of these anions. This charge neutralization effect was found to depend solely on the nature of the anionic species and was independent of the source of the anion (acid or salt), with the propensity for neutralization following the order: CCl3COO- > CF3COO- > CH3COO- approximately Cl-. A mechanism for the observed charge reduction effect is proposed that involves two steps. The first step occurs in solution, where an anion pairs with a positively charged basic group on the peptide. The second step occurs during the process of desolvation or in the gas phase, where the ion pair dissociates to yield the neutral acid and the peptide with reduced charge state. The different propensities for charge neutralization of the different anionic species is presumed to reflect the avidity of the anion-peptide interaction. These findings demonstrate that any attempt to correlate the distribution of charge states observed on proteins in the gas phase (by positive ion electrospray ionization mass spectrometry) with the net charge residing on the protein in solution will require that the described anion effect be taken into account. In addition, it appears that some control over the distribution of charge states on peptides and protein ions can be exercised by an appropriate choice of anion in the electrospray solution. PMID:7978296

  1. Temperature and ion-mass dependence of amorphization dose for ion beam irradiated zircon (ZrSiO{sub 4})

    SciTech Connect

    Wang, L.M.; Ewing, R.C.; Weber, W.J.; Eby, R.K.

    1992-12-01

    The temperature dependence of amorphization dose for zircon under 1.5 MeV Kr ion irradiation has been investigated using the ANL HVEM-Tandem Facility. Three regimes were observed in the amorphization dose-temperature curve. In the first regime (15 to 300 K), the critical amorphization dose increased from 3.06 to 4.5 ions/nm{sup 2}. In the second regime (300 to 473 K), there is little change in the amorphizationdose. In the third regime (> 473 K), the amorphization dose increased exponentially to 8.3 ions/nm{sup 2} at 913 K. This temperature dependence of amorphization dose can be described by two processes with different activation energies (0.018 and 0.31 eV respectively) which are attributed to close pair recombination in the cascades at low temperatures and radiation-enhanced epitaxial recrystallization at higher temperatures. The upper temperature limit for amorphization of zircon is estimated to be 1100 K. The ion-mass dependence of the amorphization dose (in dpa) has also been discussed in terms of the energy to recoils based on data obtained from He, Ne, Ar, Kr, Xe irradiations and a {sup 238}Pu-doped sample.

  2. Temperature and ion-mass dependence of amorphization dose for ion beam irradiated zircon (ZrSiO[sub 4])

    SciTech Connect

    Wang, L.M.; Ewing, R.C. . Dept. of Geology); Weber, W.J. ); Eby, R.K. . Dept. of Geological Sciences)

    1992-12-01

    The temperature dependence of amorphization dose for zircon under 1.5 MeV Kr ion irradiation has been investigated using the ANL HVEM-Tandem Facility. Three regimes were observed in the amorphization dose-temperature curve. In the first regime (15 to 300 K), the critical amorphization dose increased from 3.06 to 4.5 ions/nm[sup 2]. In the second regime (300 to 473 K), there is little change in the amorphizationdose. In the third regime (> 473 K), the amorphization dose increased exponentially to 8.3 ions/nm[sup 2] at 913 K. This temperature dependence of amorphization dose can be described by two processes with different activation energies (0.018 and 0.31 eV respectively) which are attributed to close pair recombination in the cascades at low temperatures and radiation-enhanced epitaxial recrystallization at higher temperatures. The upper temperature limit for amorphization of zircon is estimated to be 1100 K. The ion-mass dependence of the amorphization dose (in dpa) has also been discussed in terms of the energy to recoils based on data obtained from He, Ne, Ar, Kr, Xe irradiations and a [sup 238]Pu-doped sample.

  3. Resonance enhanced multiphoton ionization/secondary neutral mass spectrometry and cesium attachment secondary ion mass spectrometry of bronze : a comparison.

    SciTech Connect

    McCann, M. P.; Calaway, W. F.; Pellin, M. J.; Veryovkin, I. V.; Constantinides, I.; Adriaens, A.; Adams, F.; Materials Science Division; Sam Houston State Univ.; Univ. of Antwerp

    2002-05-01

    Archaeologists have considerable interests in ancient bronzes. They want to know how these alloys were produced and how they corroded with time. Modern bronzes, with compositions very close to that of some ancient bronzes, have been produced and two methods were examined to characterize one of these modern bronzes. Analysis of this modern bronze using resonance enhanced multiphoton ionization/secondary neutral mass spectrometry (REMPI/SNMS) is examined in detail and compared to cesium attachment secondary ion mass spectrometry (CsAMS) results. Both REMPI/SNMS and CsAMS were used to quantify the composition of Fe, Ni and Mn in a modern quaternary bronze designed to serve as a certified reference material for an ancient bronze. Both methods exhibit reduced matrix effects when compared to secondary ion mass spectrometry (SIMS) and thus quantification should be simplified. It was found that when relative sensitivity factors obtained from a standard bronze material are used to calibrate the instruments, the REMPI/SNMS measurements yield results that were more sensitive and more accurate.

  4. 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. PMID:22528201

  5. Photoluminescence Spectroscopy of Mass-Selected Electrosprayed Ions Embedded in Cryogenic Rare-Gas Matrixes.

    PubMed

    Kern, Bastian; Greisch, Jean-François; Strelnikov, Dmitry; Weis, Patrick; Böttcher, Artur; Ruben, Mario; Schäfer, Bernhard; Schooss, Detlef; Kappes, Manfred M

    2015-12-01

    An apparatus is presented which combines nanoelectrospray ionization for isolation of large molecular ions from solution, mass-to-charge ratio selection in gas-phase, low-energy-ion-beam deposition into a (co-condensed) inert gas matrix and UV laser-induced visible-region photoluminescence (PL) of the matrix isolated ions. Performance is tested by depositing three different types of lanthanoid diketonate cations including also a dissociation product species not directly accessible by chemical synthesis. For these strongly photoluminescent ions, accumulation of some femto- to picomoles in a neon matrix (over a time scale of tens of minutes to several hours) is sufficient to obtain well-resolved dispersed emission spectra. We have ruled out contributions to these spectra due to charge neutralization or fragmentation during deposition by also acquiring photoluminescence spectra of the same ionic species in the gas phase. PMID:26553589

  6. Preparation of high-purity Cu films by non-mass separated ion beam deposition

    NASA Astrophysics Data System (ADS)

    Lim, J.-W.; Mimura, K.; Miyake, K.; Yamashita, M.; Isshiki, M.

    2003-05-01

    Cu films were deposited on Si(1 0 0) substrates by applying a negative substrate bias voltage using non-mass separated ion beam deposition (IBD) method. By the SIMS results with Cs + ion beam, the Cu film deposited at VS=0 V was found to contain more impurities than the Cu film deposited at VS=-50 V. On the other hand, from the SIMS results with O 2+ ion beam, it was found that elements which are easy to be positive ions such as B, Mg, Na, Al, K, Ca and Fe seem to be increased slightly as compared to the those of the Cu film deposited at VS=0 V. As a result, higher-purity Cu film deposited at VS=-50 V could be obtained in comparison with the film deposited at VS=0 V. The purification effect of the Cu film deposited at VS=-50 V was described in details.

  7. Nuclear induces effects and mass correlations in low and multiply charged helium-like ions

    NASA Astrophysics Data System (ADS)

    Stoyanov, Zh K.; Pavlov, R. L.; Mihailov, L. M.; Velchev, Ch J.; Mutafchieva, Y. D.; Tonev, D.; Chamel, N.

    2016-06-01

    The ground-state electron energies, the mass correction and mass polarization of low and multiply charged helium-like ions are analytically and numerically calculated. Approximately 3500 different kinds of ions with charge Z = 2 ÷ 118 are considered. The two-electron Schrodinger equation was solved using a discrete variational-perturbation approach developed by the authors and based on explicitly correlated wave functions. This approach takes into account the motion of the nucleus and yields accurate values for the electron characteristics. The results are presented with and without the inclusion of the mass polarization in the minimization procedure. The relative importance of mass correlations and relativistic effects in the formation of the electron energy characteristics of the helium-like ions are studied for different values of Z. The role of the inclusion of the mass polarization in the minimization procedure as an instrument to present and take into account the effects induced by the nuclear properties, structure and characteristics has been shown.

  8. Bayesian Deconvolution of Mass and Ion Mobility Spectra: From Binary Interactions to Polydisperse Ensembles

    PubMed Central

    Marty, Michael T.; Baldwin, Andrew J.; Marklund, Erik G.; Hochberg, Georg K. A.; Benesch, Justin L. P.; Robinson, Carol V.

    2015-01-01

    Interpretation of mass spectra is challenging because they report a ratio of two physical quantities, mass and charge, which may each have multiple components that overlap in m/z. Previous approaches to disentangling the two have focused on peak assignment or fitting. However, the former struggle with complex spectra, and the latter are generally computationally intensive and may require substantial manual intervention. We propose a new data analysis approach that employs a Bayesian framework to separate the mass and charge dimensions. Based on this approach, we developed UniDec (Universal Deconvolution), software that provides a rapid, robust, and flexible deconvolution of mass spectra and ion mobility-mass spectra with minimal user intervention. Incorporation of the charge-state distribution in the Bayesian prior probabilities provides separation of the m/z spectrum into its physical mass and charge components. We have evaluated our approach using systems of increasing complexity, enabling us to deduce lipid binding to membrane proteins, to probe the dynamics of subunit exchange reactions, and to characterize polydispersity in both protein assemblies and lipoprotein Nanodiscs. The general utility of our approach will greatly facilitate analysis of ion mobility and mass spectra. PMID:25799115

  9. Ion chemistry of VX surrogates and ion energetics properties of VX: new suggestions for VX chemical ionization mass spectrometry detection.

    PubMed

    Midey, Anthony J; Miller, Thomas M; Viggiano, A A; Bera, Narayan C; Maeda, Satoshi; Morokuma, Keiji

    2010-05-01

    Room temperature rate constants and product ion branching ratios have been measured for the reactions of numerous positive and negative ions with VX chemical warfare agent surrogates representing the amine (triethylamine) and organophosphonate (diethyl methythiomethylphosphonate (DEMTMP)) portions of VX. The measurements have been supplemented by theoretical calculations of the proton affinity, fluoride affinity, and ionization potential of VX and the simulants. The results show that many proton transfer reactions are rapid and that the proton affinity of VX is near the top of the scale. Many proton transfer agents should detect VX selectively and sensitively in chemical ionization mass spectrometers. Charge transfer with NO(+) should also be sensitive and selective since the ionization potential of VX is small. The surrogate studies confirm these trends. Limits of detection for commercial and research grade CIMS instruments are estimated at 80 pptv and 5 ppqv, respectively. PMID:20384284

  10. Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species (Au11L53+, L = 1,3-bis(diphenylphosphino)propane) which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (TOF-SIMS) it is demonstrated that the Au11L53+ cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-

  11. Mass Spectrometric Observation of Doubly Charged Alkaline-Earth Argon Ions.

    PubMed

    Hattendorf, Bodo; Gusmini, Bianca; Dorta, Ladina; Houk, Robert S; Günther, Detlef

    2016-09-01

    Doubly charged diatomic ions MAr(2+) where M=Mg, Ca, Sr or Ba have been observed by mass spectrometry with an inductively coupled plasma ion source. Abundance ratios are quite high, 0.1 % for MgAr(2+) , 0.4 % for CaAr(2+) , 0.2 % for SrAr(2+) and 0.1 % for BaAr(2+) relative to the corresponding doubly charged atomic ions M(2+) . It is assumed that these molecular ions are formed through reactions of the doubly charged metal ions with neutral argon atoms within the ion source. Bond dissociation energies (D0 ) were calculated and agree well with previously published values. The abundance ratios MAr(+) /M(+) and MAr(2+) /M(2+) generally follow the predicted bond dissociation energies with the exception of MgAr(2+) . Mg(2+) should form the strongest bond with Ar [D0 (MgAr(2+) )=124 to 130 kJ mol(-1) ] but its relative abundance is similar to that of the weakest bound BaAr(2+) (D0 =34 to 42 kJ mol(-1) ). The relative abundances of the various MAr(2+) ions are higher than those expected from an argon plasma at T=6000 K, indicating that collisions during ion extraction reduce the abundance of the MAr(2+) ions relative to the composition in the source. The corresponding singly charged MAr(+) ions are also observed but occur at about three orders of magnitude lower intensity than MAr(2+) . PMID:27252087

  12. Interlaboratory study of the ion source memory effect in 36Cl accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pavetich, Stefan; Akhmadaliev, Shavkat; Arnold, Maurice; Aumaître, Georges; Bourlès, Didier; Buchriegler, Josef; Golser, Robin; Keddadouche, Karim; Martschini, Martin; Merchel, Silke; Rugel, Georg; Steier, Peter

    2014-06-01

    Understanding and minimization of contaminations in the ion source due to cross-contamination and long-term memory effect is one of the key issues for accurate accelerator mass spectrometry (AMS) measurements of volatile elements. The focus of this work is on the investigation of the long-term memory effect for the volatile element chlorine, and the minimization of this effect in the ion source of the Dresden accelerator mass spectrometry facility (DREAMS). For this purpose, one of the two original HVE ion sources at the DREAMS facility was modified, allowing the use of larger sample holders having individual target apertures. Additionally, a more open geometry was used to improve the vacuum level. To evaluate this improvement in comparison to other up-to-date ion sources, an interlaboratory comparison had been initiated. The long-term memory effect of the four Cs sputter ion sources at DREAMS (two sources: original and modified), ASTER (Accélérateur pour les Sciences de la Terre, Environnement, Risques) and VERA (Vienna Environmental Research Accelerator) had been investigated by measuring samples of natural 35Cl/37Cl-ratio and samples highly-enriched in 35Cl (35Cl/37Cl ∼ 999). Besides investigating and comparing the individual levels of long-term memory, recovery time constants could be calculated. The tests show that all four sources suffer from long-term memory, but the modified DREAMS ion source showed the lowest level of contamination. The recovery times of the four ion sources were widely spread between 61 and 1390 s, where the modified DREAMS ion source with values between 156 and 262 s showed the fastest recovery in 80% of the measurements.

  13. Identification of ion series using ion mobility mass spectrometry: the example of alkyl-benzothiophene and alkyl-dibenzothiophene ions in diesel fuels.

    PubMed

    Maire, Florian; Neeson, Kieran; Denny, Richard; McCullagh, Michael; Lange, Catherine; Afonso, Carlos; Giusti, Pierre

    2013-06-01

    Ion mobility-mass spectrometry (IMMS) has been presented as a promising method for analysis of highly complex mixtures. This coupling adds an additional postionization separation dimension to MS. The IM separation of ions is obtained in the millisecond time scale and can be particularly helpful when chromatographic separation is not possible. For obtaining relevant information about the samples, data processing is usually the bottleneck because of the high amount of data generated with IMMS. In the current work, we present a new workflow using specific comparison software dedicated to IMMS data, which allows one to compare m/z-drift time plots to highlight differences between samples. Two diesel fuels have been compared, i.e., the feed and the product of hydrodesulfurization (HDS) process, and this approach allowed us to clearly highlight the variation of intensity of several ions distributed along the plots of both samples. Accurate mass measurements and post IM collision induced dissociation experiments allowed us to identify two series of polycyclic aromatic sulfur-containing heterocycle (PASH) compounds among the matrix ions. PMID:23638962

  14. DIRECT TRACE ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN AIR USING ION TRAP MASS SPECTROMETERS WITH FILTERED NOISE FIELDS

    EPA Science Inventory

    Two ion trap mass spectrometers and direct air sampling interfaces are being evaluated in the laboratory for monitoring toxic air pollutants in real time. he mass spectrometers are the large, laboratory-based Finnigan MAT ion trap (ITMS) and the compact, field-deployable Teledyne...

  15. Development of an ion trap/multi-turn time-of-flight mass spectrometer with potential- lift.

    PubMed

    Iwamoto, Kenichi; Nagao, Hirofumi; Toyoda, Michisato

    2009-01-01

    An ion trap/multi-turn time-of-flight (ToF) mass spectrometer with potential-lift has been developed. This system consists of an external ion source, a lens system, an ion trap, a potential-lift, a multi-turn ToF mass spectrometer and a detector. The ion trap consists of hyperbolic electrode cross-sections (Paul trap) and is used as an ion storage device. The potential-lift, which is part of the flight tube, was attached between the ion trap and the multi-turn ToF mass spectrometer. The potential-lift is known to be useful for increasing the kinetic energy of the ions. In order to check the ability of the potential-lift, mass distributions of [(CsI)(n) Cs]+ clusters (n = 1-9) were measured. The relative intensity ratios of the [(CsI)(n)Cs]+ clusters were consistent with the results obtained using other apparatus. To check the properties of the new apparatus, Xe+ isotopes were analyzed using either a linear or multi-turn ToF mass spectrometer. In the linear mode, the mass resolution was 500. In the multi-turn mode, the resolution depended on the number of cycles of the multi-turn ToF mass spectrometer; the mass resolution was 4400 (FWHM) after nine cycles. This new apparatus with a high resolution will be useful for measurements of ion-molecule reactions and photodissociations. PMID:19423910

  16. Screening and identification of glyceollins and their metabolites by electrospray ionization tandem mass spectrometry with precursor ion scanning

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A method has been developed for screening glyceollins and their metabolites based upon precursor ion scanning. Under higher-energy collision conditions, employing a triple quadrupole mass spectrometer in the negative ion mode, deprotonated glyceollin precursors yield a diagnostic radical product ion...

  17. ESTIMATION OF MUTAGENIC/CARCINOGENIC POTENTIAL OF ENVIRONMENTAL CONTAMINANTS BY ION-MOLECULE REACTIONS AND TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    The ability to produce and detect products of model DNA/carcinogen ion-molecule reactions is demonstrated in the ion source and the collision cell of a triple quadrupole tandem mass spectrometer. eaction between adenine and benzoyl chloride in the ion source is shown to produce t...

  18. Computer simulations of a new three rods ion optic (TRIPOLE) with high focusing and mass filtering capabilities.

    PubMed

    Salazar, Gary Abdiel; Masujima, Tsutomu

    2007-03-01

    A novel three rod (tripole) ion optic to which three AC voltages with symmetrically delayed phase shifts were applied to each electrode. We studied its ion guiding, focusing, and mass filtering capabilities by SIMION ver. 7.0 computer simulations. An electric field mathematical model was developed to calculate the pseudopotential of the tripole radial AC force. The tripole showed stable ion guiding for wide ranges of AC amplitude; better collisional focusing than hexapole and octapole and similar focusing as quadrupole (rod pole). Also, the ion optic clearly showed interesting mass filtering potential when the phase shift was asymmetrically delayed. The symmetric shape of the pseudopotential field explained the tripole ion guiding and focusing capabilities. For mass filtering, the pseudopotential was asymmetric and its effect was balanced with DC voltage to separate the ions, depending in their masses. The resolution was much lower than quadrupole but useful when rough filtering was required. PMID:17142055

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

    SciTech Connect

    Greenwood, J. B.; Kelly, O.; Calvert, C. R.; Duffy, M. J.; King, R. B.; Belshaw, L.; Graham, L.; Alexander, J. D.; Williams, I. D.; Bryan, W. A.; Turcu, I. C. E.; Cacho, C. M.; Springate, E.

    2011-04-15

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

  20. Time resolved mass spectrometry of positive ions originated from atmospheric-pressure plasma jet

    NASA Astrophysics Data System (ADS)

    Selakovic, Nenad; Puac, Nevena; Maletic, Dejan; Malovic, Gordana; Petrovic, Zoran Lj.

    2013-09-01

    We present time-resolved measurements of positive ions originated from the atmospheric pressure plasma jet (APPJ) by using HIDEN HPR60 mass energy analyzer. APPJ was made of Pyrex glass tube with two transparent electrodes (15 mm wide PET foil). The gap between the electrodes was 15 mm, excitation frequency 80 kHz and applied voltage 6-10 kVpeak - to - peak. Helium flow rate was kept constant at 4 slm. In all measurements the distance between the plasma source and mass spectrometer orifice was 15 mm. Spectrometer detector gating was synchronized with the applied current and voltage signals in order to track in time the signal of detected ions. The internal gate width of HPR60 analyzer was 0.1 μs. We performed time resolved mass spectrometry of most abundant ion species originated from plasma jet: N2+(36%),N+(20%), O2+(18.5%),O+(16.8%), H2O+(6.1%), OH+, NO+, N2H+ and Ar+ (a few percentage). Results have shown that maximum intensity of nitrogen ions is lagging the maximum of current and voltage signal and maximum intensity for oxygen species is in opposite phase with current-voltage signals. Supported by MESTD, RS, III41011 and ON171037.

  1. Advanced Automation for Ion Trap Mass Spectrometry-New Opportunities for Real-Time Autonomous Analysis

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Wong, C. M.; Salmonson, J. D.; Yost, R. A.; Griffin, T. P.; Yates, N. A.; Lawless, James G. (Technical Monitor)

    1994-01-01

    The utility of MS/MS for both target compound analysis and the structure elucidation of unknowns has been described in a number of references. A broader acceptance of this technique has not yet been realized as it requires large, complex, and costly instrumentation which has not been competitive with more conventional techniques. Recent advancements in ion trap mass spectrometry promise to change this situation. Although the ion trap's small size, sensitivity, and ability to perform multiple stages of mass spectrometry have made it eminently suitable for on-line, real-time monitoring applications, advance automation techniques are required to make these capabilities more accessible to non-experts. Towards this end we have developed custom software for the design and implementation of MS/MS experiments. This software allows the user to take full advantage of the ion trap's versatility with respect to ionization techniques, scan proxies, and ion accumulation/ejection methods. Additionally, expert system software has been developed for autonomous target compound analysis. This software has been linked to ion trap control software and a commercial data system to bring all of the steps in the analysis cycle under control of the expert system. These software development efforts and their utilization for a number of trace analysis applications will be described.

  2. Ion trace detection algorithm to extract pure ion chromatograms to improve untargeted peak detection quality for liquid chromatography/time-of-flight mass spectrometry-based metabolomics data.

    PubMed

    Wang, San-Yuan; Kuo, Ching-Hua; Tseng, Yufeng J

    2015-03-01

    Able to detect known and unknown metabolites, untargeted metabolomics has shown great potential in identifying novel biomarkers. However, elucidating all possible liquid chromatography/time-of-flight mass spectrometry (LC/TOF-MS) ion signals in a complex biological sample remains challenging since many ions are not the products of metabolites. Methods of reducing ions not related to metabolites or simply directly detecting metabolite related (pure) ions are important. In this work, we describe PITracer, a novel algorithm that accurately detects the pure ions of a LC/TOF-MS profile to extract pure ion chromatograms and detect chromatographic peaks. PITracer estimates the relative mass difference tolerance of ions and calibrates the mass over charge (m/z) values for peak detection algorithms with an additional option to further mass correction with respect to a user-specified metabolite. PITracer was evaluated using two data sets containing 373 human metabolite standards, including 5 saturated standards considered to be split peaks resultant from huge m/z fluctuation, and 12 urine samples spiked with 50 forensic drugs of varying concentrations. Analysis of these data sets show that PITracer correctly outperformed existing state-of-art algorithm and extracted the pure ion chromatograms of the 5 saturated standards without generating split peaks and detected the forensic drugs with high recall, precision, and F-score and small mass error. PMID:25622715

  3. Microfabricated ion trap mass spectrometry for characterization of organics and potential biomarkers

    NASA Astrophysics Data System (ADS)

    Austin, Daniel

    Mass spectrometry is a powerful analytical technique with a strong history in planetary exploration, and is the method of choice for detection and identification of organic and biological molecules. MS instrumentation can also be combined with techniques such as gas chromatography, liquid chromatography, or chiral separation, which are particularly important for analysis of complex mixtures or possible homochirality. Ion traps have several inherent advantages, including speed of analysis (important for GC-MS), MS/MS capabilities (important to identification of unknown compounds), excellent sensitivity, and ease of coupling with ambient ionization techniques that are under development for biomolecule detection. We report on progress in using microfabrication techniques to produce radiofrequency quadrupole ion traps that are much smaller, lighter, and lower power than existing instruments. We produce ion traps using an assembly of two ceramic plates, the facing surfaces of which are lithographically patterned with electrodes. This approach allows great flexibility in the trap geometry, and we have demonstrated working mass spectrometers with quadrupole, linear, and toroidal trapping fields. The approach also allows correction of higher-order terms in the electric field. With this system, mass resolution of up to 1300 has been demonstrated, which is adequate for identification of a wide range of potential biomarkers. Capabilities such as tandem analysis have also been demonstrated. Of particular interest is an ion trap that contains both quadrupole and toroidal trapping regions simultaneously and coaxially. Ions can be trapped as a large reservoir in the toroidal region and introduced in small batches to the quadrupole region for mass analysis. This capability is particularly valuable where the sample of interest is very small, such as microfossil with trace organics, and where the organic inventory is both complex and unknown. Development and results of this device

  4. Electrically compensated Fourier transform ion cyclotron resonance cell for complex mixture mass analysis.

    PubMed

    Kaiser, Nathan K; Savory, Joshua J; McKenna, Amy M; Quinn, John P; Hendrickson, Christopher L; Marshall, Alan G

    2011-09-01

    Complex natural organic mixtures such as petroleum require ultrahigh mass spectral resolution to separate and identify thousands of elemental compositions. Here, we incorporate a custom-built, voltage-compensated ICR cell for Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS), based on a prior design by Tolmachev to produce optimal mass resolution. The compensated ICR cell installed in a custom-built 9.4 T FTICR mass spectrometer consists of seven cylindrical segments with axial proportions designed to generate a dc trapping potential that approaches an ideal three-dimensional axial quadrupolar potential. However, the empirically optimized compensation voltages do not correspond to the most quadrupolar trapping field. The compensation electrodes minimize variation in the reduced cyclotron frequency by balancing imperfections in the magnetic and electric field. The optimized voltages applied to compensation electrodes preserve ion cloud coherence for longer transient duration by approximately a factor of 2, enabling separation and identification of isobaric species (compounds with the same nominal mass but different exact mass) common in petroleum, such as C(3) vs SH(4) (separated by 3.4 mDa) and SH(3)(13)C vs (12)C(4) (separated by 1.1 mDa). The improved performance of the ICR cell provides more symmetric peak shape and better mass measurement accuracy. A positive ion atmospheric pressure photoionization (APPI) petroleum spectrum yields more than 26,000 assigned peaks, Fourier-limited resolving power of 800,000 at m/z 500 (6.6 s transient duration), and 124 part per billion root mean square (rms) error. The tunability of the compensation electrodes is critical for optimal performance. PMID:21838231

  5. Ion trap mass spectrometry on a comet nucleus: the Ptolemy instrument and the Rosetta space mission.

    PubMed

    Todd, John F J; Barber, Simeon J; Wright, Ian P; Morgan, Geraint H; Morse, Andrew D; Sheridan, Simon; Leese, Mark R; Maynard, Jon; Evans, Suzanne T; Pillinger, Colin T; Drummond, Duncan L; Heys, Samantha C; Huq, S Ejaz; Kent, Barry J; Sawyer, Eric C; Whalley, Martin S; Waltham, Nicholas R

    2007-01-01

    In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials. PMID:17154436

  6. Ion funnel augmented Mars atmospheric pressure photoionization mass spectrometry for in situ detection of organic molecules.

    PubMed

    Johnson, Paul V; Hodyss, Robert; Beauchamp, J L

    2014-11-01

    Laser desorption is an attractive technique for in situ sampling of organics on Mars given its relative simplicity. We demonstrate that under simulated Martian conditions (~2.5 Torr CO(2)) laser desorption of neutral species (e.g., polycyclic aromatic hydrocarbons), followed by ionization with a simple ultraviolet light source such as a discharge lamp, offers an effective means of sampling organics for detection and identification with a mass spectrometer. An electrodynamic ion funnel is employed to provide efficient ion collection in the ambient Martian environment. This experimental methodology enables in situ sampling of Martian organics with minimal complexity and maximum flexibility. PMID:24986759

  7. The Spontaneous Loss of Coherence Catastrophe in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    PubMed Central

    Aizikov, Konstantin; Mathur, Raman; O’Connor, Peter B.

    2009-01-01

    The spontaneous loss of coherence catastrophe (SLCC) is a frequently observed, yet poorly studied, space-charge related effect in Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). This manuscript presents an application of the filter diagonalization method (FDM) in the analysis of this phenomenon. The temporal frequency behavior reproduced by frequency shift analysis using the FDM shows the complex nature of the SLCC, which can be explained by a combination of factors occurring concurrently, governed by electrostatics and ion packet trajectories inside the ICR cell. PMID:19013078

  8. Mass analysis addition to the Differential Ion Flux Probe (DIFP) study

    NASA Technical Reports Server (NTRS)

    Wright, K. H., Jr.; Jolley, Richard

    1994-01-01

    The objective of this study is to develop a technique to measure the characteristics of space plasmas under highly disturbed conditions; e.g., non-Maxwellian plasmas with strong drifting populations and plasmas contaminated by spacecraft outgassing. The approach, conducted in conjunction with current MSFC activities, is to extend the capabilities of the Differential Ion Flux Probe (DIFP) to include a high throughput mass measurement that does not require either high voltage or contamination sensitive devices such as channeltron electron multipliers or microchannel plates. This will significantly reduce the complexity and expense of instrument fabrication, testing, and integration of flight hardware compared to classical mass analyzers. The feasibility of the enhanced DIFP has been verified by using breadboard test models in a controlled plasma environment. The ability to manipulate particles through the instrument regardless of incident angle, energy, or ionic component has been amply demonstrated. The energy analysis mode is differential and leads directly to a time-of-flight mass measurement. With the new design, the DIFP will separate multiple ion streams and analyze each stream independently for ion flux intensity, velocity (including direction of motion), mass, and temperature (or energy distribution). In particular, such an instrument will be invaluable on follow-on electrodynamic TSS missions and, possibly, for environmental monitoring on the space station.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  10. Selective injection and isolation of ions in quadrupole ion trap mass spectrometry using notched waveforms created using the inverse Fourier transform

    SciTech Connect

    Soni, M.H.; Cooks, R.G. )

    1994-08-01

    Broad-band excitation of ions is accomplished in the quadrupole ion trap mass spectrometer using notched waveforms created by the SWIFT (stored waveform inverse Fourier transform) technique. A series of notched SWIFT pulses are applied during the period of ion injection from an external Cs[sup +] source to resonantly eject all ions whose resonance frequencies fall within the frequency range of the pulse while injecting only those analyte ions whose resonance frequencies fall within the limits of the notch. This allows selective injection and accumulation of the ions of interest and continuous ejection of the unwanted ions. This is shown to result in significant improvement in S/N ratio, resolution, and sensitivity for the analyte ions of interest. Selective ion injection is demonstrated by injecting the protonated molecules of peptides VSV and gramicidin S and the intact cation of l-carnitine hydrochloride, using singly notched SWIFT pulses. Multiply notched SWIFT pulses are used to simultaneously inject ions of different m/z values of l-carnitine hydrochloride into the ion trap. A new coarse/fine ion isolation procedure, which employs a doubly notched SWIFT pulse, is demonstrated for isolating ions of a single m/z value of 4-bromobiphenyl from a population of trapped ions. 36 refs., 10 figs., 2 tabs.

  11. Neutron-encoded signatures enable product ion annotation from tandem mass spectra.

    PubMed

    Richards, Alicia L; Vincent, Catherine E; Guthals, Adrian; Rose, Christopher M; Westphall, Michael S; Bandeira, Nuno; Coon, Joshua J

    2013-12-01

    We report the use of neutron-encoded (NeuCode) stable isotope labeling of amino acids in cell culture for the purpose of C-terminal product ion annotation. Two NeuCode labeling isotopologues of lysine, (13)C6(15)N2 and (2)H8, which differ by 36 mDa, were metabolically embedded in a sample proteome, and the resultant labeled proteins were combined, digested, and analyzed via liquid chromatography and mass spectrometry. With MS/MS scan resolving powers of ~50,000 or higher, product ions containing the C terminus (i.e. lysine) appear as a doublet spaced by exactly 36 mDa, whereas N-terminal fragments exist as a single m/z peak. Through theory and experiment, we demonstrate that over 90% of all y-type product ions have detectable doublets. We report on an algorithm that can extract these neutron signatures with high sensitivity and specificity. In other words, of 15,503 y-type product ion peaks, the y-type ion identification algorithm correctly identified 14,552 (93.2%) based on detection of the NeuCode doublet; 6.8% were misclassified (i.e. other ion types that were assigned as y-type products). Searching NeuCode labeled yeast with PepNovo(+) resulted in a 34% increase in correct de novo identifications relative to searching through MS/MS only. We use this tool to simplify spectra prior to database searching, to sort unmatched tandem mass spectra for spectral richness, for correlation of co-fragmented ions to their parent precursor, and for de novo sequence identification. PMID:24043425

  12. Neutron-encoded Signatures Enable Product Ion Annotation From Tandem Mass Spectra*

    PubMed Central

    Richards, Alicia L.; Vincent, Catherine E.; Guthals, Adrian; Rose, Christopher M.; Westphall, Michael S.; Bandeira, Nuno; Coon, Joshua J.

    2013-01-01

    We report the use of neutron-encoded (NeuCode) stable isotope labeling of amino acids in cell culture for the purpose of C-terminal product ion annotation. Two NeuCode labeling isotopologues of lysine, 13C615N2 and 2H8, which differ by 36 mDa, were metabolically embedded in a sample proteome, and the resultant labeled proteins were combined, digested, and analyzed via liquid chromatography and mass spectrometry. With MS/MS scan resolving powers of ∼50,000 or higher, product ions containing the C terminus (i.e. lysine) appear as a doublet spaced by exactly 36 mDa, whereas N-terminal fragments exist as a single m/z peak. Through theory and experiment, we demonstrate that over 90% of all y-type product ions have detectable doublets. We report on an algorithm that can extract these neutron signatures with high sensitivity and specificity. In other words, of 15,503 y-type product ion peaks, the y-type ion identification algorithm correctly identified 14,552 (93.2%) based on detection of the NeuCode doublet; 6.8% were misclassified (i.e. other ion types that were assigned as y-type products). Searching NeuCode labeled yeast with PepNovo+ resulted in a 34% increase in correct de novo identifications relative to searching through MS/MS only. We use this tool to simplify spectra prior to database searching, to sort unmatched tandem mass spectra for spectral richness, for correlation of co-fragmented ions to their parent precursor, and for de novo sequence identification. PMID:24043425

  13. Electrospray liquid chromatography quadrupole ion trap mass spectrometry determination of phenyl urea herbicides in water.

    PubMed

    Draper, W M

    2001-06-01

    Phenyl urea herbicides were determined in water by electrospray quadrupole ion trap liquid chromatography-mass spectrometry (ES-QIT-LC-MS). Over a wide concentration range [M - H](-) and MH(+) ions were prominent in ES spectra. At high concentrations dimer and trimer ions appeared, and sodium, potassium, and ammonium adducts also were observed. In the case of isopturon, source collision-induced dissociation (CID) fragmentation with low offset voltages increased the ion current associated with MH(+) and diminished dimer and trimer ion abundance. In the mass analyzer CID involved common pathways, for example, daughter ions of [M - H](-) resulted from loss of R(2)NH in N',N'-dialkyl ureas or loss of C(3)H(5)NO(2) (87 amu) in N'-methoxy ureas. A 2 mm (i.d.) x 15 cm C(18) reversed phase column was used for LC-MS with a linear methanol/water gradient and 0.5 mL/min flow rate. Between 1 and 100 pg/microg/L the response was highly linear with instrument detection limits ranging from <10 to 50 pg injected. Whereas the positive ES signal intensity was greater for each of the compounds except fluometuron, negative ion monitoring gave the highest signal-to-noise ratio. Analysis of spiked Colorado River water, a source high in total dissolved solids and total organic carbon, demonstrated that ES-QIT-LC-MS was routinely capable of quantitative analysis at low nanogram per liter concentrations in conjunction with a published C(18) SPE method. Under these conditions experimental method detection limits were between 8.0 and 36 ng/L, and accuracy for measurements in the 20-50 parts per trillion range was from 77 to 96%. Recoveries were slightly lower in surface water (e.g., 39-76%), possibly due to suppression of ionization. PMID:11409961

  14. Characterization of methyl methacrylate oligomers using secondary ion mass spectrometry, APCI mass spectrometry and molecular orbital theory

    NASA Astrophysics Data System (ADS)

    Takeuchi, T.; Iwai, K.; Momoji, K.; Miyamoto, I.; Saiki, K.; Hashimoto, K.

    2003-01-01

    The ionization efficiency and fragmentation mechanism of methyl methacrylate (MMA) oligomers (3-mer˜8-mer) were investigated by using secondary ion mass spectrometry (SIMS) and APCI mass spectrometry (APCI-MS). Protonation and fragmentation mechanisms of MMA oligomers were clarified by using molecular orbital (MO) methods. MMA oligomers were synthesized in anionic polymerization, and the oligomers were fractionated into 3-mer˜8-mer using gel permeation chromatography (GPC). In SIMS of MMA oligomers (3-mer˜8-mer), [MH] +, [MH-CH 3OH] +, [MH-methyl formate] + and [MH-2CH 3OH-methyl formate] + appeared. The peak intensities of adduct ions [M+Li] +, [M+Na] + and [M+K] + increased with the increase of the polymerization degree. The optimized geometries and H +, Li +, Na + and K + affinities of MMA monomer (1-mer), dimer (2-mer), and trimer (3-mer) were calculated using the PM3 and ab initio MO methods. The calculated H +, Li +, Na + and K + affinities increased in order of 1-mer, 2-mer and 3-mer of MMA.

  15. High Resolution Studies of the Origins of Polyatomic Ions in Inductively Coupled Plasma-Mass Spectrometry

    SciTech Connect

    Jill Wisnewski Ferguson

    2006-08-09

    The inductively coupled plasma (ICP) is an atmospheric pressure ionization source. Traditionally, the plasma is sampled via a sampler cone. A supersonic jet develops behind the sampler, and this region is pumped down to a pressure of approximately one Torr. A skimmer cone is located inside this zone of silence to transmit ions into the mass spectrometer. The position of the sampler and skimmer cones relative to the initial radiation and normal analytical zones of the plasma is key to optimizing the useful analytical signal [1]. The ICP both atomizes and ionizes the sample. Polyatomic ions form through ion-molecule interactions either in the ICP or during ion extraction [l]. Common polyatomic ions that inhibit analysis include metal oxides (MO{sup +}), adducts with argon, the gas most commonly used to make up the plasma, and hydride species. While high resolution devices can separate many analytes from common interferences, this is done at great cost in ion transmission efficiency--a loss of 99% when using high versus low resolution on the same instrument [2]. Simple quadrupole devices, which make up the bulk of ICP-MS instruments in existence, do not present this option. Therefore, if the source of polyatomic interferences can be determined and then manipulated, this could potentially improve the figures of merit on all ICP-MS devices, not just the high resolution devices often utilized to study polyatomic interferences.

  16. Ion Mobility-Mass Spectrometry Analysis of Serum N-linked Glycans from Esophageal Adenocarcinoma Phenotypes

    PubMed Central

    Gaye, M. M.; Valentine, S. J.; Hu, Y.; Mirjankar, N.; Hammoud, Z. T.; Mechref, Y.; Lavine, B. K.; Clemmer, D. E.

    2012-01-01

    Three disease phenotypes, Barrett’s esophagus (BE), high-grade dysplasia (HGD), esophageal adenocarcinoma (EAC), and a set of normal control (NC) serum samples are examined using a combination of ion mobility spectrometry (IMS), mass spectrometry (MS) and principal component analysis (PCA) techniques. Samples from a total of 136 individuals were examined, including: 7 characterized as BE, 12 as HGD, 56 as EAC and 61 as NC. In typical datasets it was possible to assign ~20 to 30 glycan ions based on MS measurements. Ion mobility distributions for these ions show multiple features. In some cases, such as the [S1H5N4+3Na]3+ and [S1F1H5N4+3Na]3+ glycan ions, the ratio of intensities of high-mobility features to low-mobility features vary significantly for different groups. The degree to which such variations in mobility profiles can be used to distinguish phenotypes is evaluated for eleven N-linked glycan ions. An outlier analysis on each sample class followed by an unsupervised PCA using a genetic algorithm for pattern recognition reveals that EAC samples are separated from NC samples based on 46 features originating from the 11-glycan composite IMS distribution. PMID:23126309

  17. Surface-Induced Dissociation of Ions Produced by Matrix-Assisted Laser Desorption Ionization in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    SciTech Connect

    Laskin, Julia; Beck, Kenneth M.; Hache, John J.; Futrell, Jean H.

    2004-01-15

    Intermediate pressure matrix assisted laser ionization (MALDI) source was constructed and interfaced with a 6T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for surface-induced dissociation (SID) studies.

  18. Proposal for a novel method of precisely determining the atomic mass unit by the accumulation of ions

    NASA Astrophysics Data System (ADS)

    Gläser, Michael

    1991-10-01

    An experiment for direct measurement of the atomic mass unit is proposed. A mononuclidic ion flux is collected and accumulated to an amount that can be weighed with high accuracy. Simultaneously, the ion current is measured and integrated. By means of voltage and resistance references based on the Josephson and the quantum Hall effect, the mass is then related to atomic mass by frequency counting over a certain time interval. This experiment may enable a new, physical definition of the kilogram.

  19. Compact E ×B mass separator for heavy ion beamsa)

    NASA Astrophysics Data System (ADS)

    Wada, M.; Hashino, T.; Hirata, F.; Kasuya, T.; Sakamoto, Y.; Nishiura, M.

    2008-02-01

    A compact E ×B mass separator that deflects beam by 30° has been designed and built to prove its principle of operation. The main part of the separator is contained in a shielding box of 11cm long, 9cm wide, and 1.5cm high. An electromagnet of 7cm pole diameter produced variable magnetic field in the mass separation region instead of a couple of permanent magnets which is to be used in the final design. The experimental result agreed well with the theoretical prediction, and larger mass ions is bent with less magnetic field with the aid of the deflection electric field. The reduction in resolving power for mass separation due to the deflection electric field has been investigated experimentally.

  20. High Spatial Resolution Isotopic Abundance Measurements by Secondary Ion Mass Spectrometry: Status and Prospects

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.

    2007-12-01

    Secondary Ion Mass Spectrometry, SIMS or ion microprobe analysis, has become an important tool for geochemistry because of its ability study the distributions of elemental and isotopic abundances in situ on polished samples with high (typically a few microns to sub-micron) spatial resolution. In addition, SIMS exhibits high sensitivity for a wide range of elements (H to Pu) so that isotope analyses can sometimes be performed for elements that comprise only trace quantities of some mineral phase (e.g., Pb in zircon) or on major and/or minor elements in very small samples (e.g., presolar dust grains). Offsetting these positive attributes are analytical difficulties due to the complexity of the sputtering source of analyte ions: (1) relatively efficient production of molecular ion species (especially from a complex matrix such as most natural minerals) that cause interferences at the same nominal mass as atomic ions of interest, and (2) quantitation problems caused by variations in the ionization efficiencies of different elements and/or isotopes depending upon the chemical state of the sample surface during sputtering--the so-called "matrix effects". Despite the availability of high mass resolution instruments (e.g., SHRIMP II/RG, CAMECA 1270/1280/NanoSIMS), the molecular ion interferences effectively limit the region of the mass table that can be investigated in most samples to isotope systems at Ni or lighter or at Os or heavier. The matrix effects and the sensitivity of instrumental mass discrimination to the physical state of the sample surface can hamper reproducibility and have contributed to a view that SIMS analyses, especially for so- called stable isotopes, are most appropriate for extraterrestrial samples which are often small, rare, and can exhibit large magnitude isotopic effects. Recent improvements in instrumentation and technique have extended the scope of SIMS isotopic analyses and applications now range from geochronology to paleoclimatology to

  1. AN ION CORRELATION PROGRAM FOR DECONVOLUTING COMPOSITE MASS SPECTRA ACQUIRED USING A DIRECT SURFACE IONIZATION SOURCE INTERFACED TO A TIME-OF-FLIGHT MASS SPECTROMETER

    EPA Science Inventory

    The rapid sampling provided by the DART in ambient air will allow rapid delineation of areas of dispersed chemicals after natural or man-made disasters. Exact masses and RIAs of dimer, precursor, and product ions measured by the oa-TOFMS entered dinto the Ion Correlation Program...

  2. Characterizing the gas phase ion chemistry of an ion trap mobility spectrometry based explosive trace detector using a tandem mass spectrometer.

    PubMed

    Kozole, Joseph; Tomlinson-Phillips, Jill; Stairs, Jason R; Harper, Jason D; Lukow, Stefan R; Lareau, Richard T; Boudries, Hacene; Lai, Hanh; Brauer, Carolyn S

    2012-09-15

    A commercial-off-the-shelf (COTS) ion trap mobility spectrometry (ITMS) based explosive trace detector (ETD) has been interfaced to a triple quadrupole mass spectrometer (MS/MS) for the purpose of characterizing the gas phase ion chemistry intrinsic to the ITMS instrument. The overall objective of the research is to develop a fundamental understanding of the gas phase ionization processes in the ITMS based ETD to facilitate the advancement of its operational effectiveness as well as guide the development of next generation ETDs. Product ion masses, daughter ion masses, and reduced mobility values measured by the ITMS/MS/MS configuration for a suite of nitro, nitrate, and peroxide containing explosives are reported. Molecular formulas, molecular structures, and ionization pathways for the various product ions are inferred using the mass and mobility data in conjunction with density functional theory. The predominant product ions are identified as follows: [TNT-H](-) for trinitrotoluene (TNT), [RDX+Cl](-) for cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), [NO(3)](-) for ethylene glycol dinitrate (EGDN), [NG+NO(3)](-) for nitroglycerine (NG), [PETN+NO(3)](-) for pentaerythritol tetranitrate (PETN), [HNO(3)+NO(3)](-) for ammonium nitrate (NH(4)NO(3)), [HMTD-NC(3)H(6)O(3)+H+Cl](-) for hexamethylene triperoxide diamine (HMTD), and [(CH(3))(2)CNH(2)](+) for triacetone triperoxide (TATP). The predominant ionization pathways for the formation of the various product ions are determined to include proton abstraction, ion-molecule attachment, autoionization, first-order and multi-order thermolysis, and nucleophilic substitution. The ion trapping scheme in the reaction region of the ITMS instrument is shown to increase predominant ion intensities relative to the secondary ion intensities when compared to non-ion trap operation. PMID:22967626

  3. Ion neutral mass spectrometer results from the first flyby of Titan.

    PubMed

    Waite, J Hunter; Niemann, Hasso; Yelle, Roger V; Kasprzak, Wayne T; Cravens, Thomas E; Luhmann, Janet G; McNutt, Ralph L; Ip, Wing-Huen; Gell, David; De La Haye, Virginie; Müller-Wordag, Ingo; Magee, Brian; Borggren, Nathan; Ledvina, Steve; Fletcher, Greg; Walter, Erin; Miller, Ryan; Scherer, Stefan; Thorpe, Rob; Xu, Jing; Block, Bruce; Arnett, Ken

    2005-05-13

    The Cassini Ion Neutral Mass Spectrometer (INMS) has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, molecular hydrogen, argon, and a host of stable carbon-nitrile compounds in Titan's upper atmosphere. INMS in situ mass spectrometry has also provided evidence for atmospheric waves in the upper atmosphere and the first direct measurements of isotopes of nitrogen, carbon, and argon, which reveal interesting clues about the evolution of the atmosphere. The bulk composition and thermal structure of the moon's upper atmosphere do not appear to have changed considerably since the Voyager 1 flyby. PMID:15890873

  4. Bremsstrahlung production of low mass dielectrons in relativistic heavy ion collisions

    SciTech Connect

    Pal, D.; Srivastava, D.K.

    1996-09-01

    The distribution of low mass dielectrons likely to be produced in relativistic heavy ion collisions due to bremsstrahlung processes in quark matter and hadronic matter is obtained. Effort is made to minimize uncertainty and restore Lorentz covariance as compared with past calculations performed in a similar vein. It is found that the excess of dielectrons in S+Au collisions at 200{ital A}GeV measured by the CERES Collaboration at the CERN Super Proton Synchrotron may have an important contribution from these processes at very low masses. {copyright}{ital 1996 The American Physical Society.}

  5. Evaluation of the ion trap mass spectrometer for potential application in the space station

    SciTech Connect

    Glish, G.L.; McLuckey, S.A.

    1988-04-01

    This report describes preliminary experiments with an ion trap mass spectrometer, which were done to evaluate its potential for use in the environmental monitoring system of the proposed space station. The first section of the report describes various modes of operation of the instrument, discusses some of the present limitations, and discusses some of the potential solutions to these limitations. The next section discusses the experimental results obtained on sixteen compounds with particular emphasis on comparing these data to that expected from a standard mass spectrometer. The last section consists of a conclusion and comments on suggested future work. 16 figs.

  6. Avogadro constant and ion accumulation: steps towards a redefinition of the SI unit of mass

    NASA Astrophysics Data System (ADS)

    Becker, Peter; Gläser, Michael

    2003-08-01

    This paper summarizes the activities of the several national metrology institutes and one transnational institute in replacing the kilogram artefact by the mass of a certain number of atoms. This task is based on two different experiments: a very accurate determination of the Avogadro constant, NA, and the accumulation of decelerated gold ions, which lead to the atomic mass of silicon and gold respectively. The relative uncertainties reached so far are in the first case two parts in 107, and in the latter of the order of 1% due to the early state of the research work.

  7. Comparison of reactant and analyte ions for ⁶³Nickel, corona discharge, and secondary electrospray ionization sources with ion mobility-mass spectrometry.

    PubMed

    Crawford, C L; Hill, H H

    2013-03-30

    (63)Nickel radioactive ionization ((63)Ni) is the most common and widely used ion source for ion mobility spectrometry (IMS). Regulatory, financial, and operational concerns with this source have promoted recent development of non-radioactive sources, such as corona discharge ionization (CD), for stand-alone IMS systems. However, there has been no comparison of the negative ion species produced by all three sources in the literature. This study compares the negative reactant and analyte ions produced by three sources on an ion mobility-mass spectrometer: conventional (63)Ni, CD, and secondary electrospray ionization (SESI). Results showed that (63)Ni and SESI produced the same reactant ion species while CD produced only the nitrate monomer and dimer ions. The analyte ions produced by each ion source were the same except for the CD source which produced a different ion species for the explosive RDX than either the (63)Ni or SESI source. Accurate and reproducible reduced mobility (K0) values, including several values reported here for the first time, were found for each explosive with each ion source. Overall, the SESI source most closely reproduced the reactant ion species and analyte ion species profiles for (63)Ni. This source may serve as a non-radioactive, robust, and flexible alternative for (63)Ni. PMID:23598216

  8. Automated Gain Control Ion Funnel Trap for Orthogonal Time-of-Flight Mass Spectrometry

    PubMed Central

    Ibrahim, Yehia M.; Belov, Mikhail E.; Liyu, Andrei V.; Smith, Richard D.

    2009-01-01

    Time-of-flight mass spectrometry (TOF MS) is increasingly used in proteomics research. Herein, we report on the development and characterization of a TOF MS instrument with improved sensitivity equipped with an electrodynamic ion funnel trap (IFT) that employs an automated gain control (AGC) capability. The IFT-TOF MS was coupled to a reversed-phase capillary liquid chromatography (RPLC) separation and evaluated in experiments with complex proteolytic digests. When applied to a global tryptic digest of Shewanella oneidensis proteins, an order-of-magnitude increase in sensitivity compared to that of the conventional continuous mode of operation was achieved due to efficient ion accumulation prior to TOF MS analysis. As a result of this sensitivity improvement and related improvement in mass measurement accuracy, the number of unique peptides identified in the AGC-IFT mode was 5-fold greater than that obtained in the continuous mode. PMID:18512944

  9. Characterization of dihydrostreptomycin-related substances by liquid chromatography coupled to ion trap mass spectrometry.

    PubMed

    Pendela, Murali; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin

    2009-06-01

    Dihydrostreptomycin sulphate (DHS) is a water-soluble, broad-spectrum aminoglycoside antibiotic. For quantitative analysis, the European Pharmacopoeia (Ph. Eur.) prescribes an ion-pairing liquid chromatography/ultraviolet (LC/UV) method using a C18 stationary phase. Several unknown compounds were detected in commercial samples. Hence, for characterization of these unknown peaks in a commercial DHS sample, the Ph. Eur. method was coupled to mass spectrometry (MS). However, since the Ph. Eur. method uses a non-volatile mobile phase, each peak eluted was collected and desalted before introduction into the mass spectrometer. The desalting procedure was applied to remove the non volatile salt, buffer and ion-pairing reagent in the collected fraction. In total, 20 impurities were studied and 14 of them were newly characterized. Five impurities which are already reported in the literature were also traced in this LC/UV method. PMID:19449319

  10. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    DOE PAGESBeta

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-05-06

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts andmore » noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.« less

  11. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    NASA Astrophysics Data System (ADS)

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin S.; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-12-01

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm employs an analytical approach to identify and remove artifacts from the data, decreasing the likelihood of false identifications in subsequent data processing. Following application of the algorithm, IMS-MS measurement sensitivity is greatly increased and artifacts that previously limited the utility of applying the Hadamard transform to IMS are avoided. [Figure not available: see fulltext.

  12. The Neutral Gas and Ion Mass Spectrometer on the Mars Atmosphere and Volatile Evolution Mission

    NASA Technical Reports Server (NTRS)

    Mahaffy, Paul R.; Benna, Mehdi; King, Todd; Harpold, Daniel N.; Arvey, Robert; Barciniak, Michael; Bendt, Mirl; Carrigan, Daniel; Errigo, Therese; Holmes, Vincent; Kellogg, James; Jaeger, Ferzan; Raaen, Eric; Tan, Florence

    2014-01-01

    The Neutral Gas and Ion Mass Spectrometer (NGIMS) of the Mars Atmosphere and Volatile Evolution Mission (MAVEN) is designed to measure the composition, structure, and variability of the upper atmosphere of Mars. The NGIMS complements two other instrument packages on the MAVEN spacecraft designed to characterize the neutral upper atmosphere and ionosphere of Mars and the solar wind input to this region of the atmosphere. The combined measurement set is designed to quantify atmosphere escape rates and provide input to models of the evolution of the martian atmosphere. The NGIMS is designed to measure both surface reactive and inert neutral species and ambient ions along the spacecraft track over the 125-500 km altitude region utilizing a dual ion source and a quadrupole analyzer.

  13. Organic secondary ion mass spectrometry: signal enhancement by water vapor injection.

    PubMed

    Mouhib, Taoufiq; Delcorte, Arnaud; Poleunis, Claude; Bertrand, Patrick

    2010-12-01

    The enhancement of the static secondary ion mass spectrometry (SIMS) signals resulting from the injection, closely to the sample surface, of H(2)O vapor at relatively high-pressure, was investigated for a set of organic materials. While the ion signals are generally improved with increasing H(2)O pressure upon 12 keV Ga(+) bombardment, a specific enhancement of the protonated ion intensity is clearly demonstrated in each case. For instance, the presence of H(2)O vapor induces an enhancement by one order of magnitude of the [M + H](+) static SIMS intensity for the antioxidant Irgafos 168 and a ∼1.5-fold increase for polymers such as poly(vinyl pyrrolidone). PMID:20864353

  14. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    SciTech Connect

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-12-01

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts and noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.

  15. Human Biomonitoring of DNA Adducts by Ion Trap Multistage Mass Spectrometry.

    PubMed

    Guo, Jingshu; Turesky, Robert J

    2016-01-01

    Humans are continuously exposed to hazardous chemicals in the environment. These chemicals or their electrophilic metabolites can form adducts with genomic DNA, which can lead to mutations and the initiation of cancer. The identification of DNA adducts is required for understanding exposure and the etiological role of a genotoxic chemical in cancer risk. The analytical chemist is confronted with a great challenge because the levels of DNA adducts generally occur at <1 adduct per 10(7) nucleotides, and the amount of tissue available for measurement is limited. Ion trap mass spectrometry has emerged as an important technique to screen for DNA adducts because of the high level sensitivity and selectivity, particularly when employing multi-stage scanning (MS(n) ). The product ion spectra provide rich structural information and corroborate the adduct identities even at trace levels in human tissues. Ion trap technology represents a significant advance in measuring DNA adducts in humans. © 2016 by John Wiley & Sons, Inc. PMID:27584705

  16. Automatic control of the ion-illumination angle in a spark-source mass spectrometer.

    PubMed

    Conzemius, R J; Svec, H J

    1973-05-01

    Automatic adjustment of only the spark-gap width in a spark-source mass spectrometer does not ensure that optimum conditions of electrode geometry are maintained with respect to the ion-optics system. A device has been developed which simultaneously maintains a constant gap width and also a more constant z-axis ion-illumination angle. This is the first development to utilize ion-optics parameters to adjust the sparking electrodes automatically. The system maintains the electrodes in an optimum configuration such that higher and more constant instrument sensitivity is maintained automatically. In addition, a significant improvement in the precision of instrumental response is demonstrated. It appears that relative isotopic abundances can be determined directly by the spark-source method which are comparable to those obtained in some cases by surface ionization or by electron bombardment. Results are given that support this contention. PMID:18961307

  17. EVIDENCE FOR LOCAL ACCELERATION OF SUPRATHERMAL HEAVY ION OBSERVATIONS DURING INTERPLANETARY CORONAL MASS EJECTIONS

    SciTech Connect

    Gruesbeck, Jacob R.; Lepri, Susan T.; Zurbuchen, Thomas H.; Christian, Eric R.

    2015-01-20

    Suprathermal particles are an important seed population for a variety of energetic particles found throughout the heliosphere, but their origin is in debate. We present, for the first time, high-cadence observations of suprathermal heavy ions during interplanetary coronal mass ejections (ICMEs), from the Suprathermal Ion Composition Spectrometer on board the Wind spacecraft, and investigate their ionic composition and compare it to the bulk solar wind plasma composition, observed from the Solar Wind Ion Composition Spectrometer on board the Advanced Composition Explorer. We find that the composition of the suprathermal plasma is related to the local bulk solar wind plasma and not to the plasma upstream of the ICME. This implies that the suprathermal plasma is accelerated from the local bulk solar wind plasma and not the upstream solar wind plasma.

  18. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    SciTech Connect

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-05-06

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts and noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.

  19. Label free biochemical 2D and 3D imaging using secondary ion mass spectrometry

    PubMed Central

    Fletcher, John S.; Vickerman, John C.; Winograd, Nicholas

    2011-01-01

    Time-of-flight Secondary ion mass spectrometry (ToF-SIMS) provides a method for the detection of native and exogenous compounds in biological samples on a cellular scale. Through the development of novel ion beams the amount of molecular signal available from the sample surface has been increased. Through the introduction of polyatomic ion beams, particularly C60, ToF-SIMS can now be used to monitor molecular signals as a function of depth as the sample is eroded thus proving the ability to generate 3D molecular images. Here we describe how this new capability has led to the development of novel instrumentation for 3D molecular imaging while also highlighting the importance of sample preparation and discuss the challenges that still need to be overcome to maximise the impact of the technique. PMID:21664172

  20. Mass spectrometry of refractory black carbon particles from six sources: carbon-cluster and oxygenated ions

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Sierau, B.; Gysel, M.; Laborde, M.; Keller, A.; Kim, J.; Petzold, A.; Onasch, T. B.; Lohmann, U.; Mensah, A. A.

    2013-10-01

    We discuss the major mass spectral features of different types of refractory carbonaceous particles, ionized after laser vapourization with an Aerodyne High-Resolution Soot-Particle Aerosol Mass Spectrometer (SP-AMS). The SP-AMS was operated with a switchable 1064 nm laser and a 600 °C thermal vapourizer, yielding respective measurements of the refractory and non-refractory particle components. Six samples were investigated, all of which were composed primarily of refractory material: fuel-rich and fuel-lean propane/air diffusion-flame combustion particles; graphite-spark-generated particles; a commercial Fullerene-enriched Soot; Regal Black, a commercial carbon black; and nascent aircraft-turbine combustion particles. All samples exhibited a spectrum of carbon-cluster ions Cxn+ in their refractory mass spectrum. Smaller clusters (x<6) were found to dominate the Cxn+ distribution. For Fullerene Soot, fuel-rich-flame particles and spark-generated particles, significant Cxn+ clusters at x≫6 were present, with significant contributions from multiply-charged ions (n>1). In all six cases, the ions C1+ and C3+ contributed over 60% to the total C1ions C1+/C3+ could be used to predict whether significant Cxn+ signals with x>5 were present. When such signals were present, C1+/C3+ was close to 1. When absent, C1+/C3+ was <0.8. This ratio may therefore serve as a proxy to distinguish between the two types of spectra in atmospheric SP-AMS measurements. Significant refractory oxygenated ions such as CO+ and CO2+ were also observed for all samples. We discuss these signals in detail for Regal Black, and describe their formation via decomposition of oxygenated moieties incorporated into the refractory carbon structure. These species may be of importance in atmospheric processes such as water uptake, aging and heterogeneous chemistry.

  1. Characterization of the Cathode Electrolyte Interface in Lithium Ion Batteries by Desorption Electrospray Ionization Mass Spectrometry.

    PubMed

    Liu, Yao-Min; G Nicolau, Bruno; Esbenshade, Jennifer L; Gewirth, Andrew A

    2016-07-19

    The solid electrolyte interface (SEI) formed via electrolyte decomposition on the anode of lithium ion batteries is largely responsible for the stable cycling of conventional lithium ion batteries. Similarly, there is a lesser-known analogous layer on the cathode side of a lithium ion battery, termed the cathode electrolyte interface (CEI), whose composition and role are debated. To confirm the existence and composition of the CEI, desorption electrospray ionization mass spectrometry (DESI-MS) is applied to study common lithium ion battery cathodes. We observe CEI formation on the LiMn2O4 cathode material after cycling between 3.5 and 4.5 V vs Li/Li(+) in electrolyte solution containing 1 M LiPF6 or LiClO4 in 1:1 (v/v) ethylene carbonate (EC) and dimethyl carbonate (DMC). Intact poly(ethylene glycol) dimethyl ether is identified as the electrolyte degradation product on the cathode surface by the high mass-resolution Orbitrap mass spectrometer. When EC is paired with ethyl methyl carbonate (EMC), poly(ethylene glycol) dimethyl ether, poly(ethylene glycol) ethyl methyl ether, and poly(ethylene glycol) are found on the surface simultaneously. The presence of ethoxy and methoxy end groups indicates both methoxide and ethoxide are produced and involved in the process of oligomerization. Au surfaces cycled under different electrochemical windows as model systems for Li-ion battery anodes are also examined. Interestingly, the identical oligomeric species to those found in the CEI are found on Au surfaces after running five cycles between 2.0 and 0.1 V vs Li/Li(+) in half-cells. These results show that DESI-MS provides intact molecular information on battery electrodes, enabling deeper understanding of the SEI or CEI composition. PMID:27346184

  2. Reduction of plyatomic ion interferences in indictively coupled plasma mass spectrometry with cryogenic desolvation

    SciTech Connect

    Alves, L.C.

    1993-09-01

    A desolvation scheme for introducing aqueous and organic samples into an argon inductively coupled plasma is described; the aerosol generated by nebulizer is heated (+140 C) and cooled ({minus}80 C) repeatedly, and the dried aerosol is then injected into the mass spectrometer. Polyatomic ions are greatly suppressed. This scheme was validated with analysis of seawater and urine reference samples. Finally, the removal of organic solvents by cryogenic desolvation was studied.

  3. Modeling of the mass transfer rates of metal ions across supported liquid membranes. 1: Theory

    SciTech Connect

    Elhassadi, A.A.; Do, D.D.

    1999-01-01

    This paper deals with the modeling of the transport and separation of metal ions across supported liquid membranes. The mass transfer resistance at the liquid-membrane interfaces and the interfacial chemical reactions at both the extracting side and the stripping side are taken into account in the model equations. Simple analysis of the time scale of the system shows the influence of various important parameters and their interactions on the overall transport rate. Parametric studies are also dealt with in this paper.

  4. Secondary Ion Mass Spectrometry for Mg Tracer Diffusion: Issues and Solutions

    SciTech Connect

    Tuggle, Jay; Giordani, Andrew; Kulkarni, Nagraj S; Warmack, Robert J Bruce; Coffey, Kevin; Sohn, Yong Ho; HunterJr., Jerry

    2014-01-01

    A Secondary Ion Mass Spectrometry (SIMS) method has been developed to measure stable Mg isotope tracer diffusion. This SIMS method was then used to calculate Mg self- diffusivities and the data was verified against historical data measured using radio tracers. The SIMS method has been validated as a reliable alternative to the radio-tracer technique for the measurement of Mg self-diffusion coefficients and can be used as a routine method for determining diffusion coefficients.

  5. Non-mass-analyzed ion implantation equipment for high volume solar cell production

    NASA Technical Reports Server (NTRS)

    Armini, A. J.; Bunker, S. N.; Spitzer, M. B.

    1982-01-01

    Equipment designed for junction formation in silicon solar cells is described. The equipment, designed for a production level of approximately one megawatt per year, consists of an ion implanter and annealer. Low cost is achieved by foregoing the use of mass analysis during the implantation, and by the use of a belt furnace for annealing. Results of process development, machine design and cost analysis are presented.

  6. Distance-of-Flight Mass Spectrometry with IonCCD Detection and an Inductively Coupled Plasma Source

    NASA Astrophysics Data System (ADS)

    Dennis, Elise A.; Ray, Steven J.; Enke, Christie G.; Gundlach-Graham, Alexander W.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2016-03-01

    Distance-of-flight mass spectrometry (DOFMS) is demonstrated for the first time with a commercially available ion detector—the IonCCD camera. Because DOFMS is a velocity-based MS technique that provides spatially dispersive, simultaneous mass spectrometry, a position-sensitive ion detector is needed for mass-spectral collection. The IonCCD camera is a 5.1-cm long, 1-D array that is capable of simultaneous, multichannel ion detection along a focal plane, which makes it an attractive option for DOFMS. In the current study, the IonCCD camera is evaluated for DOFMS with an inductively coupled plasma (ICP) ionization source over a relatively short field-free mass-separation distance of 25.3-30.4 cm. The combination of ICP-DOFMS and the IonCCD detector results in a mass-spectral resolving power (FWHM) of approximately 900 and isotope-ratio precision equivalent to or slightly better than current ICP-TOFMS systems. The measured isotope-ratio precision in % relative standard deviation (%RSD) was ≥0.008%RSD for nonconsecutive isotopes at 10-ppm concentration (near the ion-signal saturation point) and ≥0.02%RSD for all isotopes at 1-ppm. Results of DOFMS with the IonCCD camera are also compared with those of two previously characterized detection setups.

  7. Distance-of-Flight Mass Spectrometry with IonCCD Detection and an Inductively Coupled Plasma Source.

    PubMed

    Dennis, Elise A; Ray, Steven J; Enke, Christie G; Gundlach-Graham, Alexander W; Barinaga, Charles J; Koppenaal, David W; Hieftje, Gary M

    2016-03-01

    Distance-of-flight mass spectrometry (DOFMS) is demonstrated for the first time with a commercially available ion detector-the IonCCD camera. Because DOFMS is a velocity-based MS technique that provides spatially dispersive, simultaneous mass spectrometry, a position-sensitive ion detector is needed for mass-spectral collection. The IonCCD camera is a 5.1-cm long, 1-D array that is capable of simultaneous, multichannel ion detection along a focal plane, which makes it an attractive option for DOFMS. In the current study, the IonCCD camera is evaluated for DOFMS with an inductively coupled plasma (ICP) ionization source over a relatively short field-free mass-separation distance of 25.3-30.4 cm. The combination of ICP-DOFMS and the IonCCD detector results in a mass-spectral resolving power (FWHM) of approximately 900 and isotope-ratio precision equivalent to or slightly better than current ICP-TOFMS systems. The measured isotope-ratio precision in % relative standard deviation (%RSD) was ≥0.008%RSD for nonconsecutive isotopes at 10-ppm concentration (near the ion-signal saturation point) and ≥0.02%RSD for all isotopes at 1-ppm. Results of DOFMS with the IonCCD camera are also compared with those of two previously characterized detection setups. Graphical Abstract ᅟ. PMID:26552388

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

    NASA Astrophysics Data System (ADS)

    Laudien, Robert; Schultze, Rainer; Wieser, Jochen

    2010-10-01

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

  9. Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

    PubMed Central

    Melvin Blaze, M.T.; Takahashi, Lynelle K.; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald L.; Pleticha, F. Douglas; Hanley, Luke

    2011-01-01

    The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 – 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by ≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~8.3±0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at ≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3+ secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. However, the negative ion SIMS appeared strongly dependent on the high electron affinity of this specific analyte and the analyte’s condensed phase environment. PMID:21548612

  10. Brominated Tyrosine and Polyelectrolyte Multilayer Analysis by Laser Desorption VUV Postionization and Secondary Ion Mass Spectrometry

    SciTech Connect

    University of Illinois at Chicago; Blaze, Melvin M. T.; Takahashi, Lynelle; Zhou, Jia; Ahmed, Musahid; Gasper, Gerald; Pleticha, F. Douglas; Hanley, Luke

    2011-03-14

    The small molecular analyte 3,5-dibromotyrosine (Br2Y) and chitosan-alginate polyelectrolyte multilayers (PEM) with and without adsorbed Br2Y were analyzed by laser desorption postionization mass spectrometry (LDPI-MS). LDPI-MS using 7.87 eV laser and tunable 8 ? 12.5 eV synchrotron vacuum ultraviolet (VUV) radiation found that desorption of clusters from Br2Y films allowed detection by≤8 eV single photon ionization. Thermal desorption and electronic structure calculations determined the ionization energy of Br2Y to be ~;;8.3?0.1 eV and further indicated that the lower ionization energies of clusters permitted their detection at≤8 eV photon energies. However, single photon ionization could only detect Br2Y adsorbed within PEMs when using either higher photon energies or matrix addition to the sample. All samples were also analyzed by 25 keV Bi3 + secondary ion mass spectrometry (SIMS), with the negative ion spectra showing strong parent ion signal which complemented that observed by LDPI-MS. The negative ion SIMS depended strongly on the high electron affinity of this specific analyte and the analyte?s condensed phase environment.

  11. Characterization of drug-eluting stent (DES) materials with cluster secondary ion mass spectrometry (SIMS)

    NASA Astrophysics Data System (ADS)

    Mahoney, Christine M.; Patwardhan, Dinesh V.; Ken McDermott, M.

    2006-07-01

    Secondary ion mass spectrometry (SIMS) employing an SF 5+ polyatomic primary ion source was utilized to analyze several materials commonly used in drug-eluting stents (DES). Poly(ethylene- co-vinyl acetate) (PEVA), poly(lactic- co-glycolic acid) (PLGA) and various poly(urethanes) were successfully depth profiled using SF 5+ bombardment. The resultant molecular depth profiles obtained from these polymeric films showed very little degradation in molecular signal as a function of increasing SF 5+ primary ion dose when experiments were performed at low temperatures (signal was maintained for doses up to ˜5 × 10 15 ions/cm 2). Temperature was determined to be an important parameter in both the success of the depth profiles and the mass spectral analysis of the polymers. In addition to the pristine polymer films, paclitaxel (drug released in Taxus™ stent) containing PLGA films were also characterized, where it was confirmed that both drug and polymer signals could be monitored as a function of depth at lower paclitaxel concentrations (10 wt%).

  12. Uranium passivation by C+ implantation: a photoemission and secondary ion mass spectrometry study

    SciTech Connect

    Nelson, A J; Felter, T E; Wu, K J; Evans, C; Ferreira, J; Siekhaus, W; McLean, W

    2005-01-20

    Implantation of 33 keV C{sup +} ions into polycrystalline U{sup 238} with a dose of 4.3 x 10{sup 17} cm{sup -2} produces a physically and chemically modified surface layer that prevents further air oxidation and corrosion. X-ray photoelectron spectroscopy and secondary ion mass spectrometry were used to investigate the surface chemistry and electronic structure of this C{sup +} ion implanted polycrystalline uranium and a non-implanted region of the sample, both regions exposed to air for more than a year. In addition, scanning electron microscopy was used to examine and compare the surface morphology of the two regions. The U 4f, O 1s and C 1s core-level and valence band spectra clearly indicate carbide formation in the modified surface layer. The time-of-flight secondary ion mass spectrometry depth profiling results reveal an oxy-carbide surface layer over an approximately 200 nm thick UC layer with little or no residual oxidation at the carbide layer/U metal transitional interface.

  13. The Laser Ablation Ion Funnel: Sampling for in situ Mass Spectrometry on Mars

    NASA Technical Reports Server (NTRS)

    Johnson, Paul V.; Hodyss, Robert; Tang, Keqi; Brinckerhoff, William B.; Smith, Richard D.

    2011-01-01

    A considerable investment has been made by NASA and other space agencies to develop instrumentation suitable for in situ analytical investigation of extra terrestrial bodies including various mass spectrometers (time-of-flight, quadrupole ion trap, quadrupole mass filters, etc.). However, the front-end sample handling that is needed to collect and prepare samples for interrogation by such instrumentation remains underdeveloped. Here we describe a novel approach tailored to the exploration of Mars where ions are created in the ambient atmosphere via laser ablation and then efficiently transported into a mass spectrometer for in situ analysis using an electrodynamic ion funnel. This concept would enable elemental and isotopic analysis of geological samples with the analysis of desorbed organic material a possibility as well. Such an instrument would be suitable for inclusion on all potential missions currently being considered such as the Mid-Range Rover, the Astrobiology Field Laboratory, and Mars Sample Return (i.e., as a sample pre-selection triage instrument), among others.

  14. Sizing Large Proteins and Protein Complexes by Electrospray Ionization Mass Spectrometry and Ion Mobility

    PubMed Central

    Kaddis, Catherine S.; Lomeli, Shirley H.; Yin, Sheng; Berhane, Beniam; Apostol, Marcin I.; Kickhoefer, Valerie A.; Rome, Leonard H.; Loo, Joseph A.

    2009-01-01

    Mass spectrometry (MS) and ion mobility with electrospray ionization (ESI) have the capability to measure and detect large noncovalent protein-ligand and protein-protein complexes. Using an ion mobility method termed GEMMA (Gas-Phase Electrophoretic Mobility Molecular Analysis), protein particles representing a range of sizes can be separated by their electrophoretic mobility in air. Highly charged particles produced from a protein complex solution using electrospray can be manipulated to produce singly charged ions which can be separated and quantified by their electrophoretic mobility. Results from ESI-GEMMA analysis from our laboratory and others were compared to other experimental and theoretically determined parameters, such as molecular mass and cryoelectron microscopy and x-ray crystal structure dimensions. There is a strong correlation between the electrophoretic mobility diameter determined from GEMMA analysis and the molecular mass for protein complexes up to 12 MDa, including the 93 kDa enolase dimer, the 480 kDa ferritin 24-mer complex, the 4.6 MDa cowpea chlorotic mottle virus (CCMV), and the 9 MDa MVP-vault assembly. ESI-GEMMA is used to differentiate a number of similarly sized vault complexes that are composed of different N-terminal protein tags on the MVP subunit. The average effective density of the proteins and protein complexes studied was 0.6 g/cm3. Moreover, there is evidence that proteins and protein complexes collapse or become more compact in the gas phase in the absence of water. PMID:17434746

  15. Metabolic Profiling of Human Blood by High Resolution Ion Mobility Mass Spectrometry (IM-MS)

    PubMed Central

    Dwivedi, Prabha; Schultz, Albert J.; Hill, Herbert H.

    2010-01-01

    A high resolution ion mobility time-of-flight mass spectrometer with electrospray ionization source (ESI-IM-MS) was evaluated as an analytical method for rapid analysis of complex biological samples such as human blood metabolome was investigated. The hybrid instrument (IM-MS) provided an average ion mobility resolving power of ~90 and a mass resolution of ~1500 (at m/z 100). A few µL of whole blood was extracted with methanol, centrifuged and infused into the IM-MS via an electrospray ionization source. Upon IM-MS profiling of the human blood metabolome approximately 1,100 metabolite ions were detected and 300 isomeric metabolites separated in short analyses time (30 minutes). Estimated concentration of the metabolites ranged from the low micromolar to the low nanomolar level. Various classes of metabolites (amino acids, organic acids, fatty acids, carbohydrates, purines and pyrimidines etc) were found to form characteristic mobility-mass correlation curves (MMCC) that aided in metabolite identification. Peaks corresponding to various sterol derivatives, estrogen derivatives, phosphocholines, prostaglandins, and cholesterol derivatives detected in the blood extract were found to occupy characteristic two dimensional IM-MS space. Low abundance metabolite peaks that can be lost in MS random noise were resolved from noise peaks by differentiation in mobility space. In addition, the peak capacity of MS increased six fold by coupling IMS prior to MS analysis. PMID:21113320

  16. Secondary ion mass spectrometry and x-ray analysis of superconducting Nb/Pd multilayers

    NASA Astrophysics Data System (ADS)

    Gerardi, C.; Tagliente, M. A.; Del Vecchio, A.; Tapfer, L.; Coccorese, C.; Attanasio, C.; Mercaldo, L. V.; Maritato, L.; Slaughter, J. M.; Falco, C. M.

    2000-01-01

    We report on accurate structural investigations of sputtered Nb/Pd multilayers by means of high-resolution secondary ion mass spectrometry and x-ray reflectivity. The combined use of secondary ion mass spectrometry and x-ray specular reflectivity techniques allows us to study the chemical configuration of the interfaces and to relate it to the observed superconducting properties. Secondary ion mass spectrometry analyses reveal a distinct Nb and Pd modulation and very sharp profiles with abrupt interfaces indicating a negligible interdiffusion of Nb and Pd at the interfaces. Moreover, analyzing the features in the Nb and Pd profiles and correlating them to the oxygen distribution in the multilayers and to the low-angle x-ray patterns, thin layers (3-4 nm thick) of niobium oxide were noticed at the Nb/Pd interfaces, while no oxide layers at the Pd/Nb interfaces could be detected. The role of this oxide layer in the determination of the crossover between three- and two-dimensional superconducting behavior in parallel external magnetic field, is discussed.

  17. Preparation and in situ Characterization of Surfaces Using Soft-Landing in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    SciTech Connect

    Alvarez, Jormarie; Cooks, Robert G.; Barlow, Stephan E.; Gaspar, Dan J.; Futrell, Jean H.; Laskin, Julia

    2005-06-01

    Mass-selected peptide ions produced by electrospray ionization were deposited onto fluorinated self-assembled monolayer surfaces (FSAM) surfaces by soft-landing using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially designed for studying interactions of large ions with surfaces. Analysis of the modified surface was performed in situ by combining 2 keV Cs+ secondary ion mass spectrometry with FT-ICR detection of the sputtered ions (FT-ICR-SIMS). Regardless of the initial charge state of the precursor ion, the SIMS mass spectra included singly-protonated peptide fragment ions and peaks characteristic of the surfaces in all cases. In some experiments multiply-protonated peptide ions and [M+Au]+ ions were also observed upon SIMS analysis of modified surfaces. For comparison with the in situ analysis of the modified surfaces, ex situ analysis of some of the modified surfaces was performed by 25 kV Ga+ time of flight ? secondary ion mass spectrometry (ToF-SIMS). The ex situ analysis demonstrated that a significant number of soft-landed peptide ions remain charged on the surface even when exposed to air for several hours after deposition. Charge retention of soft-landed ions dramatically increases the ion yields obtained during SIMS analysis very sensitive detection of deposited material at less than 1% of monolayer coverage. Accumulation of charged species on the surface undergoes saturation due to Coulomb repulsion between charges at close to 30% coverage. We estimated that close to 1 ng of peptide could be deposited on the spot area of 4 mm2 of the FSAM surface without reaching saturation.

  18. Analysis of explosives using corona discharge ionization combined with ion mobility spectrometry-mass spectrometry.

    PubMed

    Lee, Jihyeon; Park, Sehwan; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sung-Suk; Kim, Jeongkwon

    2014-03-01

    Corona discharge ionization combined with ion mobility spectrometry-mass spectrometry (IMS-MS) was utilized to investigate five common explosives: cyclonite (RDX), trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotetramethylenetetranitramine (HMX), and 2,4-dinitrotoluene (DNT). The MS scan and the selected ion IMS analyses confirmed the identities of the existing ion species and their drift times. The ions observed were RDX·NO3(-), TNT(-), PETN·NO3(-), HMX·NO3(-), and DNT(-), with average drift times of 6.93 ms, 10.20 ms, 9.15 ms, 12.24 ms, 11.30 ms, and 8.89 ms, respectively. The reduced ion mobility values, determined from a standard curve calculated by linear regression of (normalized drift times)(-1) versus literature K0 values, were 2.09, 1.38, 1.55, 1.15, 1.25, and 1.60 cm(2) V(-1) s(-1), respectively. The detection limits were found to be 0.1 ng for RDX, 10 ng for TNT, 0.5 ng for PETN, 5.0 ng for HMX, and 10 ng for DNT. Simplified chromatograms were observed when nitrogen, as opposed to air, was used as the drift gas, but the detection limits were approximately 10 times worse (i.e., less sensitivity of detection). PMID:24468343

  19. Large-Scale Collision Cross-Section Profiling on a Traveling Wave Ion Mobility Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Lietz, Christopher B.; Yu, Qing; Li, Lingjun

    2014-12-01

    Ion mobility (IM) is a gas-phase electrophoretic method that separates ions according to charge and ion-neutral collision cross-section (CCS). Herein, we attempt to apply a traveling wave (TW) IM polyalanine calibration method to shotgun proteomics and create a large peptide CCS database. Mass spectrometry methods that utilize IM, such as HDMSE, often use high transmission voltages for sensitive analysis. However, polyalanine calibration has only been demonstrated with low voltage transmission used to prevent gas-phase activation. If polyalanine ions change conformation under higher transmission voltages used for HDMSE, the calibration may no longer be valid. Thus, we aimed to characterize the accuracy of calibration and CCS measurement under high transmission voltages on a TW IM instrument using the polyalanine calibration method and found that the additional error was not significant. We also evaluated the potential error introduced by liquid chromatography ( LC)-HDMSE analysis, and found it to be insignificant as well, validating the calibration method. Finally, we demonstrated the utility of building a large-population peptide CCS database by investigating the effects of terminal lysine position, via LysC or LysN digestion, on the formation of two structural sub-families formed by triply charged ions.

  20. Mass spectrometric characterization of a high-field asymmetric waveform ion mobility spectrometer

    NASA Astrophysics Data System (ADS)

    Purves, Randy W.; Guevremont, Roger; Day, Stephen; Pipich, Charles W.; Matyjaszczyk, Matthew S.

    1998-12-01

    Ion mobility spectrometry (IMS) has become an important method for the detection of many compounds because of its high sensitivity and amenability to miniaturization for field-portable monitoring; applications include detection of narcotics, explosives, and chemical warfare agents. High-field asymmetric waveform ion mobility spectrometry (FAIMS) differs from IMS in that the electric fields are applied using a high-frequency periodic asymmetric waveform, rather than a dc voltage. Furthermore, in FAIMS the compounds are separated by the difference in the mobility of ions at high electric field relative to low field, rather than by compound to compound differences in mobility at low electric field (IMS). We report here the first cylindrical-geometry-FAIMS interface with mass spectrometry (FAIMS-MS) and the MS identification of the peaks observed in a FAIMS compensation voltage (CV) spectrum. Using both an electrometer-based-FAIMS (FAIMS-E) and FAIMS-MS, several variables that affect the sensitivity of ion detection were examined for two (polarity reversed) asymmetric waveforms (modes 1 and 2) each of which yields a unique spectrum. An increase in the dispersion voltage (DV) was found to improve the sensitivity and separation observed in the FAIMS CV spectrum. This increase in sensitivity and the unexpected dissimilarity in modes 1 and 2 suggest that atmospheric pressure ion focusing is occurring in the FAIMS analyzer. The sensitivity and peak locations in the CV spectra were affected by temperature, gas flow rates, operating pressure, and analyte concentration.

  1. Large-scale collision cross-section profiling on a travelling wave ion mobility mass spectrometer

    PubMed Central

    Lietz, Christopher B.; Yu, Qing; Li, Lingjun

    2014-01-01

    Ion mobility (IM) is a gas-phase electrophoretic method that separates ions according to charge and ion-neutral collision cross-section (CCS). Herein, we attempt to apply a travelling wave (TW) IM polyalanine calibration method to shotgun proteomics and create a large peptide CCS database. Mass spectrometry methods that utilize IM, such as HDMSE, often use high transmission voltages for sensitive analysis. However, polyalanine calibration has only been demonstrated with low voltage transmission used to prevent gas-phase activation. If polyalanine ions change conformation under higher transmission voltages used for HDMSE, the calibration may no longer be valid. Thus, we aimed to characterize the accuracy of calibration and CCS measurement under high transmission voltages on a TW IM instrument using the polyalanine calibration method and found that the additional error was not significant. We also evaluated the potential error introduced by liquid chromatography (LC)-HDMSE analysis, and found it to be insignificant as well, validating the calibration method. Finally, we demonstrated the utility of building a large-population peptide CCS database by investigating the effects of terminal lysine position, via LysC or LysN digestion, on the formation of two structural sub-families formed by triply charged ions. PMID:24845359

  2. Rapid determination of nicotine in urine by direct thermal desorption ion trap mass spectrometry

    SciTech Connect

    Wise, M.B.; Ilgner, R.H.; Guerin, M.R.

    1990-01-01

    The measurement of nicotine and cotinine in physiological fluids (urine, blood serum, and saliva) is widely used as a means of assessing human exposure to environmental tobacco smoke (ETS). Although numerous analytical methods exist for these measurements, they generally involve extensive sample preparation which increases cost and decreases sample throughput. We report the use of thermal desorption directly into an ion trap mass spectrometer (ITMS) for the rapid determination of nicotine and cotinine in urine. A 1{mu}L aliquot of urine is injected into a specially designed inlet and flash vaporized directly into an ITMS through an open-split capillary restrictor interface. Isobutane chemical ionization is used to generate (M+H){sup +} ions of the analytes and collision induced dissociation is used to generate characteristic fragment ions which are used to confirm their identity. Quantification is achieved by integrating the ion current for the characteristic ions and comparing with an external working curve. Detection limits are approximately 50 pg per analyte and the sample turnaround time is approximately 3 minutes without the need for extensive sample preparation. 12 refs., 5 figs.

  3. Online deuterium hydrogen exchange and protein digestion coupled with ion mobility spectrometry and tandem mass spectrometry.

    PubMed

    Donohoe, Gregory C; Arndt, James R; Valentine, Stephen J

    2015-05-19

    Online deuterium hydrogen exchange (DHX) and pepsin digestion (PD) is demonstrated using drift tube ion mobility spectrometry (DTIMS) coupled with linear ion trap (LTQ) mass spectrometry (MS) with electron transfer dissociation (ETD) capabilities. DHX of deuterated ubiquitin, followed by subsequent quenching and digestion, is performed within ∼60 s, yielding 100% peptide sequence coverage. The high reproducibility of the IMS separation allows spectral feature matching between two-dimensional IMS-MS datasets (undeuterated and deuterated) without the need for dataset alignment. Extracted ion drift time distributions (XIDTDs) of deuterated peptic peptides are mobility-matched to corresponding XIDTDs of undeuterated peptic peptides that were identified using collision-induced dissociation (CID). Matching XIDTDs allows a straightforward identification and deuterium retention evaluation for labeled peptides. Aside from the mobility separation, the ion trapping capabilities of the LTQ, combined with ETD, are demonstrated to provide single-residue resolution. Deuterium retention for the c- series ions across residues M(1)-L(15) and N(25)-R(42) are in good agreement with the known secondary structural elements within ubiquitin. PMID:25893550

  4. Kinetic electron and ion instability of the lunar wake simulated at physical mass ratio

    NASA Astrophysics Data System (ADS)

    Haakonsen, Christian Bernt; Hutchinson, Ian H.; Zhou, Chuteng

    2015-03-01

    The solar wind wake behind the moon is studied with 1D electrostatic particle-in-cell (PIC) simulations using a physical ion to electron mass ratio (unlike prior investigations); the simulations also apply more generally to supersonic flow of dense magnetized plasma past non-magnetic objects. A hybrid electrostatic Boltzmann electron treatment is first used to investigate the ion stability in the absence of kinetic electron effects, showing that the ions are two-stream unstable for downstream wake distances (in lunar radii) greater than about three times the solar wind Mach number. Simulations with PIC electrons are then used to show that kinetic electron effects can lead to disruption of the ion beams at least three times closer to the moon than in the hybrid simulations. This disruption occurs as the result of a novel wake phenomenon: the non-linear growth of electron holes spawned from a narrow dimple in the electron velocity distribution. Most of the holes arising from the dimple are small and quickly leave the wake, approximately following the unperturbed electron phase-space trajectories, but some holes originating near the center of the wake remain and grow large enough to trigger disruption of the ion beams. Non-linear kinetic-electron effects are therefore essential to a comprehensive understanding of the 1D electrostatic stability of such wakes, and possible observational signatures in ARTEMIS data from the lunar wake are discussed.

  5. Kinetic electron and ion instability of the lunar wake simulated at physical mass ratio

    SciTech Connect

    Haakonsen, Christian Bernt Hutchinson, Ian H. Zhou, Chuteng

    2015-03-15

    The solar wind wake behind the moon is studied with 1D electrostatic particle-in-cell (PIC) simulations using a physical ion to electron mass ratio (unlike prior investigations); the simulations also apply more generally to supersonic flow of dense magnetized plasma past non-magnetic objects. A hybrid electrostatic Boltzmann electron treatment is first used to investigate the ion stability in the absence of kinetic electron effects, showing that the ions are two-stream unstable for downstream wake distances (in lunar radii) greater than about three times the solar wind Mach number. Simulations with PIC electrons are then used to show that kinetic electron effects can lead to disruption of the ion beams at least three times closer to the moon than in the hybrid simulations. This disruption occurs as the result of a novel wake phenomenon: the non-linear growth of electron holes spawned from a narrow dimple in the electron velocity distribution. Most of the holes arising from the dimple are small and quickly leave the wake, approximately following the unperturbed electron phase-space trajectories, but some holes originating near the center of the wake remain and grow large enough to trigger disruption of the ion beams. Non-linear kinetic-electron effects are therefore essential to a comprehensive understanding of the 1D electrostatic stability of such wakes, and possible observational signatures in ARTEMIS data from the lunar wake are discussed.

  6. Mechanisms of ablation and ion formation in infrared laser mass spectrometry

    NASA Astrophysics Data System (ADS)

    Papantonakis, Michael Robert

    The studies described in this work take advantage of a unique infrared light source that allowed the exploration of previously uninvestigated vibrational modes and excitation densities, plus other laser systems that allowed us to compare the importance of pulse duration and electronic excitation in the ultraviolet. Results from several experiments were compared to current models of ion formation, allowing us to observe their applicability to our systems. One experiment assembled the most extensive range of excitation conditions to date to challenge the contribution of primary excitation events to the final ion yield. Despite the vastly different charged species and densities necessarily created, the results showed qualitatively similar spectra in all cases. We therefore concluded that the similarity of mass spectra alone offers a poor or incomplete picture from which to determine the operative mechanisms for ion formation, and that the observed ions are likely formed in the expanding plume. A second set of experiments utilized vibrational excitation of an intrinsic mode of a sample, eliminating the need for addition of an exogenous matrix. From a practical point of view, this represents a promising new approach to the analysis of complex mixtures. From a mechanistic point of view, the optical and thermal properties of the material, which control the degree of vibrational or electronic excitation upon irradiation, were found to determine the ablation pathways, which subsequently determines the ion formation process. This degree of excitation density, which determines whether ion formation occurs under conditions of thermodynamic equilibrium or kinetic control, may or may not determine the efficiency of ion production, depending on the particular vibrational mode under consideration.

  7. Characterization of oligodeoxynucleotides by electron detachment dissociation fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Yang, Jiong; Mo, Jingjie; Adamson, Julie T; Håkansson, Kristina

    2005-03-15

    Electron detachment dissociation (EDD), recently introduced by Zubarev and co-workers for the dissociation of multiply charged biomolecular anions via a radical ion intermediate, has been shown to be analogous to electron capture dissociation (ECD) in several respects, including more random peptide fragmentation and retention of labile posttranslational modifications. We have previously demonstrated unique fragmentation behavior in ECD compared to vibrational excitation for oligodeoxynucleotide cations. However, that approach is limited by the poor sensitivity for oligonucleotide ionization in positive ion mode. Here, we show implementation of EDD on a commercial Fourier transform ion cyclotron resonance mass spectrometer utilizing two different configurations: a heated filament electron source and an indirectly heated hollow dispenser cathode electron source. The dispenser cathode configuration provides higher EDD efficiency and additional fragmentation channels for hexamer oligodeoxynucleotides. As in ECD, even-electron d/w ion series dominate the spectra, but we also detect numerous a/z (both even-electron and radical species), (a/z - B), c/x, (c/x - B), and (d/w - B) ions with minimal nucleobase loss from the precursor ions. In contrast to previous high-energy collision-activated dissociation (CAD) and ion trap CAD of radical oligonucleotide anions, we only observe minimum sugar cross-ring cleavage, possibly due to the short time scale of EDD, which limits secondary fragmentation. Thus, EDD provides fragmentation similar to ECD for oligodeoxynucleotides but at enhanced sensitivity. Finally, we show that noncovalent bonding in a DNA duplex can be preserved following EDD, illustrating another analogy with ECD. We believe the latter finding implies EDD has promise for characterization of nucleic acid structure and folding. PMID:15762599

  8. Tandem mass spectrometry and ion mobility mass spectrometry for the analysis of molecular sequence and architecture of hyperbranched glycopolymers

    PubMed Central

    Liu, Xiumin; Cool, Lydia R.; Lin, Kenneth; Kasko, Andrea M.; Wesdemiotis, Chrys

    2015-01-01

    Multidimensional mass spectrometry techniques, combining matrix-assisted laser desorption/ionization (MALDI) or electrospray ionization (ESI) with tandem mass spectrometry (MS2), multistage mass spectrometry (MSn) or ion mobility mass spectrometry (IM-MS), have been employed to gain precise structural insight on the compositions, sequences and architectures of small oligomers of a hyperbranched glycopolymer, prepared by atom transfer radical copolymerization of an acrylate monomer (A) and an acrylate inimer (B), both carrying mannose ester pendants. The MS data confirmed the incorporation of multiple inimer repeat units, which ultimately lead to the hyperbranched material. The various possible structures of n-mers with the same composition were subsequently elucidated based on MS2 and MSn studies. The characteristic elimination of bromomethane molecule provided definitive information about the comonomer connectivity in the copolymeric AB2 trimer and A2B2 tetramer, identifying as present only one of the three possible trimeric isomers (viz. sequence BBA) and only two of the six possible tetrameric isomers (viz. sequences BBA2 and BABA). Complementary IM-MS studies confirmed that only one of the tetrameric structures is formed. Comparison of the experimentally determined collision cross-section of the detected isomer with those predicted by molecular simulations for the two possible sequences ascertained BBA2 as the predominant tetrameric architecture. The multidimensional MS approaches presented provide connectivity information at the atomic level without requiring high product purity (due to the dispersive nature of MS) and, hence, should be particularly useful for the microstructure characterization of novel glycopolymers and other types of complex copolymers. PMID:25519163

  9. NEGATIVE ION ELECTROSPRAY OF BROMO- AND CHLORACETIC ACIDS AND AN EVALUATION OF EXACT MASS MEASUREMENTS WITH A BENCH-TOP TIME-OF-FLIGHT MASS SPECTROMETER

    EPA Science Inventory

    The negative ion electrospray mass spectra of six bromo- and chloroacetic acids were measured using two different electrospray interfaces and single quadrupole and bench-top time-of-flight mass spectrometers. With each acid at 50 ug/mL in aqueous methanol at pH 10, the anions ob...

  10. MEMS Fabrication of Micro Cylindrical Ion Trap Mass Spectrometer for CubeSats Application

    NASA Astrophysics Data System (ADS)

    Zheng, Y.

    2015-10-01

    Microelectromechanical Systems (MEMS) technology is used to fabricate arrays of micro Cylindrical Ion Traps (μCIT) which are integrated into a miniaturized mass spectrometer (MS). The micro μCITs are built from silicon wafers and requires high machining precision, smooth surface, and high dimensional uniformity across the array for optimum mass spectrometer performance. In order to build these 3D miniature structures several MEMS processing techniques were explored and a process was developed and tested. By using the developed MEMS process, the required μCIT 4 x 4 arrays were fabricated. This included a chip design variation in which mechanical locking pits and posts were machined in the Ring Electrode (RE) chip and End Plate (EP) chips respectively, for self-assembly. The size of the assembled μCIT is only 12 mm x 12 mm x 1.5 mm. It is a key component for the miniature mass spectrometer. The micro cylindrical ion trap mass spectrometer has the advantages of low-power operation, simpler electronics and less-stringent vacuum system requirements. The MEMS batch production capabilities will also greatly lower the cost. It is a promising candidate for CubeSat and nanoSats applications for exploration of chemical distributions in space.

  11. Systematic Comparison of a Two-dimensional Ion Trap and a Three-dimensional Ion Trap Mass Spectrometer in Proteomics*S

    PubMed Central

    Mayya, Viveka; Rezaul, Karim; Cong, Yu-Sheng; Han, David

    2006-01-01

    The utility and advantages of the recently introduced two-dimensional quadrupole ion trap mass spectrometer in proteomics over the traditional three-dimensional ion trap mass spectrometer have not been systematically characterized. Here we rigorously compared the performance of these two platforms by using over 100,000 tandem mass spectra acquired with identical complex peptide mixtures and acquisition parameters. Specifically we compared four factors that are critical for a successful proteomic study: 1) the number of proteins identified, 2) sequence coverage or the number of peptides identified for every protein, 3) the data base matching SEQUEST Xcorr and Sp score, and 4) the quality of the fragment ion series of peptides. We found a 4–6-fold increase in the number of peptides and proteins identified on the two-dimensional ion trap mass spectrometer as a direct result of improvement in all the other parameters examined. Interestingly more than 70% of the doubly and triply charged peptides, but not the singly charged peptides, showed better quality of fragmentation spectra on the two-dimensional ion trap. These results highlight specific advantages of the two-dimensional ion trap over the conventional three-dimensional ion traps for protein identification in proteomic experiments. PMID:15608339

  12. A Compact Ion and Neutral Mass Spectrometer for the Exocube Mission

    NASA Astrophysics Data System (ADS)

    Jones, S.; Paschalidis, N.; Rodriguez, M.; Sittler, E. C., Jr.; Chornay, D. J.

    2014-12-01

    Demand is high for in situ measurements of atmospheric neutral and ion composition and density, not only for studies of the dynamic ionosphere-theremosphere-mesosphere system but simply to define the steady state background atmospheric conditions. The ExoCube mission is designed to acquire global knowledge of in-situ densities of [H], [He], [O] and [H+], [He+], [O+] in the upper ionosphere and lower exosphere in combination with incoherent scatter radar ground stations distributed in the north polar region. The Heliophysic Division of GSFC has developed a compact Ion and Neutral Mass Spectrometer (INMS) for in situ measurements of ions and neutrals H, He, N, O, N2, O2 with M/dM of approximately 10 at an incoming energy range of 0-50eV. The INMS is based on front end optics, post acceleration, gated time of flight, ESA and CEM or MCP detectors. The compact sensor has a dual symmetric configuration with the ion and neutral sensor heads on opposite sides and with full electronics in the middle. The neutral front end optics includes thermionic emission ionization and ion blocking grids, and the ion front end optics includes spacecraft potential compensation grids. The electronics include front end, fast gating, HVPS, ionizer, TOF binning and full bi directional C&DH digital electronics. The data package includes 400 mass bins each for ions and neutrals and key housekeeping data for instrument health and calibration. The data sampling can be commanded as fast as 10 msec per frame (corresponding to ~80 m spatial separation) in burst mode, and has significant onboard storage capability and data compression scheme. Experimental data from instrument testing with both ions and neutrals will be presented. The instrument is successfully integrated in the CubeSat and passed vibration, thermal and shock testing. The ExoCube mission is scheduled to fly in Nov 2014 in a 445 x 670 km polar orbit with the INMS aperture oriented in the ram direction. This miniaturized instrument (1

  13. Evaluating Multiplexed Quantitative Phosphopeptide Analysis on a Hybrid Quadrupole Mass Filter/Linear Ion Trap/Orbitrap Mass Spectrometer

    PubMed Central

    2015-01-01

    As a driver for many biological processes, phosphorylation remains an area of intense research interest. Advances in multiplexed quantitation utilizing isobaric tags (e.g., TMT and iTRAQ) have the potential to create a new paradigm in quantitative proteomics. New instrumentation and software are propelling these multiplexed workflows forward, which results in more accurate, sensitive, and reproducible quantitation across tens of thousands of phosphopeptides. This study assesses the performance of multiplexed quantitative phosphoproteomics on the Orbitrap Fusion mass spectrometer. Utilizing a two-phosphoproteome model of precursor ion interference, we assessed the accuracy of phosphopeptide quantitation across a variety of experimental approaches. These methods included the use of synchronous precursor selection (SPS) to enhance TMT reporter ion intensity and accuracy. We found that (i) ratio distortion remained a problem for phosphopeptide analysis in multiplexed quantitative workflows, (ii) ratio distortion can be overcome by the use of an SPS-MS3 scan, (iii) interfering ions generally possessed a different charge state than the target precursor, and (iv) selecting only the phosphate neutral loss peak (single notch) for the MS3 scan still provided accurate ratio measurements. Remarkably, these data suggest that the underlying cause of interference may not be due to coeluting and cofragmented peptides but instead from consistent, low level background fragmentation. Finally, as a proof-of-concept 10-plex experiment, we compared phosphopeptide levels from five murine brains to five livers. In total, the SPS-MS3 method quantified 38 247 phosphopeptides, corresponding to 11 000 phosphorylation sites. With 10 measurements recorded for each phosphopeptide, this equates to more than 628 000 binary comparisons collected in less than 48 h. PMID:25521595

  14. Structural Characterization of Anticancer Drug Paclitaxel and Its Metabolites Using Ion Mobility Mass Spectrometry and Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hong Hee; Hong, Areum; Cho, Yunju; Kim, Sunghwan; Kim, Won Jong; Kim, Hugh I.

    2016-02-01

    Paclitaxel (PTX) is a popular anticancer drug used in the treatment of various types of cancers. PTX is metabolized in the human liver by cytochrome P450 to two structural isomers, 3'- p-hydroxypaclitaxel (3 p-OHP) and 6α-hydroxypaclitaxel (6α-OHP). Analyzing PTX and its two metabolites, 3 p-OHP and 6α-OHP, is crucial for understanding general pharmacokinetics, drug activity, and drug resistance. In this study, electrospray ionization ion mobility mass spectrometry (ESI-IM-MS) and collision induced dissociation (CID) are utilized for the identification and characterization of PTX and its metabolites. Ion mobility distributions of 3 p-OHP and 6α-OHP indicate that hydroxylation of PTX at different sites yields distinct gas phase structures. Addition of monovalent alkali metal and silver metal cations enhances the distinct dissociation patterns of these structural isomers. The differences observed in the CID patterns of metalated PTX and its two metabolites are investigated further by evaluating their gas-phase structures. Density functional theory calculations suggest that the observed structural changes and dissociation pathways are the result of the interactions between the metal cation and the hydroxyl substituents in PTX metabolites.

  15. Advances in ion mobility spectrometry–mass spectrometry reveal key insights into amyloid assembly☆

    PubMed Central

    Woods, L.A.; Radford, S.E.; Ashcroft, A.E.

    2013-01-01

    Interfacing ion mobility spectrometry to mass spectrometry (IMS–MS) has enabled mass spectrometric analyses to extend into an extra dimension, providing unrivalled separation and structural characterization of lowly populated species in heterogeneous mixtures. One biological system that has benefitted significantly from such advances is that of amyloid formation. Using IMS–MS, progress has been made into identifying transiently populated monomeric and oligomeric species for a number of different amyloid systems and has led to an enhanced understanding of the mechanism by which small molecules modulate amyloid formation. This review highlights recent advances in this field, which have been accelerated by the commercial availability of IMS–MS instruments. This article is part of a Special Issue entitled: Mass spectrometry in structural biology. PMID:23063533

  16. Systematic Temperature Effects in the Argon Cluster Ion Sputter Depth Profiling of Organic Materials Using Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Seah, Martin P.; Havelund, Rasmus; Gilmore, Ian S.

    2016-08-01

    A study is presented of the effects of sample temperature on the sputter depth profiling of two organic materials, NPB ( N,N'-Di(1-naphthyl)- N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) and Irganox 1010, using a 5 keV Ar2000 + cluster ion beam and analysis by secondary ion mass spectrometry. It is shown that at low temperatures, the yields increase slowly with temperature in accordance with the Universal Sputtering Yield equation where the energy term is now modified by Trouton's rule. This occurs up to a transition temperature, T T, which is, in turn, approximately 0.8 T M, where T M is the sample melting temperature in Kelvin. For NPB and Irganox 1010, these transition temperatures are close to 15 °C and 0 °C, respectively. Above this temperature, the rate of increase of the sputtering yield rises by an order of magnitude. During sputtering, the depth resolution also changes with temperature with a very small change occurring below T T. At higher temperatures, the depth resolution improves but then rapidly degrades, possibly as a result first of local crater surface diffusion and then of bulk inter-diffusion. The secondary ion spectra also change with temperature with the intensities of the molecular entities increasing least. This agrees with a model in which the molecular entities arise near the crater rim. It is recommended that for consistent results, measurements for organic materials are always made at temperatures significantly below T T or 0.8 T M, and this is generally below room temperature.

  17. Systematic Temperature Effects in the Argon Cluster Ion Sputter Depth Profiling of Organic Materials Using Secondary Ion Mass Spectrometry.

    PubMed

    Seah, Martin P; Havelund, Rasmus; Gilmore, Ian S

    2016-08-01

    A study is presented of the effects of sample temperature on the sputter depth profiling of two organic materials, NPB (N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) and Irganox 1010, using a 5 keV Ar2000 (+) cluster ion beam and analysis by secondary ion mass spectrometry. It is shown that at low temperatures, the yields increase slowly with temperature in accordance with the Universal Sputtering Yield equation where the energy term is now modified by Trouton's rule. This occurs up to a transition temperature, T T, which is, in turn, approximately 0.8T M, where T M is the sample melting temperature in Kelvin. For NPB and Irganox 1010, these transition temperatures are close to 15 °C and 0 °C, respectively. Above this temperature, the rate of increase of the sputtering yield rises by an order of magnitude. During sputtering, the depth resolution also changes with temperature with a very small change occurring below T T. At higher temperatures, the depth resolution improves but then rapidly degrades, possibly as a result first of local crater surface diffusion and then of bulk inter-diffusion. The secondary ion spectra also change with temperature with the intensities of the molecular entities increasing least. This agrees with a model in which the molecular entities arise near the crater rim. It is recommended that for consistent results, measurements for organic materials are always made at temperatures significantly below T T or 0.8 T M, and this is generally below room temperature. Graphical Abstract ᅟ. PMID:27106601

  18. Hydrolysis of VX on concrete: rate of degradation by direct surface interrogation using an ion trap secondary ion mass spectrometer.

    PubMed

    Groenewold, Gary S; Williams, John M; Appelhans, Anthony D; Gresham, Garold L; Olson, John E; Jeffery, Mark T; Rowland, Brad

    2002-11-15

    The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min(-1) at 25 degrees C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 degrees C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol(-1). This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface. PMID:12487301

  19. Hydrolysis of VX on Concrete: Rate of Degradation by Direct Surface Interrogation using an Ion Trap Secondary Ion Mass Spectrometer

    SciTech Connect

    Groenewold, Gary Steven; Appelhans, Anthony David; Gresham, Garold Linn; Olson, John Eric; Rowland, B.; Williams, j.; Jeffery, M. T.

    2002-09-01

    The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min-1 at 25 C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol-1. This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.

  20. Systematic Temperature Effects in the Argon Cluster Ion Sputter Depth Profiling of Organic Materials Using Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Seah, Martin P.; Havelund, Rasmus; Gilmore, Ian S.

    2016-04-01

    A study is presented of the effects of sample temperature on the sputter depth profiling of two organic materials, NPB (N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) and Irganox 1010, using a 5 keV Ar2000 + cluster ion beam and analysis by secondary ion mass spectrometry. It is shown that at low temperatures, the yields increase slowly with temperature in accordance with the Universal Sputtering Yield equation where the energy term is now modified by Trouton's rule. This occurs up to a transition temperature, T T, which is, in turn, approximately 0.8T M, where T M is the sample melting temperature in Kelvin. For NPB and Irganox 1010, these transition temperatures are close to 15 °C and 0 °C, respectively. Above this temperature, the rate of increase of the sputtering yield rises by an order of magnitude. During sputtering, the depth resolution also changes with temperature with a very small change occurring below T T. At higher temperatures, the depth resolution improves but then rapidly degrades, possibly as a result first of local crater surface diffusion and then of bulk inter-diffusion. The secondary ion spectra also change with temperature with the intensities of the molecular entities increasing least. This agrees with a model in which the molecular entities arise near the crater rim. It is recommended that for consistent results, measurements for organic materials are always made at temperatures significantly below T T or 0.8 T M, and this is generally below room temperature.