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Sample records for waveform ion mobility

  1. Field Asymmetric Waveform Ion Mobility Spectrometry Studies of Proteins: Dipole Alignment in Ion Mobility Spectrometry?

    Energy Technology Data Exchange (ETDEWEB)

    Shvartsburg, Alexandre A.; Bryskiewicz, Tadeusz; Purves, Randy; Tang, Keqi; Guevremont, Roger; Smith, Richard D.

    2006-11-02

    Approaches to characterization and separation of ions involving their mobilities in gases were developed since 1960-s. Conventional ion mobility spectrometry (IMS) measures the absolute mobility and the field asymmetric waveform IMS (FAIMS) exploits the difference between mobilities at high and low electric fields. However, all previous work was based on the orientationally averaged cross-sections Ωavg between ions and buffer gas molecules. Virtually all large ions are electric dipoles that will be oriented by a sufficiently strong electric field. At typical FAIMS conditions, that must happen for dipole moments > ~400 Debye, found for many macroions including most proteins above ~30 kDa. Mobilities of aligned dipoles depend on directional cross-sections Ωdir (rather than Ωavg), which should have a major effect on FAIMS separation parameters. Here we study the FAIMS behavior of ESI-generated ions for ten proteins up to ~70 kDa. Those above 29 kDa exhibit a strong increase of mobility at high field, which is consistent with predicted ion dipole alignment. This effect expands the FAIMS peak capacity by an order of magnitude, allowing separation of up to ~102 distinct protein conformers and revealing information about Ωdir and ion dipole moment that is of potential utility for structural characterization. Possible means to extend the dipole alignment to smaller ions are discussed.

  2. Isotope separation using high-field asymmetric waveform ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, David A.; Purves, Randy W.; Guevremont, Roger E-mail: roger.guevremont@nrc.ca

    2000-08-01

    A new apparatus for gas-phase separation of stable elemental isotopes at atmospheric pressure is described. A gaseous mixture of chloride isotopes was generated using electrospray ionization and introduced into the analyzer region of a high-field asymmetric waveform ion mobility spectrometer (FAIMS). The ion current exiting the FAIMS was sampled into a quadrupole mass spectrometer for isotope identification.

  3. Separation of Opiate Isomers Using Electrospray Ionization and Paper Spray Coupled to High-Field Asymmetric Waveform Ion Mobility Spectrometry

    Science.gov (United States)

    Manicke, Nicholas E.; Belford, Michael

    2015-05-01

    One limitation in the growing field of ambient or direct analysis methods is reduced selectivity caused by the elimination of chromatographic separations prior to mass spectrometric analysis. We explored the use of high-field asymmetric waveform ion mobility spectrometry (FAIMS), an ambient pressure ion mobility technique, to separate the closely related opiate isomers of morphine, hydromorphone, and norcodeine. These isomers cannot be distinguished by tandem mass spectrometry. Separation prior to MS analysis is, therefore, required to distinguish these compounds, which are important in clinical chemistry and toxicology. FAIMS was coupled to a triple quadrupole mass spectrometer, and ionization was performed using either a pneumatically assisted heated electrospray ionization source (H-ESI) or paper spray, a direct analysis method that has been applied to the direct analysis of dried blood spots and other complex samples. We found that FAIMS was capable of separating the three opiate structural isomers using both H-ESI and paper spray as the ionization source.

  4. Separation and identification of isomeric glycopeptides by high field asymmetric waveform ion mobility spectrometry.

    Science.gov (United States)

    Creese, Andrew J; Cooper, Helen J

    2012-03-01

    The analysis of intact glycopeptides by mass spectrometry is challenging due to the numerous possibilities for isomerization, both within the attached glycan and the location of the modification on the peptide backbone. Here, we demonstrate that high field asymmetric wave ion mobility spectrometry (FAIMS), also known as differential ion mobility, is able to separate isomeric O-linked glycopeptides that have identical sequences but differing sites of glycosylation. Two glycopeptides from the glycoprotein mucin 5AC, GT(GalNAc)TPSPVPTTSTTSAP and GTTPSPVPTTST(GalNAc)TSAP (where GalNAc is O-linked N-acetylgalactosamine), were shown to coelute following reversed-phase liquid chromatography. However, FAIMS analysis of the glycopeptides revealed that the compensation voltage ranges in which the peptides were transmitted differed. Thus, it is possible at certain compensation voltages to completely separate the glycopeptides. Separation of the glycopeptides was confirmed by unique reporter ions produced by supplemental activation electron transfer dissociation mass spectrometry. These fragments also enable localization of the site of glycosylation. The results suggest that glycan position plays a key role in determining gas-phase glycopeptide structure and have implications for the application of FAIMS in glycoproteomics.

  5. High-field asymmetric waveform ion mobility spectrometry with solvent vapor addition: a potential greener bioanalytical technique.

    Science.gov (United States)

    Tsai, Chia-Wei; Yost, Richard A; Garrett, Timothy J

    2012-06-01

    Green chemistry is a way to avoid threats to human health and the environment in chemical processes, including analytical methodology. According to the 12 principles provided by ACS Green Chemistry Institute, first described by Anastas and Warner, prevention of waste generation should be first considered as an alternative to ways of treating waste. Therefore, analytical techniques that may reduce solvent waste are of great interest towards greener analysis. High-field asymmetric waveform ion mobility spectrometry (FAIMS) utilizes electrical fields to achieve separation, post an ionization source, and could provide an alternative method for separation and reduce solvent use in comparison with traditional HPLC methodologies. In this article, the operational principles and developments of FAIMS will be discussed, including the advantages of adding solvent vapor to the carrier gas. In addition, applications and challenges of implementing FAIMS technology will also be discussed.

  6. Analysis of paralytic shellfish toxins using high-field asymmetric waveform ion mobility spectrometry with liquid chromatography-mass spectrometry.

    Science.gov (United States)

    Beach, Daniel G; Melanson, Jeremy E; Purves, Randy W

    2015-03-01

    The analysis of paralytic shellfish toxins (PSTs) by liquid chromatography-mass spectrometry remains a challenge because of their high polarity, large number of analogues and the complex matrix in which they occur. Here we investigate the potential utility of high-field asymmetric waveform ion mobility spectrometry (FAIMS) as a gas-phase ion separation tool for analysis of PSTs by mass spectrometry. We investigate the separation of PSTs using FAIMS with two divergent goals: using FAIMS as a primary separation tool for rapid screening by electrospray ionization (ESI)-FAIMS-MS or combined with LC in a multidimensional LC-ESI-FAIMS-MS separation. First, a survey of the parameters that affect the sensitivity and selectivity of PST analysis by FAIMS was carried out using ESI-FAIMS-MS. In particular, the use of acetonitrile as a gas additive in the carrier gas flow offered good separation of all PST epimeric pairs. A second set of FAIMS conditions was also identified, which focussed PSTs to a relatively narrow CV range allowing development of an LC-ESI-FAIMS-MS method for analysis of PST toxins in complex mussel tissue extracts. The quantitative capabilities of this method were evaluated by analysing a PST containing mussel tissue matrix material. Results compared favourably with analysis by an established LC-post-column oxidation-fluorescence method with recoveries ranging from 70 to 106%, although sensitivity was somewhat reduced. The current work represents the first successful separation of PST isomers using ion mobility and shows the promise of FAIMS as a tool for analysis of algal biotoxins in complex samples and outlines some critical requirements for its future improvement.

  7. High-field asymmetric waveform ion mobility spectrometry for determining the location of in-source collision-induced dissociation in electrospray ionization mass spectrometry.

    Science.gov (United States)

    Xia, Yuan-Qing; Jemal, Mohammed

    2009-09-15

    The understanding and control of the in-source collision-induced dissociation (CID) of analytes is important for the accurate LC-MS/MS quantitation of drugs and metabolites in biological samples. Accordingly, it was of interest to us to establish whether such in-source CID takes place after and/or before the orifice of an electrospray ionization (ESI) mass spectrometer. A high-field asymmetric waveform ion mobility spectrometry (FAIMS) system that is physically located between the sprayer and the orifice of a mass spectrometer can serve as an ion filter to control ions entering the orifice of the mass spectrometer. In such a configuration, FAIMS could conceivably be used to determine if the in-source CID of an analyte occurs after and/or before the mass spectrometer orifice. We demonstrated this capability of FAIMS using ifetroban acylglucuronide metabolite as a model compound. Under the conditions used, the results showed that the in-source CID conversion of the acylglucuronide metabolite to its parent drug ifetroban occurred almost entirely after the orifice of the mass spectrometer, with the conversion upstream of the orifice accounting for only 5.6% of the conversion. Under the circumstance, the term "post-orifice CID" rather than "in-source CID" may be more appropriate in describing such a dissociation occurring in the front end of a mass spectrometer.

  8. Trace level impurity method development with high-field asymmetric waveform ion mobility spectrometry: systematic study of factors affecting the performance.

    Science.gov (United States)

    Champarnaud, Elodie; Laures, Alice M-F; Borman, Phil J; Chatfield, Marion J; Kapron, James T; Harrison, Mark; Wolff, Jean-Claude

    2009-01-01

    For the determination of trace level impurities, analytical chemists are confronted with complex mixtures and difficult separations. New technologies such as high-field asymmetric waveform ion mobility spectrometry (FAIMS) have been developed to make their work easier; however, efficient method development and troubleshooting can be quite challenging if little prior knowledge of the factors or their settings is available. We present the results of an investigation performed in order to obtain a better understanding of the FAIMS technology. The influence of eight factors (polarity of dispersion voltage, outer bias voltage, total gas flow rate, composition of the carrier gas (e.g. %He), outer electrode temperature, ratio between the temperatures of the inner and outer electrodes, flow rate and composition of the make-up mobile phase) was assessed. Five types of responses were monitored: value of the compensation voltage (CV), intensity, width and asymmetry of the compensation voltage peak, and resolution between two peaks. Three types of studies were performed using different test mixtures and various ionisation modes to assess whether the same conclusions could be drawn across these conditions for a number of different types of compounds. To extract the maximum information from as few experiments as possible, a Design of Experiment (DoE) approach was used. The results presented in this work provide detailed information on the factors affecting FAIMS separations and therefore should enable the user to troubleshoot more effectively and to develop efficient methods.

  9. Ion mobility spectrometry

    CERN Document Server

    Eiceman, GA

    2005-01-01

    Key Developments for Faster, More Precise Detection Capabilities Driven by the demand for the rapid and advanced detection of explosives, chemical and biological warfare agents, and narcotics, ion mobility spectrometry (IMS) undergone significant refinements in technology, computational capabilities, and understanding of the principles of gas phase ion chemistry and mobility. Beginning with a thorough discussion of the fundamental theories and physics of ion mobility, Ion Mobility Spectrometry, Second Edition describes the recent advances in instrumentation and newly

  10. Ion mobility sensor system

    Science.gov (United States)

    Xu, Jun; Watson, David B.; Whitten, William B.

    2013-01-22

    An ion mobility sensor system including an ion mobility spectrometer and a differential mobility spectrometer coupled to the ion mobility spectrometer. The ion mobility spectrometer has a first chamber having first end and a second end extending along a first direction, and a first electrode system that generates a constant electric field parallel to the first direction. The differential mobility spectrometer includes a second chamber having a third end and a fourth end configured such that a fluid may flow in a second direction from the third end to the fourth end, and a second electrode system that generates an asymmetric electric field within an interior of the second chamber. Additionally, the ion mobility spectrometer and the differential mobility spectrometer form an interface region. Also, the first end and the third end are positioned facing one another so that the constant electric field enters the third end and overlaps the fluid flowing in the second direction.

  11. Correlation ion mobility spectroscopy

    Science.gov (United States)

    Pfeifer, Kent B.; Rohde, Steven B.

    2008-08-26

    Correlation ion mobility spectrometry (CIMS) uses gating modulation and correlation signal processing to improve IMS instrument performance. Closely spaced ion peaks can be resolved by adding discriminating codes to the gate and matched filtering for the received ion current signal, thereby improving sensitivity and resolution of an ion mobility spectrometer. CIMS can be used to improve the signal-to-noise ratio even for transient chemical samples. CIMS is especially advantageous for small geometry IMS drift tubes that can otherwise have poor resolution due to their small size.

  12. Miniaturized Ion Mobility Spectrometer

    Science.gov (United States)

    Kaye, William J. (Inventor); Stimac, Robert M. (Inventor)

    2015-01-01

    By utilizing the combination of a unique electronic ion injection control circuit in conjunction with a particularly designed drift cell construction, the instantly disclosed ion mobility spectrometer achieves increased levels of sensitivity, while achieving significant reductions in size and weight. The instant IMS is of a much simpler and easy to manufacture design, rugged and hermetically sealed, capable of operation at high temperatures to at least 250.degree. C., and is uniquely sensitive, particularly to explosive chemicals.

  13. Fundamentals of traveling wave ion mobility spectrometry.

    Science.gov (United States)

    Shvartsburg, Alexandre A; Smith, Richard D

    2008-12-15

    Traveling wave ion mobility spectrometry (TW IMS) is a new IMS method implemented in the Synapt IMS/mass spectrometry system (Waters). Despite its wide adoption, the foundations of TW IMS were only qualitatively understood and factors governing the ion transit time (the separation parameter) and resolution remained murky. Here we develop the theory of TW IMS using derivations and ion dynamics simulations. The key parameter is the ratio (c) of ion drift velocity at the steepest wave slope to wave speed. At low c, the ion transit velocity is proportional to the squares of mobility (K) and electric field intensity (E), as opposed to linear scaling in drift tube (DT) IMS and differential mobility analyzers. At higher c, the scaling deviates from quadratic in a way controlled by the waveform profile, becoming more gradual with the ideal triangular profile but first steeper and then more gradual for realistic profiles with variable E. At highest c, the transit velocity asymptotically approaches the wave speed. Unlike with DT IMS, the resolving power of TW IMS depends on mobility, scaling as K(1/2) in the low-c limit and less at higher c. A nonlinear dependence of the transit time on mobility means that the true resolving power of TW IMS differs from that indicated by the spectrum. A near-optimum resolution is achievable over an approximately 300-400% range of mobilities. The major predicted trends are in agreement with TW IMS measurements for peptide ions as a function of mobility, wave amplitude, and gas pressure. The issues of proper TW IMS calibration and ion distortion by field heating are also discussed. The new quantitative understanding of TW IMS separations allows rational optimization of instrument design and operation and improved spectral calibration.

  14. Arbitrary Waveform Generator for Quantum Information Processing with Trapped Ions

    CERN Document Server

    Bowler, R; Britton, J W; Sawyer, B C; Amini, J

    2013-01-01

    Atomic ions confined in multi-electrode traps have been proposed as a basis for scalable quantum information processing. This scheme involves transporting ions between spatially distinct locations by use of time-varying electric potentials combined with laser or microwave pulses for quantum logic in specific locations. We report the development of a fast multi-channel arbitrary waveform generator for applying the time-varying electric potentials used for transport and for shaping quantum logic pulses. The generator is based on a field-programmable gate array controlled ensemble of 16-bit digital-to-analog converters with an update frequency of 50 MHz and an output range of $\\pm$10 V. The update rate of the waveform generator is much faster than relevant motional frequencies of the confined ions in our experiments, allowing diabatic control of the ion motion. Numerous pre-loaded sets of time-varying voltages can be selected with 40 ns latency conditioned on real-time signals. Here we describe the device and de...

  15. Control of ion energy and angular distributions using voltage waveform

    Energy Technology Data Exchange (ETDEWEB)

    Rauf, S.

    1999-07-01

    A number of plasma-aided microelectronics manufacturing processes sensitively depend on the ion characteristics at the substrate, in particular the ion energy (IEDF) and angular (IADF) distribution functions. The outcome of these processes can be much more precisely controlled if one has direct control over the IEDFs and IADFs. Past studies have explored the influence of rb bias voltage amplitude and frequency, inductive power deposition and gas pressure on the ion characteristics at the substrate. The factor that influences the ion dynamics most is however the time-dependent sheath voltage and, as demonstrated in this paper, sheath voltage can be accurately controlled using the rf bias voltage waveform. In this paper, the authors computationally examine the influence of the rf bias voltage waveform on the IEDFs and IADFs at the substrate in an inductively coupled plasma (ICP) reactor. This study has been conducted using a coupled set of the Hybrid Plasma Equipment Model (HPEM) and a circuit model, and the Plasma Chemistry Monte Carlo Simulation (PCMCS).

  16. High sensitivity field asymmetric ion mobility spectrometer

    Science.gov (United States)

    Chavarria, Mario A.; Matheoud, Alessandro V.; Marmillod, Philippe; Liu, Youjiang; Kong, Deyi; Brugger, Jürgen; Boero, Giovanni

    2017-03-01

    A high sensitivity field asymmetric ion mobility spectrometer (FAIMS) was designed, fabricated, and tested. The main components of the system are a 10.6 eV UV photoionization source, an ion filter driven by a high voltage/high frequency n-MOS inverter circuit, and a low noise ion detector. The ion filter electronics are capable to generate square waveforms with peak-to-peak voltages up to 1000 V at frequencies up to 1 MHz with adjustable duty cycles. The ion detector current amplifier has a gain up to 1012 V/A with an effective equivalent input noise level down to about 1 fA/Hz1/2 during operation with the ion filter at the maximum voltage and frequency. The FAIMS system was characterized by detecting different standard chemical compounds. Additionally, we investigated the use of a synchronous modulation/demodulation technique to improve the signal-to-noise ratio in FAIMS measurements. In particular, we implemented the modulation of the compensation voltage with the synchronous demodulation of the ion current. The analysis of the measurements at low concentration levels led to an extrapolated limit of detection for acetone of 10 ppt with an averaging time of 1 s.

  17. Detection, identification, and occurrence of thiotetronic acids in drinking water from underground sources by electrospray ionization-high field asymmetric waveform ion mobility spectrometry-quadrupole time-of-flight-mass spectrometry.

    Science.gov (United States)

    Lyczko, Jadwiga; Beach, Daniel; Gabryelski, Wojciech

    2015-10-01

    This paper demonstrates that electrospray ionization (ESI) with differential ion mobility spectroscopy (FAIMS) and "soft" mass spectrometry (MS) provide unique analytical capabilities that led to the discovery of sulfur-containing polar congeners of thiotetronic acid (TA) in drinking water from underground sources in Canada and the United States. Polar TAs accumulate in underground aquifers and appear to be the most abundant class of organic compounds in bottled water but cannot be detected by conventional mass spectrometry methods. We show that normally stable TAs are converted into very reactive ions in ESI which have to be analyzed using special conditions in ESI-FAIMS-MS to avoid extensive dissociation and ion/molecule reactions. De novo identification of 10 TAs was accomplished by the comparative tandem mass spectrometry analysis of authentic TA derivatives from groundwater samples and synthetic TA analogues prepared for this study. We present highlights of gas phase ion chemistry of polar TAs to explain their unique properties and reactivity. TA derivatives were originally isolated from soil bacteria and are of interest in the pharmaceutical industry due to their potent activity against a broad spectrum of pathogenic bacteria and negligible toxicity to mammals. We suspect that TAs are natural disinfection agents protecting groundwater from bacterial contamination, but these compound undergo modifications or decompose during an ozonation water treatment.

  18. Tailored-waveform Collisional Activation of Peptide Ion Electron Transfer Survivor Ions in Cation Transmission Mode Ion/Ion Reaction Experiments

    Science.gov (United States)

    Han, Hongling; Londry, Frank A.; Erickson, David E.; McLuckey, Scott A.

    2010-01-01

    SUMMARY Broad-band resonance excitation via a tailored waveform in a high pressure collision cell (Q2) on a hybrid quadrupole/time-of-flight (QqTOF) tandem mass spectrometer has been implemented for cation transmission mode electron transfer ion/ion reactions of tryptic polypeptides. The frequency components in the broadband waveform were defined to excite the first generation intact electron transfer products for relatively large tryptic peptides. The optimum amplitude of the arbitrary waveform applied has been determined empirically to be 3.0 Vp-p, which is effective for relatively high mass-to-charge (m/z) ratio precursor ions with little elimination of sequence information for low m/z ions. The application of broadband activation during the transmission mode ion/ion reaction obviates frequency and amplitude tuning normally associated with ion trap collision induced dissociation (CID). This approach has been demonstrated with triply and doubly charged tryptic peptides with and without post-translational modifications. Enhanced structural information was achieved by production of a larger number of informative c- and z-type fragments using the tailored waveform on unmodified and modified (phosphorylated and glycosylated) peptides when the first generation intact electron transfer products fell into the defined frequency range. This approach can be applied to a wide range of tryptic peptide ions, making it attractive as a rapid and general approach for ETD LC-MS/MS of tryptic peptides in a QqTOF instrument. PMID:19305916

  19. Characterization of Traveling Wave Ion Mobility Separations in Structures for Lossless Ion Manipulations.

    Science.gov (United States)

    Hamid, Ahmed M; Ibrahim, Yehia M; Garimella, Sandilya V B; Webb, Ian K; Deng, Liulin; Chen, Tsung-Chi; Anderson, Gordon A; Prost, Spencer A; Norheim, Randolph V; Tolmachev, Aleksey V; Smith, Richard D

    2015-11-17

    We report on the development and characterization of a traveling wave (TW)-based Structures for Lossless Ion Manipulations (TW-SLIM) module for ion mobility separations (IMS). The TW-SLIM module uses parallel arrays of rf electrodes on two closely spaced surfaces for ion confinement, where the rf electrodes are separated by arrays of short electrodes, and using these TWs can be created to drive ion motion. In this initial work, TWs are created by the dynamic application of dc potentials. The capabilities of the TW-SLIM module for efficient ion confinement, lossless ion transport, and ion mobility separations at different rf and TW parameters are reported. The TW-SLIM module is shown to transmit a wide mass range of ions (m/z 200-2500) utilizing a confining rf waveform (∼1 MHz and ∼300 Vp-p) and low TW amplitudes (<20 V). Additionally, the short TW-SLIM module achieved resolutions comparable to existing commercially available low pressure IMS platforms and an ion mobility peak capacity of ∼32 for TW speeds of <210 m/s. TW-SLIM performance was characterized over a wide range of rf and TW parameters and demonstrated robust performance. The combined attributes of the flexible design and low voltage requirements for the TW-SLIM module provide a basis for devices capable of much higher resolution and more complex ion manipulations.

  20. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: vibrational kinetics and negative ions control

    NARCIS (Netherlands)

    Diomede, P.; Bruneau, B.; Longo, S.; Johnson, E.; Booth, J. P.

    2017-01-01

    A comprehensive hybrid model of a hydrogen capacitively coupled plasmas (CCP), including a detailed description of the molecular vibrational kinetics, has been applied to the study of the effect of tailored voltage waveforms (TVWs) on the production kinetics and transport of negative ions in these

  1. Method and device for ion mobility separations

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Yehia M.; Garimella, Sandilya V. B.; Smith, Richard D.

    2017-07-11

    Methods and devices for ion separations or manipulations in gas phase are disclosed. The device includes a single non-planar surface. Arrays of electrodes are coupled to the surface. A combination of RF and DC voltages are applied to the arrays of electrodes to create confining and driving fields that move ions through the device. The DC voltages are static DC voltages or time-dependent DC potentials or waveforms.

  2. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: vibrational kinetics and negative ions control

    Science.gov (United States)

    Diomede, P.; Bruneau, B.; Longo, S.; Johnson, E.; Booth, J.-P.

    2017-07-01

    A comprehensive hybrid model of a hydrogen capacitively coupled plasma, including a detailed description of the molecular vibrational kinetics, has been applied to the study of the effect of tailored voltage waveforms (TVWs) on the production kinetics and transport of negative ions in these discharges. Two kinds of TVWs are considered, valleys-to-peaks and saw-tooth, with amplitude and slope asymmetry respectively. By tailoring the voltage waveform only, it is possible to exert substantial control over the peak density and position of negative ions inside the discharge volume. This control is particularly effective for saw-tooth waveforms. Insight into the mechanisms allowing this control is provided by an analysis of the model results. This reveals the roles of the vibrational distribution function and of the electron energy distribution and their correlations, as well as changes in the negative ion transport in the electric field when using different TVWs. Considering the chemical reactivity of H- ions, the possibility of a purely electrical control of the negative ion cloud in a reactor operating with a feedstock gas diluted by hydrogen may find interesting applications. This is the first study of vibrational kinetics in the context of TVWs in molecular gases.

  3. Ion mobility spectrometer with virtual aperture grid

    Science.gov (United States)

    Pfeifer, Kent B.; Rumpf, Arthur N.

    2010-11-23

    An ion mobility spectrometer does not require a physical aperture grid to prevent premature ion detector response. The last electrodes adjacent to the ion collector (typically the last four or five) have an electrode pitch that is less than the width of the ion swarm and each of the adjacent electrodes is connected to a source of free charge, thereby providing a virtual aperture grid at the end of the drift region that shields the ion collector from the mirror current of the approaching ion swarm. The virtual aperture grid is less complex in assembly and function and is less sensitive to vibrations than the physical aperture grid.

  4. Pendular Proteins in Gases and New Avenues for Characterization of Macromolecules by Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Shvartsburg, Alexandre A.; Noskov, Sergei; Purves, Randy; Smith, Richard D.

    2009-04-21

    Polar molecules align in electric fields when the dipole energy (proportional to field intensity E × dipole moment p) exceeds the thermal rotational energy. Small molecules have low p and align only at inordinately high E or upon extreme cooling. Many biomacromolecules and ions are strong permanent dipoles and may align at E achievable in gases and room temperature. The collision cross sections of aligned ions with gas molecules generally differ from orientationally averaged quantities, affecting ion mobilities measured in ion mobility spectrometry (IMS). Field asymmetric waveform IMS (FAIMS) separates ions by the difference between mobilities at high and low E and hence can resolve and identify macroion conformers based on the mobility difference between pendular and free rotor states. An exceptional sensitivity of that difference to the ion geometry and charge distribution holds the potential for a powerful new method for separation and characterization of macromolecular species. Theory predicts that the pendular alignment of ions in gases at any E requires a minimum p depending on the ion mobility, gas pressure, and temperature. At ambient conditions used in current FAIMS systems, the p for realistic ions must exceed ~300 - 400 Debye. The dipole moments of proteins statistically increase with increasing mass, and such values are typical above ~30 kDa. FAIMS analyses of protein ions and complexes of ~30 - 130 kDa show an order-of-magnitude expansion of separation space compared to smaller proteins and other ions, consistent with expectations for the dipole-aligned regime.

  5. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: excitation dynamics and ion flux asymmetry

    Science.gov (United States)

    Bruneau, B.; Diomede, P.; Economou, D. J.; Longo, S.; Gans, T.; O'Connell, D.; Greb, A.; Johnson, E.; Booth, J.-P.

    2016-08-01

    Parallel plate capacitively coupled plasmas in hydrogen at relatively high pressure (~1 Torr) are excited with tailored voltage waveforms containing up to five frequencies. Predictions of a hybrid model combining a particle-in-cell simulation with Monte Carlo collisions and a fluid model are compared to phase resolved optical emission spectroscopy measurements, yielding information on the dynamics of the excitation rate in these discharges. When the discharge is excited with amplitude asymmetric waveforms, the discharge becomes electrically asymmetric, with different ion energies at each of the two electrodes. Unexpectedly, large differences in the \\text{H}2+ fluxes to each of the two electrodes are caused by the different \\text{H}3+ energies. When the discharge is excited with slope asymmetric waveforms, only weak electrical asymmetry of the discharge is observed. In this case, electron power absorption due to fast sheath expansion at one electrode is balanced by electron power absorption at the opposite electrode due to a strong electric field reversal.

  6. Dual mode ion mobility spectrometer and method for ion mobility spectrometry

    Science.gov (United States)

    Scott, Jill R [Idaho Falls, ID; Dahl, David A [Idaho Falls, ID; Miller, Carla J [Idaho Falls, ID; Tremblay, Paul L [Idaho Falls, ID; McJunkin, Timothy R [Idaho Falls, ID

    2007-08-21

    Ion mobility spectrometer apparatus may include an ion interface that is operable to hold positive and negative ions and to simultaneously release positive and negative ions through respective positive and negative ion ports. A first drift chamber is operatively associated with the positive ion port of the ion interface and encloses an electric field therein. A first ion detector operatively associated with the first drift chamber detects positive ions from the first drift chamber. A second drift chamber is operatively associated with the negative ion port of the ion interface and encloses an electric field therein. A second ion detector operatively associated with the second drift chamber detects negative ions from said second drift chamber.

  7. The development of ion mobility technology

    Science.gov (United States)

    Beliakov, V. V.; Golovin, A. V.; Vasilev, V. K.; Malkin, E. K.; Gromov, E. A.; Ivanov, I. A.; Matusko, M. A.; Lipatov, D. Y.

    2016-10-01

    Increased terrorist threat in recent years makes it especially important to improve the custom equipment including the development of ion mobility spectrometers for reliable, realtime and sensitive identification of illicit substances. The paper summarizes different approaches used in recent developments in the last years: statistical analysis, sampling automation and construction materials study.

  8. Ion mobility analysis of lipoproteins

    Science.gov (United States)

    Benner, W. Henry; Krauss, Ronald M.; Blanche, Patricia J.

    2007-08-21

    A medical diagnostic method and instrumentation system for analyzing noncovalently bonded agglomerated biological particles is described. The method and system comprises: a method of preparation for the biological particles; an electrospray generator; an alpha particle radiation source; a differential mobility analyzer; a particle counter; and data acquisition and analysis means. The medical device is useful for the assessment of human diseases, such as cardiac disease risk and hyperlipidemia, by rapid quantitative analysis of lipoprotein fraction densities. Initially, purification procedures are described to reduce an initial blood sample to an analytical input to the instrument. The measured sizes from the analytical sample are correlated with densities, resulting in a spectrum of lipoprotein densities. The lipoprotein density distribution can then be used to characterize cardiac and other lipid-related health risks.

  9. Separation of peptides from detergents using ion mobility spectrometry.

    Science.gov (United States)

    Bagag, Aïcha; Giuliani, Alexandre; Canon, Francis; Réfrégiers, Matthieu; Le Naour, François

    2011-11-30

    Mass spectrometry (MS) has dramatically evolved in the last two decades and has been the driving force of the spectacular expansion of proteomics during this period. However, the very poor compatibility of MS with detergents is still a technical obstacle in some studies, in particular on membrane proteins. Indeed, the high hydrophobicity of membrane proteins necessitates the use of detergents for their extraction and solubilization. Here, we address the analytical potential of high-field asymmetric waveform ion mobility spectrometry (FAIMS) for separating peptides from detergents. The study was focused on peptides from the human integral membrane protein CD9. A tryptic peptide was mixed with the non-ionic detergents Triton X-100 or beta-D-dodecyl maltoside (DDM) as well as with the ionic detergents sodium dodecyl sulfate (SDS) or sodium deoxycholate (SDC). Although electrospray ionization (ESI) alone led to a total suppression of the peptide ion signal on mass spectra with only detection of the detergents, use of FAIMS allowed separation and clear identification of the peptide with any of the detergents studied. The detection and identification of the target compound in the presence of an excess of detergents are then feasible. FAIMS should prove especially useful in the structural and proteomic analysis of membrane proteins.

  10. Ion-molecule clustering in differential mobility spectrometry: lessons learned from tetraalkylammonium cations and their isomers.

    Science.gov (United States)

    Campbell, J Larry; Zhu, Mabel; Hopkins, W Scott

    2014-09-01

    Differential mobility spectrometry (DMS) can distinguish ions based upon the differences in their high- and low-field ion mobilities as they experience the asymmetric waveform applied to the DMS cell. These mobilities are known to be influenced by the ions' structure, m/z, and charge distribution (i.e., resonance structures) within the ions themselves, as well as by the gas-phase environment of the DMS cell. While these associations have been developed over time through empirical observations, the exact role of ion structures or their interactions with clustering molecules remains generally unknown. In this study, that relationship is explored by observing the DMS behaviors of a series of tetraalkylammonium ions as a function of their structures and the gas-phase environment of the DMS cell. To support the DMS experiments, the basin-hopping search strategy was employed to identify candidate cluster structures for density functional theory treatment. More than a million cluster structures distributed across 72 different ion-molecule cluster systems were sampled to determine global minimum structures and cluster binding energies. This joint computational and experimental approach suggests that cluster geometry, in particular ion-molecule intermolecular separation, plays a critical role in DMS.

  11. Proton-bound cluster ions in ion mobility spectrometry.

    Science.gov (United States)

    Ewing, R G; Eiceman, G A; Stone, J A

    1999-10-28

    Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

  12. Hybrid ion mobility and mass spectrometry as a separation tool.

    Science.gov (United States)

    Ewing, Michael A; Glover, Matthew S; Clemmer, David E

    2016-03-25

    Ion mobility spectrometry (IMS) coupled to mass spectrometry (MS) has seen spectacular growth over the last two decades. Increasing IMS sensitivity and capacity with improvements in MS instrumentation have driven this growth. As a result, a diverse new set of techniques for separating ions by their mobility have arisen, each with characteristics that make them favorable for some experiments and some mass spectrometers. Ion mobility techniques can be broken down into dispersive and selective techniques based upon whether they pass through all mobilities for later analysis by mass spectrometry or select ions by mobility or a related characteristic. How ion mobility techniques fit within a more complicated separation including mass spectrometry and other techniques such as liquid chromatography is of fundamental interest to separations scientists. In this review we explore the multitude of ion mobility techniques hybridized to different mass spectrometers, detailing current challenges and opportunities for each ion mobility technique and for what experiments one technique might be chosen over another. The underlying principles of ion mobility separations, including: considerations regarding separation capabilities, ion transmission, signal intensity and sensitivity, and the impact that the separation has upon the ion structure (i.e., the possibility of configurational changes due to ion heating) are discussed.

  13. Aspirated capacitor measurements of air conductivity and ion mobility spectra

    CERN Document Server

    Aplin, K L

    2005-01-01

    Measurements of ions in atmospheric air are used to investigate atmospheric electricity and particulate pollution. Commonly studied ion parameters are (1) air conductivity, related to the total ion number concentration, and (2) the ion mobility spectrum, which varies with atmospheric composition. The physical principles of air ion instrumentation are long-established. A recent development is the computerised aspirated capacitor, which measures ions from (a) the current of charged particles at a sensing electrode, and (b) the rate of charge exchange with an electrode at a known initial potential, relaxing to a lower potential. As the voltage decays, only ions of higher and higher mobility are collected by the central electrode and contribute to the further decay of the voltage. This enables extension of the classical theory to calculate ion mobility spectra by inverting voltage decay time series. In indoor air, ion mobility spectra determined from both the novel voltage decay inversion, and an established volt...

  14. Energy landscapes for mobile ions in ion conducting solids

    Indian Academy of Sciences (India)

    S Adams

    2006-11-01

    Structure property function relationships provide valuable guidelines in the systematic development of advanced functional materials with tailored properties. It is demonstrated that an augmented bond valence approach can be effectively used to establish such relationships for solid electrolytes. A bond valence analysis of local structure models for disordered systems or interfaces based on reverse Monte Carlo (RMC) fits or molecular dynamics (MD) simulations yields quantitative predictions of the ion transport characteristics. As demonstrated here for a range of metaphosphate and diborate glasses, the complete description of the energy landscape for mobile ions also provides an effective tool for achieving a more detailed understanding of ion transport in glasses. The investigation of time evolutions can be included, if the bond valence analysis is based on MD trajectories. In principle, this allows quantifying the time and temperature dependence of pathway characteristics, provided that a suitable empirical force-field is available. For the example of LiPO3, the remaining differences between simulated and experimental structures are investigated and a compensation method is discussed.

  15. Method for enhancing the resolving power of ion mobility separations over a limited mobility range

    Science.gov (United States)

    Shvartsburg, Alexandre A; Tang, Keqi; Smith, Richard D

    2014-09-23

    A method for raising the resolving power, specificity, and peak capacity of conventional ion mobility spectrometry is disclosed. Ions are separated in a dynamic electric field comprising an oscillatory field wave and opposing static field, or at least two counter propagating waves with different parameters (amplitude, profile, frequency, or speed). As the functional dependencies of mean drift velocity on the ion mobility in a wave and static field or in unequal waves differ, only single species is equilibrated while others drift in either direction and are mobility-separated. An ion mobility spectrum over a limited range is then acquired by measuring ion drift times through a fixed distance inside the gas-filled enclosure. The resolving power in the vicinity of equilibrium mobility substantially exceeds that for known traveling-wave or drift-tube IMS separations, with spectra over wider ranges obtainable by stitching multiple segments. The approach also enables low-cutoff, high-cutoff, and bandpass ion mobility filters.

  16. A novel technique to determine atmospheric ion mobility spectra

    CERN Document Server

    Aplin, K L

    2003-01-01

    Detailed tropospheric ion measurements are needed to improve understanding of the electrical microphysics affecting clouds. Additionally, atmospheric ion mobility spectra can be used to identify ion growth processes leading to condensation nucleus formation. However these measurements are rare, particularly in the troposphere where the majority of clouds form. Developments in the operating theory of the classical instrument for ion measurement, the aspirated cylindrical capacitor, are described, which enable ion mobility spectrum information to be extracted from the rate of voltage decay of the aspirated capacitor in air. In this paper, data from historical balloon-borne ion counter ascents will be reanalysed to extract new ion mobility spectra from simple voltage time series. Such data recovery will increase the amount of atmospheric ion spectra available for analysis.

  17. Capacitively coupled hydrogen plasmas sustained by tailored voltage waveforms: excitation dynamics and ion flux asymmetry

    NARCIS (Netherlands)

    Bruneau, B.; Diomede, P.; Economou, D. J.; Longo, S.; Gans, T.; O’Connell, D.; Greb, A.; Johnson, E.; Booth, J. P.

    2016-01-01

    Parallel plate capacitively coupled plasmas in hydrogen at relatively high pressure ( 1 Torr) are excited with tailored voltage waveforms containing up to five frequencies. Predictions of a hybrid model combining a particle-in-cell simulation with Monte Carlo collisions and a fluid model

  18. Field applications of ion-mobility spectrometry

    Science.gov (United States)

    Brown, Patricia A.

    1997-02-01

    Ion mobility spectrometry (IMS) is an excellent tool for detection of controlled substances under field conditions. Plasmagrams and tables showing the results of field applications will be discussed. Residues of drugs, such as cocaine and heroin, can be left anywhere including vehicles, boats, and houses. In houses, the carpets, walls, and floors are good locations for residues to adhere. Individual clothing can also be contaminated with drug residue. Vehicles that are suspected of having previously smuggled illegal substances can be vacuumed and screened. Tablets that look similar and respond the same when screened with the Marquis reagent can be differentiated by IMS. With Southern California being the 'methamphetamine capital of the world' and the resurgence of phencyclidine, IMS has proven extremely valuable in the screening of abandoned clandestine laboratory sites and vehicles in which the clandestine laboratories; chemicals and glassware were transported. IMS is very responsive to ephedrine/pseudophedrine, a precursor of methamphetamine and 1-piperidinocyclohexanecarbonitrile, an intermediate of phencyclidine. Once residues are detected, vacuum samples, and/or methanol wipes are collected and analyzed at the DEA Laboratory for confirmation of the suspected substance using GC-IRD or Mass Spectrometry.

  19. Determination of alcohol compounds using corona discharge ion mobility spectrometry

    Institute of Scientific and Technical Information of China (English)

    HAN Hai-yan; HUANG Guo-dong; JIN Shun-ping; ZHENG Pei-chao; XU Guo-hua; LI Jian-quan; WANG Hong-mei; CHU Yan-nan

    2007-01-01

    Ion mobility spectrometry (IMS) is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions (H2O)nH+ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions (H2O)nH+. The mixture of these alcohols, including two isomers, has been detected, and the result shows that they can also be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional 63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.

  20. [Ion mobility spectrometry for the isomeric volatile organic compounds].

    Science.gov (United States)

    Han, Hai-yan; Jia, Xian-de; Huang, Guo-dong; Wang, Hong-mei; Li, Jian-quan; Jin, Shun-ping; Jiang, Hai-he; Chu, Yan-nan; Zhou, Shi-kang

    2007-10-01

    Ion mobility spectrometry (IMS) is based on determining the drift velocities, which the ionized sample molecules attain in the weak electric field of a drift tube at atmospheric pressure. The drift behavior can be affected by structural differences of the analytes, so that ion mobility spectrometry has the ability to separated isomeric compounds. In the present article, an introduction to IMS is given, followed by a description of the instrument used for the experiments to differentiate isomeric compounds. Positive ion mobility spectras of three kinds of isomeric volatile organic compounds were studied in a homemade high-resolution IMS apparatus with a discharge ionization source. The study includes the differences in the structure of carbon chain, the style of function group, and the position of function group. The reduced mobility values were determined, which are in very good agreement with the previously reported theoretical values using neural network theory. The influence of the structural features of the substances and including the size and shape of the molecule has been investigated. The reduced mobility values increases in the order: alcohols ion mobility spectra of the constitutional isomers studied reflect the influence of structural features. In order to calibrate or determine the detection limits and the sensitivity of the ion mobility spectrometry, the exponential dilution flask (EDF) was used. Using this method, the detection limit of the analytes can reach the order of magnitude of ng x L(-1).

  1. Traveling-wave ion mobility mass spectrometry of protein complexes

    DEFF Research Database (Denmark)

    Salbo, Rune; Bush, Matthew F; Naver, Helle

    2012-01-01

    The collision cross-section (Ω) of a protein or protein complex ion can be measured using traveling-wave (T-wave) ion mobility (IM) mass spectrometry (MS) via calibration with compounds of known Ω. The T-wave Ω-values depend strongly on instrument parameters and calibrant selection. Optimization...

  2. Monte Carlo Simulation of Ion Trajectories of Reacting Chemical Systems: Mobility of Small Water Clusters in Ion Mobility Spectrometry

    Science.gov (United States)

    Wissdorf, Walter; Seifert, Luzia; Derpmann, Valerie; Klee, Sonja; Vautz, Wolfgang; Benter, Thorsten

    2013-04-01

    For the comprehensive simulation of ion trajectories including reactive collisions at elevated pressure conditions, a chemical reaction simulation (RS) extension to the popular SIMION software package was developed, which is based on the Monte Carlo statistical approach. The RS extension is of particular interest to SIMION users who wish to simulate ion trajectories in collision dominated environments such as atmospheric pressure ion sources, ion guides (e.g., funnels, transfer multi poles), chemical reaction chambers (e.g., proton transfer tubes), and/or ion mobility analyzers. It is well known that ion molecule reaction rate constants frequently reach or exceed the collision limit obtained from kinetic gas theory. Thus with a typical dwell time of ions within the above mentioned devices in the ms range, chemical transformation reactions are likely to occur. In other words, individual ions change critical parameters such as mass, mobility, and chemical reactivity en passage to the analyzer, which naturally strongly affects their trajectories. The RS method simulates elementary reaction events of individual ions reflecting the behavior of a large ensemble by a representative set of simulated reacting particles. The simulation of the proton bound water cluster reactant ion peak (RIP) in ion mobility spectrometry (IMS) was chosen as a benchmark problem. For this purpose, the RIP was experimentally determined as a function of the background water concentration present in the IMS drift tube. It is shown that simulation and experimental data are in very good agreement, demonstrating the validity of the method.

  3. Differential Mobility Spectrometer with Spatial Ion Detector and Methods Related Thereto

    Science.gov (United States)

    Duong, Tuan A. (Inventor); Kanik, Isik (Inventor); Duong, Vu A. (Inventor)

    2013-01-01

    Differential mobility spectrometer with spatial ion detector and methods related thereto are disclosed. The use of one or more spatial detector within differential mobility spectrometry can provide for the identification and separation of ions with similar mobility and mass.

  4. Method of multiplexed analysis using ion mobility spectrometer

    Science.gov (United States)

    Belov, Mikhail E.; Smith, Richard D.

    2009-06-02

    A method for analyzing analytes from a sample introduced into a Spectrometer by generating a pseudo random sequence of a modulation bins, organizing each modulation bin as a series of submodulation bins, thereby forming an extended pseudo random sequence of submodulation bins, releasing the analytes in a series of analyte packets into a Spectrometer, thereby generating an unknown original ion signal vector, detecting the analytes at a detector, and characterizing the sample using the plurality of analyte signal subvectors. The method is advantageously applied to an Ion Mobility Spectrometer, and an Ion Mobility Spectrometer interfaced with a Time of Flight Mass Spectrometer.

  5. Coarse grained model for calculating the ion mobility of hydrocarbons

    Science.gov (United States)

    Kuroboshi, Y.; Takemura, K.

    2016-12-01

    Hydrocarbons are widely used as insulating compounds. However, their fundamental characteristics in conduction phenomena are not completely understood. A great deal of effort is required to determine reasonable ionic behavior from experiments because of their complicated procedures and tight controls of the temperature and the purity of the liquids. In order to understand the conduction phenomena, we have theoretically calculated the ion mobilities of hydrocarbons and investigated their characteristics using the coarse grained model in molecular dynamics simulations. We assumed a molecule of hydrocarbons to be a bead and simulated its dependence on the viscosity, electric field, and temperature. Furthermore, we verified the suitability of the conformation, scale size, and long-range interactions for the ion mobility. The results of the simulations show that the ion mobility values agree reasonably well with the values from Walden's rule and depend on the viscosity but not on the electric field. The ion mobility and self-diffusion coefficient exponentially increase with increasing temperature, while the activation energy decreases with increasing molecular size. These values and characteristics of the ion mobility are in reasonable agreement with experimental results. In the future, we can understand not only the ion mobilies of hydrocarbons in conduction, but also we can predict general phenomena in electrochemistry with molecular dynamics simulations.

  6. Tandem ion mobility spectrometry coupled to laser excitation.

    Science.gov (United States)

    Simon, Anne-Laure; Chirot, Fabien; Choi, Chang Min; Clavier, Christian; Barbaire, Marc; Maurelli, Jacques; Dagany, Xavier; MacAleese, Luke; Dugourd, Philippe

    2015-09-01

    This manuscript describes a new experimental setup that allows to perform tandem ion mobility spectrometry (IMS) measurements and which is coupled to a high resolution time-of-flight mass spectrometer. It consists of two 79 cm long drift tubes connected by a dual ion funnel assembly. The setup was built to permit laser irradiation of the ions in the transfer region between the two drift tubes. This geometry allows selecting ions according to their ion mobility in the first drift tube, to irradiate selected ions, and examine the ion mobility of the product ions in the second drift tube. Activation by collision is possible in the same region (between the two tubes) and between the second tube and the time-of-flight. IMS-IMS experiments on Ubiquitin are reported. We selected a given isomer of charge state +7 and explored its structural rearrangement following collisional activation between the two drift tubes. An example of IMS-laser-IMS experiment is reported on eosin Y, where laser irradiation was used to produce radical ions by electron photodetachment starting from doubly deprotonated species. This allowed measuring the collision cross section of the radical photo-product, which cannot be directly produced with an electrospray source.

  7. Advanced stored waveform inverse Fourier transform technique for a matrix-assisted laser desorption/ionization quadrupole ion trap mass spectrometer.

    Science.gov (United States)

    Doroshenko, V M; Cotter, R J

    1996-01-01

    The stored waveform inverse Fourier transform (SWIFT) technique is used for broadband excitation of ions in an ion-trap mass spectrometer to perform mass-selective accumulation, isolation, and fragmentation of peptide ions formed by matrix-assisted laser desorption/ionization. Unit mass resolution is achieved for isolation of ions in the range of m/z up to 1300 using a two-step isolation technique with stretched-in-time narrow band SWIFT pulses at the second stage. The effect of 'stretched-in-time' waveforms is similar to that observed previously for mass-scan-rate reduction. The asymmetry phenomenon resulting from the stretched ion-trap electrode geometry is observed during application of normal and time-reversed waveforms and is similar to the asymmetry effects observed for forward and reverse mass scans in the resonance ejection mode. Mass-selective accumulation of ions from multiple laser shots was accomplished using a method described earlier that involves increasing the trapping voltage during ion introduction for more efficient trapping of ions.

  8. Detection of Biological Materials Using Ion Mobility Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rodacy, P.J.; Sterling, J.P.; Butler, M.A.

    1999-03-01

    Traditionally, Ion Mobility Spectroscopy has been used to examine ions of relatively low molecular weight and high ion mobility. In recent years, however, biomolecules such as bradykinin, cytochrome c, bovine pancreatic trypsin inhibitor (BPTI), apomyoglobin, and lysozyme, have been successfully analyzed, but studies of whole bio-organisms have not been performed. In this study an attempt was made to detect and measure the mobility of two bacteriophages, {lambda}-phage and MS2 using electrospray methods to inject the viruses into the ion mobility spectrometer. Using data from Yeh, et al., which makes a comparison between the diameter of non-biologic particles and the specific particle mobility, the particle mobility for the MS2 virus was estimated to be 10{sup {minus}2} cm{sup 2}/volt-sec. From this mobility the drift time of these particles in our spectrometer was calculated to be approximately 65 msec. The particle mobility for the {lambda}-phage virus was estimated to be 10{sup {minus}3} cm{sup 2}/volt-sec. which would result in a drift time of 0.7 sec. Spectra showing the presence of a viral peak at the expected drift time were not observed. However, changes in the reactant ion peak that could be directly attributed to the presence of the viruses were observed. Virus clustering, excessive collisions, and the electrospray injection method limited the performance of this IMS. However, we believe that an instrument specifically designed to analyze such bioagents and utilizing other injection and ionization methods will succeed in directly detecting viruses and bacteria.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  10. Mobility-resolved ion selection in uniform drift field ion mobility spectrometry/mass spectrometry: dynamic switching in structures for lossless ion manipulations.

    Science.gov (United States)

    Webb, Ian K; Garimella, Sandilya V B; Tolmachev, Aleksey V; Chen, Tsung-Chi; Zhang, Xinyu; Cox, Jonathan T; Norheim, Randolph V; Prost, Spencer A; LaMarche, Brian; 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 the efficient switching of ions between a linear path and a 90-degree bend. By controlling switching times, ions can be efficiently directed 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 of, for example, the selection of specific mobilities for storage and accumulation, and the key component of modules for the assembly of SLIM devices enabling much more complex sequences of ion manipulations.

  11. A new ion mobility-linear ion trap instrument for complex mixture analysis.

    Science.gov (United States)

    Donohoe, Gregory C; Maleki, Hossein; Arndt, James R; Khakinejad, Mahdiar; Yi, Jinghai; McBride, Carroll; Nurkiewicz, Timothy R; Valentine, Stephen J

    2014-08-19

    A new instrument that couples a low-pressure drift tube with a linear ion trap mass spectrometer is demonstrated for complex mixture analysis. The combination of the low-pressure separation with the ion trapping capabilities provides several benefits for complex mixture analysis. These include high sensitivity, unique ion fragmentation capabilities, and high reproducibility. Even though the gas-phase separation and the mass measurement steps are each conducted in an ion filtering mode, detection limits for mobility-selected peptide ions are in the tens of attomole range. In addition to ion separation, the low-pressure drift tube can be used as an ion fragmentation cell yielding mobility-resolved fragment ions that can be subsequently analyzed by multistage tandem mass spectrometry (MS(n)) methods in the ion trap. Because of the ion trap configuration, these methods can be comprised of any number (limited by ion signal) of collision-induced dissociation (CID) and electron transfer dissociation (ETD) processes. The high reproducibility of the gas-phase separation allows for comparison of two-dimensional ion mobility spectrometry (IMS)-MS data sets in a pixel-by-pixel fashion without the need for data set alignment. These advantages are presented in model analyses representing mixtures encountered in proteomics and metabolomics experiments.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hunka Deborah Elaine; Austin, Daniel E.

    2005-07-01

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

  13. Spatial Ion Peak Compression and its Utility in Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Garimella, Sandilya V. B.; Ibrahim, Yehia M.; Tang, Keqi; Webb, Ian K.; Baker, Erin S.; Tolmachev, Aleksey V.; Chen, Tsung-Chi; Anderson, Gordon A.; Smith, Richard D.

    2016-04-06

    A novel concept for ion spatial peak compression is described, and discussed primarily in the context of ion mobility spectrometry (IMS). Using theoretical and numerical methods, the effects of using non-constant (e.g., linearly varying) electric fields on ion distributions (e.g., an ion mobility peak) is evaluated both in the physical and temporal domains. The application of linearly decreasing electric field in conjunction with conventional drift field arrangements is shown to lead to a reduction in IMS physical peak width. When multiple ion packets in a selected mobility window are simultaneously subjected to such fields, there is ion packet compression, i.e., a reduction in peak widths of all species. This peak compression occurs with a modest reduction of resolution, but which can be quickly recovered as ions drift in a constant field after the compression event. Compression also yields a significant increase in peak intensities. In addition, approaches for peak compression in traveling wave IMS are also discussed. Ion mobility peak compression can be particularly useful for mitigating diffusion driven peak spreading over very long path length separations (e.g., in cyclic multi-pass arrangements), and for achieving higher S/N and IMS resolution over a selected mobility range.

  14. Corona discharge ion mobility spectrometry at reduced pressures

    Science.gov (United States)

    Tabrizchi, Mahmoud; Rouholahnejad, Fereshteh

    2004-11-01

    Ion mobility spectrometers (IMSs) normally operate at ambient pressure. In this work an IMS cell has been designed and constructed to allow the pressure to be reduced inside the IMS cell. In this cell, corona discharge was employed as the ionization source. Reducing pressure affected both the discharge and the performance of the IMS. The discharge current was observed to increase with reducing pressure while the ignition potential decreased. The ion current received at the collector plate was also increased about 50 times when the pressure was reduced from ambient pressure to 15 Torr. The higher ion current can lead to an extended dynamic range. IMS spectra were recorded at various pressures and the results show that the drift times shift perfectly linear with pressure. This suggests that unlike temperature, pressure correction for ion mobility spectra is as simple as multiplying the drift times by a factor of 760/P.

  15. The dressed mobile atoms and ions

    CERN Document Server

    Amour, B; Guillot, L

    2005-01-01

    We consider free atoms and ions in $\\R^3$ interacting with the quantized electromagnetic field. Because of the translation invariance we consider the reduced hamiltonian associated with the total momentum. After introducing an ultraviolet cutoff we prove that the reduced hamiltonian for atoms has a ground state if the coupling constant and the total momentum are sufficiently small. In the case of ions an extra infrared regularization is needed. We also consider the case of the hydrogen atom in a constant magnetic field. Finally we determine the absolutely continuous spectrum of the reduced hamiltonian. \\end{abstract}

  16. Squeezing of Ion Populations and Peaks in Traveling Wave Ion Mobility Separations and Structures for Lossless Ion Manipulations using Compression Ratio Ion Mobility Programming

    Energy Technology Data Exchange (ETDEWEB)

    Garimella, Venkata BS; Hamid, Ahmed M.; Deng, Liulin; Ibrahim, Yehia M.; Webb, Ian K.; Baker, Erin M.; Prost, Spencer A.; Norheim, Randolph V.; Anderson, Gordon A.; Smith, Richard D.

    2016-11-02

    In this work, we report an approach for spatial and temporal gas phase ion population manipulation, and demonstrate its application for the collapse of the ion distributions in ion mobility (IM) separations into tighter packets providing higher sensitivity measurements in conjunction with mass spectrometry (MS). We do this for ions moving from a conventionally traveling wave (TW)-driven region to a region where the TW is intermittently halted or ‘stuttered’. This approach causes the ion packets spanning a number of TW-created traveling traps (TT) to be redistributed into fewer TT, resulting in spatial compression. The degree of spatial compression is controllable and determined by the ratio of stationary time of the TW in the second region to its moving time. This compression ratio ion mobility programming (CRIMP) approach has been implemented using Structures for Lossless Ion Manipulations (SLIM) in conjunction with MS. CRIMP with the SLIM-MS platform is shown to provide increased peak intensities, reduced peak widths, and improved S/N ratios with MS detection. CRIMP also provides a foundation for extremely long path length and multi-pass IM separations in SLIM providing greatly enhanced IM resolution by reducing the detrimental effects of diffusional peak broadening due to increasing peak widths.

  17. Squeezing of Ion Populations and Peaks in Traveling Wave Ion Mobility Separations and Structures for Lossless Ion Manipulations Using Compression Ratio Ion Mobility Programming.

    Science.gov (United States)

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

    2016-12-06

    In this work we report an approach for spatial and temporal gas-phase ion population manipulation, wherein we collapse ion distributions in ion mobility (IM) separations into tighter packets providing higher sensitivity measurements in conjunction with mass spectrometry (MS). We do this for ions moving from a conventional traveling wave (TW)-driven region to a region where the TW is intermittently halted or "stuttered". This approach causes the ion packets spanning a number of TW-created traveling traps (TT) to be redistributed into fewer TT, resulting in spatial compression. The degree of spatial compression is controllable and determined by the ratio of stationary time of the TW in the second region to its moving time. This compression ratio ion mobility programming (CRIMP) approach has been implemented using "structures for lossless ion manipulations" (SLIM) in conjunction with MS. CRIMP with the SLIM-MS platform is shown to provide increased peak intensities, reduced peak widths, and improved signal-to-noise (S/N) ratios with MS detection. CRIMP also provides a foundation for extremely long path length and multipass IM separations in SLIM providing greatly enhanced IM resolution by reducing the detrimental effects of diffusional peak broadening and increasing peak widths.

  18. Nonlinear Waveforms for Ion-Acoustic Waves in Weakly Relativistic Plasma of Warm Ion-Fluid and Isothermal Electrons

    Directory of Open Access Journals (Sweden)

    S. A. El-Wakil

    2012-01-01

    Full Text Available The reductive perturbation method has been employed to derive the Korteweg-de Vries (KdV equation for small- but finite-amplitude electrostatic ion-acoustic waves in weakly relativistic plasma consisting of warm ions and isothermal electrons. An algebraic method with computerized symbolic computation is applied in obtaining a series of exact solutions of the KdV equation. Numerical studies have been made using plasma parameters which reveal different solutions, that is, bell-shaped solitary pulses, rational pulses, and solutions with singularity at finite points, which called “blowup” solutions in addition to the propagation of an explosive pulses. The weakly relativistic effect is found to significantly change the basic properties (namely, the amplitude and the width of the ion-acoustic waves. The result of the present investigation may be applicable to some plasma environments, such as ionosphere region.

  19. Utilizing Ion-Mobility Data to Estimate Molecular Masses

    Science.gov (United States)

    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.

  20. Mobility-Selected Ion Trapping and Enrichment Using Structures for Lossless Ion Manipulations.

    Science.gov (United States)

    Chen, Tsung-Chi; Ibrahim, Yehia M; Webb, Ian K; Garimella, Sandilya V B; Zhang, Xing; Hamid, Ahmed M; Deng, Liulin; Karnesky, William E; Prost, Spencer A; Sandoval, Jeremy A; Norheim, Randolph V; Anderson, Gordon A; Tolmachev, Aleksey V; Baker, Erin S; Smith, Richard D

    2016-02-02

    The integration of ion mobility spectrometry (IMS) with mass spectrometry (MS) and the ability to trap ions in IMS-MS measurements is of great importance for performing reactions, accumulating ions, and increasing analytical measurement sensitivity. The development of Structures for Lossless Ion Manipulations (SLIM) offers the potential for ion manipulations in an extended and more effective manner, while opening opportunities for many more complex sequences of manipulations. Here, we demonstrate an ion separation and trapping module and a method based upon SLIM that consists of a linear mobility ion drift region, a switch/tee and a trapping region that allows the isolation and accumulation of mobility-separated species. The operation and optimization of the SLIM switch/tee and trap are described and demonstrated for the enrichment of the low abundance ions. A linear improvement in ion intensity was observed with the number of trapping/accumulation events using the SLIM trap, illustrating its potential for enhancing the sensitivity of low abundance or targeted species.

  1. Variables Affecting the Internal Energy of Peptide Ions During Separation by Differential Ion Mobility Spectrometry

    Science.gov (United States)

    Santiago, Brandon G.; Campbell, Matthew T.; Glish, Gary L.

    2017-10-01

    Differential ion mobility spectrometry (DIMS) devices separate ions on the basis of differences in ion mobility in low and high electric fields, and can be used as a stand-alone analytical method or as a separation step before further analysis. As with other ion mobility separation techniques, the ability of DIMS separations to retain the structural characteristics of analytes has been of concern. For DIMS separations, this potential loss of ion structure originates from the fact that the separations occur at atmospheric pressure and the ions, during their transit through the device, undergo repeated collisions with the DIMS carrier gas while being accelerated by the electric field. These collisions have the ability to increase the internal energy distribution of the ions, which can cause isomerization or fragmentation. The increase in internal energy of the ions is based on a number of variables, including the dispersion field and characteristics of the carrier gas such as temperature and composition. The effects of these parameters on the intra-DIMS fragmentation of multiply charged ions of the peptides bradykinin (RPPGFSPFR) and GLISH are discussed herein. Furthermore, similarities and differences in the internal energy deposition that occur during collisional activation in tandem mass spectrometry experiments are discussed, as the fragmentation pathways accessed by both are similar. [Figure not available: see fulltext.

  2. Polymers for Traveling Wave Ion Mobility Spectrometry Calibration

    Science.gov (United States)

    Duez, Quentin; Chirot, Fabien; Liénard, Romain; Josse, Thomas; Choi, ChangMin; Coulembier, Olivier; Dugourd, Philippe; Cornil, Jérôme; Gerbaux, Pascal; De Winter, Julien

    2017-07-01

    One of the main issues when using traveling wave ion mobility spectrometry (TWIMS) for the determination of collisional cross-section (CCS) concerns the need for a robust calibration procedure built from referent ions of known CCS. Here, we implement synthetic polymer ions as CCS calibrants in positive ion mode. Based on their intrinsic polydispersities, polymers offer in a single sample the opportunity to generate, upon electrospray ionization, numerous ions covering a broad mass range and a large CCS window for different charge states at a time. In addition, the key advantage of polymer ions as CCS calibrants lies in the robustness of their gas-phase structure with respect to the instrumental conditions, making them less prone to collisional-induced unfolding (CIU) than protein ions. In this paper, we present a CCS calibration procedure using sodium cationized polylactide and polyethylene glycol, PLA and PEG, as calibrants with reference CCS determined on a home-made drift tube. Our calibration procedure is further validated by testing the polymer calibration to determine CCS of numerous different ions for which CCS are reported in the literature. [Figure not available: see fulltext.

  3. Analysis of a series of chlorogenic acid isomers using differential ion mobility and tandem mass spectrometry.

    Science.gov (United States)

    Willems, Jamie L; Khamis, Mona M; Mohammed Saeid, Waleed; Purves, Randy W; Katselis, George; Low, Nicholas H; El-Aneed, Anas

    2016-08-24

    Chlorogenic acids are among the most abundant phenolics found in the human diet. Of these, the mono-caffeoylquinic acids are the predominant phenolics found in fruits, such as apples and pears, and products derived from them. In this research, a comprehensive study of the electrospray ionization (ESI) tandem mass spectrometric (MS/MS) dissociation behavior of the three most common mono-caffeoylquinic acids, namely 5-O-caffeoylquinic acid (5-CQA), 3-O-caffeoylquinic acid (3-CQA) and 4-O-caffeoylquinic acid (4-CQA), were determined using both positive and negative ionization. All proposed structures of the observed product ions were confirmed with second-generation MS(3) experiments. Similarities and differences between the dissociation pathways in the positive and negative ion modes are discussed, confirming the proposed structures and the established MS/MS fingerprints. MS/MS dissociation was primarily driven via the cleavage of the ester bond linking the quinic acid moiety to the caffeic acid moiety within tested molecules. Despite being structural isomers with the same m/z values and dissociation behaviors, the MS/MS data in the negative ion mode was able to differentiate the three isomers based on ion intensity for the major product ions, observed at m/z 191, 179 and 173. This differentiation was consistent among various MS instruments. In addition, ESI coupled with high-field asymmetric waveform ion mobility spectrometry-mass spectrometry (ESI-FAIMS-MS) was employed for the separation of these compounds for the first time. By combining MS/MS data and differential ion mobility, a method for the separation and identification of mono-caffeoylquinic in apple/pear juice samples was developed with a run time of less than 1 min. It is envisaged that this methodology could be used to identify pure juices based on their chlorogenic acid profile (i.e., metabolomics), and could also be used to detect juice-to-juice adulteration (e.g., apple juice addition to pear juice).

  4. Micro faraday-element array detector for ion mobility spectroscopy

    Science.gov (United States)

    Gresham, Christopher A.; Rodacy, Phillip J.; Denton, M. Bonner; Sperline, Roger

    2004-10-26

    An ion mobility spectrometer includes a drift tube having a collecting surface covering a collecting area at one end of the tube. The surface comprises a plurality of closely spaced conductive elements on a non-conductive substrate, each conductive element being electrically insulated from each other element. A plurality of capacitive transimpedance amplifiers (CTIA) adjacent the collecting surface are electrically connected to the plurality of elements, so charge from an ion striking an element is transferred to the capacitor of the connected CTIA. A controller counts the charge on the capacitors over a period of time.

  5. Experimental simulation of negative ion chemistry in Martian atmosphere using ion mobility spectrometry-mass spectrometry

    Science.gov (United States)

    Sabo, Martin; Lichvanová, Zuzana; Orszagh, Juraj; Mason, Nigel; Matejčík, Štefan

    2014-08-01

    We have studied the formation of negative ions in a negative Corona Discharge (CD) fed by CO2/N2 mixtures (with 0, 2, 4, 6, 8, 10% N2) using the technique of ion mobility spectrometry-orthogonal acceleration time of flight mass spectrometry (IMS-oaTOF). The composition of the negative ions was found to be dependent on the initial gas composition, the gas flow regime, the concentrations of neutral reactive species formed in the discharge and the trace amounts on water in the gases were found to play an important role in the negative ions formation. In a pure CO2 discharge operating under standard gas flow conditions of IMS (associated with strong interaction of ions with neutral reactive species formed in discharge) the ions CO3 - (H2O) and CO4 -(H2O) dominated the measured negative ion spectrum while in CO2/N2 mixtures NO3 -(H2O) n , NO3 -(HNO3) ( n = 0, 1) ions prevailed. In the case of reverse gas flow regime (low interaction of ions with neutral reactive species formed in discharge), the negative ions detected were O2 -(H2O) n , and O2 -.CO2(H2O) n both in pure CO2 and N2/CO2 mixtures. The spectra of negative ions recorded for a gas mixture containing 4% N2 in CO2 were compared with theoretical predictions of negative ion composition in the lower atmosphere of Mars.

  6. Comprehensive mapping of O-glycosylation in flagellin from Campylobacter jejuni 11168: A multienzyme differential ion mobility mass spectrometry approach.

    Science.gov (United States)

    Ulasi, Gloria N; Creese, Andrew J; Hui, Sam Xin; Penn, Charles W; Cooper, Helen J

    2015-08-01

    Glycosylation of flagellin is essential for the virulence of Campylobacter jejuni, a leading cause of bacterial gastroenteritis. Here, we demonstrate comprehensive mapping of the O-glycosylation of flagellin from Campylobacter jejuni 11168 by use of a bottom-up proteomics approach that incorporates differential ion mobility spectrometry (also known as high field asymmetric waveform ion mobility spectrometry or FAIMS) together with proteolysis with proteinase K. Proteinase K provides complementary sequence coverage to that achieved following trypsin proteolysis. The use of FAIMS increased the number of glycopeptides identified. Novel glycans for this strain were identified (pseudaminic acid and either acetamidino pseudaminic acid or legionaminic acid), as were novel glycosylation sites: Thr208, Ser343, Ser348, Ser349, Ser395, Ser398, Ser423, Ser433, Ser436, Ser445, Ser448, Ser451, Ser452, Ser454, Ser457 and Thr465. Multiply glycosylated peptides were observed, as well as variation at individual residues in the nature of the glycan and its presence or absence. Such extreme heterogeneity in the pattern of glycosylation has not been reported previously, and suggests a novel dimension in molecular variation within a bacterial population that may be significant in persistence of the organism in its natural environment. These results demonstrate the usefulness of differential ion mobility in proteomics investigations of PTMs.

  7. Ion mobility spectrometry for detection of skin volatiles

    OpenAIRE

    Ruzsanyi, Veronika; Mochalski, Pawel; Schmid, Alex; Wiesenhofer, Helmut; Klieber, Martin; Hinterhuber, Hartmann; Amann, Anton

    2012-01-01

    Volatile organic compounds (VOCs) released by humans through their skin were investigated in near real time using ion mobility spectrometry after gas chromatographic separation with a short multi-capillary column. VOCs typically found in a small nitrogen flow covering the skin are 3-methyl-2-butenal, 6-methylhept-5-en-2-one, sec-butyl acetate, benzaldehyde, octanal, 2-ethylhexanol, nonanal and decanal at volume fractions in the low part per billion-(ppb) range. The technique presented here ma...

  8. Ion mobility and transport barriers in the tokamak plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, H.; Hazeltine, R.D.; Valanju, P.M. [Texas Univ., Austin, TX (United States). Inst. for Fusion Studies; Zhang, Y.Z. [International Centre for Theoretical Physics, Trieste (Italy)

    1993-06-01

    The character of charged particle motion in an axisymmetric toroidal system with a constant radial electric field is investigated both analytically and numerically. Ion radial mobility caused by the combined effects of the radial electric field and charge exchange is found. A simple moment argument in the banana regime matches the simulation results well. Relation of present work and high confinement (H-mode) experiment is also discussed.

  9. Ion mobility derived collision cross sections to support metabolomics applications.

    Science.gov (United States)

    Paglia, Giuseppe; Williams, Jonathan P; Menikarachchi, Lochana; Thompson, J Will; Tyldesley-Worster, Richard; Halldórsson, Skarphédinn; Rolfsson, Ottar; Moseley, Arthur; Grant, David; Langridge, James; Palsson, Bernhard O; Astarita, Giuseppe

    2014-04-15

    Metabolomics is a rapidly evolving analytical approach in life and health sciences. The structural elucidation of the metabolites of interest remains a major analytical challenge in the metabolomics workflow. Here, we investigate the use of ion mobility as a tool to aid metabolite identification. Ion mobility allows for the measurement of the rotationally averaged collision cross-section (CCS), which gives information about the ionic shape of a molecule in the gas phase. We measured the CCSs of 125 common metabolites using traveling-wave ion mobility-mass spectrometry (TW-IM-MS). CCS measurements were highly reproducible on instruments located in three independent laboratories (RSD red blood cells using ultra performance liquid chromatography (UPLC) coupled with TW-IM-MS. The mean RSD was cells, an in vitro model used to study cancer development. Experimentally determined and computationally derived CCS values were used as orthogonal analytical parameters in combination with retention time and accurate mass information to confirm the identity of key metabolites potentially involved in cancer. Thus, our results indicate that adding CCS data to searchable databases and to routine metabolomics workflows will increase the identification confidence compared to traditional analytical approaches.

  10. Dynamic multiplexed analysis method using ion mobility spectrometer

    Science.gov (United States)

    Belov, Mikhail E [Richland, WA

    2010-05-18

    A method for multiplexed analysis using ion mobility spectrometer in which the effectiveness and efficiency of the multiplexed method is optimized by automatically adjusting rates of passage of analyte materials through an IMS drift tube during operation of the system. This automatic adjustment is performed by the IMS instrument itself after determining the appropriate levels of adjustment according to the method of the present invention. In one example, the adjustment of the rates of passage for these materials is determined by quantifying the total number of analyte molecules delivered to the ion trap in a preselected period of time, comparing this number to the charge capacity of the ion trap, selecting a gate opening sequence; and implementing the selected gate opening sequence to obtain a preselected rate of analytes within said IMS drift tube.

  11. Nonlinear wavelet compression of ion mobility spectra from ion mobility spectrometers mounted in an unmanned aerial vehicle.

    Science.gov (United States)

    Cao, Libo; Harrington, Peter de B; Harden, Charles S; McHugh, Vincent M; Thomas, Martin A

    2004-02-15

    Linear and nonlinear wavelet compression of ion mobility spectrometry (IMS) data are compared and evaluated. IMS provides low detection limits and rapid response for many compounds. Nonlinear wavelet compression of ion mobility spectra reduced the data to 4-5% of its original size, while eliminating artifacts in the reconstructed spectra that occur with linear compression, and the root-mean-square reconstruction error was 0.17-0.20% of the maximum intensity of the uncompressed spectra. Furthermore, nonlinear wavelet compression precisely preserves the peak location (i.e., drift time). Small variations in peak location may occur in the reconstructed spectra that were linearly compressed. A method was developed and evaluated for optimizing the compression. The compression method was evaluated with in-flight data recorded from ion mobility spectrometers mounted in an unmanned aerial vehicle (UAV). Plumes of dimethyl methylphosphonate were disseminated for interrogation by the UAV-mounted IMS system. The daublet 8 wavelet filter exhibited the best performance for these evaluations.

  12. Treatise on the measurement of molecular masses with ion mobility spectrometry.

    Science.gov (United States)

    Valentine, Stephen J; Clemmer, David E

    2009-07-15

    The ability to separate isotopes by high-resolution ion mobility spectrometry techniques is considered as a direct means for determining mass at ambient pressures. Calculations of peak shapes from the transport equation show that it should be possible to separate isotopes for low-mass ions (ion mobility analyzers. The mass accuracy associated with this isotopic separation approach based on ion mobility separation is considered. Finally, we predict several isotopes that should be separable.

  13. External Second Gate-Fourier Transform Ion Mobility Spectrometry.

    Energy Technology Data Exchange (ETDEWEB)

    Tarver, Edward E., III

    2005-01-01

    Ion mobility spectrometry (IMS) is recognized as one of the most sensitive and versatile techniques for the detection of trace levels of organic vapors. IMS is widely used for detecting contraband narcotics, explosives, toxic industrial compounds and chemical warfare agents. Increasing threat of terrorist attacks, the proliferation of narcotics, Chemical Weapons Convention treaty verification as well as humanitarian de-mining efforts has mandated that equal importance be placed on the analysis time as well as the quality of the analytical data. (1) IMS is unrivaled when both speed of response and sensitivity has to be considered. (2) With conventional (signal averaging) IMS systems the number of available ions contributing to the measured signal to less than 1%. Furthermore, the signal averaging process incorporates scan-to-scan variations decreasing resolution. With external second gate Fourier Transform ion mobility spectrometry (FT-IMS), the entrance gate frequency is variable and can be altered in conjunction with other data acquisition parameters to increase the spectral resolution. The FT-IMS entrance gate operates with a 50% duty cycle and so affords a 7 to 10-fold increase in sensitivity. Recent data on high explosives are presented to demonstrate the parametric optimization in sensitivity and resolution of our system.

  14. Ion mobility spectrometry for food quality and safety.

    Science.gov (United States)

    Vautz, W; Zimmermann, D; Hartmann, M; Baumbach, J I; Nolte, J; Jung, J

    2006-11-01

    Ion mobility spectrometry is known to be a fast and sensitive technique for the detection of trace substances, and it is increasingly in demand not only for protection against explosives and chemical warfare agents, but also for new applications in medical diagnosis or process control. Generally, a gas phase sample is ionized by help of ultraviolet light, ss-radiation or partial discharges. The ions move in a weak electrical field towards a detector. During their drift they collide with a drift gas flowing in the opposite direction and, therefore, are slowed down depending on their size, shape and charge. As a result, different ions reach the detector at different drift times, which are characteristic for the ions considered. The number of ions reaching the detector are a measure of the concentration of the analyte. The method enables the identification and quantification of analytes with high sensitivity (ng l(-1) range). The selectivity can even be increased - as necessary for the analyses of complex mixtures - using pre-separation techniques such as gas chromatography or multi-capillary columns. No pre-concentration of the sample is necessary. Those characteristics of the method are preserved even in air with up to a 100% relative humidity rate. The suitability of the method for application in the field of food quality and safety - including storage, process and quality control as well as the characterization of food stuffs - was investigated in recent years for a number of representative examples, which are summarized in the following, including new studies as well: (1) the detection of metabolites from bacteria for the identification and control of their growth; (2) process control in food production - beer fermentation being an example; (3) the detection of the metabolites of mould for process control during cheese production, for quality control of raw materials or for the control of storage conditions; (4) the quality control of packaging materials during

  15. Misfolded amyloid ion channels present mobile beta-sheet subunits in contrast to conventional ion channels.

    Science.gov (United States)

    Jang, Hyunbum; Arce, Fernando Teran; Capone, Ricardo; Ramachandran, Srinivasan; Lal, Ratnesh; Nussinov, Ruth

    2009-12-02

    In Alzheimer's disease, calcium permeability through cellular membranes appears to underlie neuronal cell death. It is increasingly accepted that calcium permeability involves toxic ion channels. We modeled Alzheimer's disease ion channels of different sizes (12-mer to 36-mer) in the lipid bilayer using molecular dynamics simulations. Our Abeta channels consist of the solid-state NMR-based U-shaped beta-strand-turn-beta-strand motif. In the simulations we obtain ion-permeable channels whose subunit morphologies and shapes are consistent with electron microscopy/atomic force microscopy. In agreement with imaged channels, the simulations indicate that beta-sheet channels break into loosely associated mobile beta-sheet subunits. The preferred channel sizes (16- to 24-mer) are compatible with electron microscopy/atomic force microscopy-derived dimensions. Mobile subunits were also observed for beta-sheet channels formed by cytolytic PG-1 beta-hairpins. The emerging picture from our large-scale simulations is that toxic ion channels formed by beta-sheets spontaneously break into loosely interacting dynamic units that associate and dissociate leading to toxic ionic flux. This sharply contrasts intact conventional gated ion channels that consist of tightly interacting alpha-helices that robustly prevent ion leakage, rather than hydrogen-bonded beta-strands. The simulations suggest why conventional gated channels evolved to consist of interacting alpha-helices rather than hydrogen-bonded beta-strands that tend to break in fluidic bilayers. Nature designs folded channels but not misfolded toxic channels.

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

    Science.gov (United States)

    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.

  17. Determination of Aflatoxins G and GUsing Ion Mobility Spectrometry

    Directory of Open Access Journals (Sweden)

    ALI SHEIBANI

    2012-12-01

    Full Text Available This work describes a rapid and sensitive ion mobility spectrometry method for the determination of aflatoxins G12 (AFG1 and AFG2. The effective instrumental parameters were investigated and optimized. After optimizing, the calibration curves for AFG1 and AFG2 were linear in the range of 1 to 300 ng. Relative standard deviation was 8 % and limit of detection was 0.5 ng. The capability of the proposed method was evaluated for the determination of AFG in spiked pistachio nut as a real sample that satisfactory results were obtained.

  18. Ion mobility spectrometry for detection of skin volatiles.

    Science.gov (United States)

    Ruzsanyi, Veronika; Mochalski, Pawel; Schmid, Alex; Wiesenhofer, Helmut; Klieber, Martin; Hinterhuber, Hartmann; Amann, Anton

    2012-12-12

    Volatile organic compounds (VOCs) released by humans through their skin were investigated in near real time using ion mobility spectrometry after gas chromatographic separation with a short multi-capillary column. VOCs typically found in a small nitrogen flow covering the skin are 3-methyl-2-butenal, 6-methylhept-5-en-2-one, sec-butyl acetate, benzaldehyde, octanal, 2-ethylhexanol, nonanal and decanal at volume fractions in the low part per billion-(ppb) range. The technique presented here may contribute to elucidating some physiological processes occurring in the human skin.

  19. Electron attachment and ion mobility in hydrocarbons and related systems

    Energy Technology Data Exchange (ETDEWEB)

    Bakale, G.

    1988-01-01

    During the last two decades, a firm base for the emerging field of liquid state electronics (LSE) has developed through studies of the transport and reaction properties of excess electrons in a variety of liquid-phase systems. Pulse-conductivity techniques were used in many of these studies to measure the mobilities of electrons and ions in pure liquids as well as the rate constants of electron attachment to a wide variety of electron-accepting solutes. Results obtained through such studies have interdisciplinary implications that are described in the discussion that follows which includes examples of the contributions of LSE to physics, chemistry and biology. 42 refs.

  20. Shutterless ion mobility spectrometer with fast pulsed electron source

    Science.gov (United States)

    Bunert, E.; Heptner, A.; Reinecke, T.; Kirk, A. T.; Zimmermann, S.

    2017-02-01

    Ion mobility spectrometers (IMS) are devices for fast and very sensitive trace gas analysis. The measuring principle is based on an initial ionization process of the target analyte. Most IMS employ radioactive electron sources, such as 63Ni or 3H. These radioactive materials have the disadvantage of legal restrictions and the electron emission has a predetermined intensity and cannot be controlled or disabled. In this work, we replaced the 3H source of our IMS with 100 mm drift tube length with our nonradioactive electron source, which generates comparable spectra to the 3H source. An advantage of our emission current controlled nonradioactive electron source is that it can operate in a fast pulsed mode with high electron intensities. By optimizing the geometric parameters and developing fast control electronics, we can achieve very short electron emission pulses for ionization with high intensities and an adjustable pulse width of down to a few nanoseconds. This results in small ion packets at simultaneously high ion densities, which are subsequently separated in the drift tube. Normally, the required small ion packet is generated by a complex ion shutter mechanism. By omitting the additional reaction chamber, the ion packet can be generated directly at the beginning of the drift tube by our pulsed nonradioactive electron source with only slight reduction in resolving power. Thus, the complex and costly shutter mechanism and its electronics can also be omitted, which leads to a simple low-cost IMS-system with a pulsed nonradioactive electron source and a resolving power of 90.

  1. Broad Separation of Isomeric Lipids by High-Resolution Differential Ion Mobility Spectrometry with Tandem Mass Spectrometry

    Science.gov (United States)

    Bowman, Andrew P.; Abzalimov, Rinat R.; Shvartsburg, Alexandre A.

    2017-08-01

    Maturation of metabolomics has brought a deeper appreciation for the importance of isomeric identity of lipids to their biological role, mirroring that for proteoforms in proteomics. However, full characterization of the lipid isomerism has been thwarted by paucity of rapid and effective analytical tools. A novel approach is ion mobility spectrometry (IMS) and particularly differential or field asymmetric waveform IMS (FAIMS) at high electric fields, which is more orthogonal to mass spectrometry. Here we broadly explore the power of FAIMS to separate lipid isomers, and find a 75% success rate across the four major types of glycero- and phospho- lipids ( sn, chain length, double bond position, and cis/ trans). The resolved isomers were identified using standards, and (for the first two types) tandem mass spectrometry. These results demonstrate the general merit of incorporating high-resolution FAIMS into lipidomic analyses.

  2. Localization of Post-Translational Modifications in Peptide Mixtures via High-Resolution Differential Ion Mobility Separations Followed by Electron Transfer Dissociation

    Science.gov (United States)

    Baird, Matthew A.; Shvartsburg, Alexandre A.

    2016-12-01

    Precise localization of post-translational modifications (PTMs) on proteins and peptides is an outstanding challenge in proteomics. While electron transfer dissociation (ETD) has dramatically advanced PTM analyses, mixtures of localization variants that commonly coexist in cells often require prior separation. Although differential or field asymmetric waveform ion mobility spectrometry (FAIMS) achieves broad variant resolution, the need for standards to identify the features has limited the utility of approach. Here we demonstrate full a priori characterization of variant mixtures by high-resolution FAIMS coupled to ETD and the procedures to systematically extract the FAIMS spectra for all variants from such data.

  3. Localization of Post-Translational Modifications in Peptide Mixtures via High-Resolution Differential Ion Mobility Separations Followed by Electron Transfer Dissociation

    Science.gov (United States)

    Baird, Matthew A.; Shvartsburg, Alexandre A.

    2016-09-01

    Precise localization of post-translational modifications (PTMs) on proteins and peptides is an outstanding challenge in proteomics. While electron transfer dissociation (ETD) has dramatically advanced PTM analyses, mixtures of localization variants that commonly coexist in cells often require prior separation. Although differential or field asymmetric waveform ion mobility spectrometry (FAIMS) achieves broad variant resolution, the need for standards to identify the features has limited the utility of approach. Here we demonstrate full a priori characterization of variant mixtures by high-resolution FAIMS coupled to ETD and the procedures to systematically extract the FAIMS spectra for all variants from such data.

  4. A Device Model for Polymer Light-Emitting Diodes with Mobile Ions

    NARCIS (Netherlands)

    Jong, M.J.M. de; Blom, P.W.M.

    1996-01-01

    A model is presented for the device operation of a polymer light-emitting diode (PLED) with mobile ions. It is calculated that the low efficiency of a PLED with a high injection barrier increases as the ions migrate.

  5. Tandem Mass Spectrometry in Combination with Product Ion Mobility for the Identification of Phospholipids

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Karin A. Zemski; Barkley, Robert M.; Berry, Joseph J.; Hankin, Joseph A.; Hoyes, Emmy; Brown, Jeffery M.; Murphy, Robert C.

    2017-01-03

    Concerted tandem and traveling wave ion mobility mass spectrometry (CTS analysis) is a unique method that results in a four-dimensional data set including nominal precursor ion mass, product ion mobility, accurate mass of product ion, and ion abundance. This nontargeted lipidomics CTS approach was applied in both positive- and negative-ion mode to phospholipids present in human serum, and the data set was used to evaluate the value of product ion mobility in identifying lipids in a complex mixture. It was determined that the combination of diagnostic product ions and unique collisional cross-section values of product ions is a powerful tool in the structural identification of lipids in a complex biological sample.

  6. Achieving High Resolution Ion Mobility Separations Using Traveling Waves in Compact Multiturn Structures for Lossless Ion Manipulations

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-20

    We report on ion mobility separations (IMS) achievable using traveling waves in a Structures for Lossless Ion Manipulations (TW-SLIM) module having a 44-cm path length and sixteen 90º turns. The performance of the TW-SLIM module was evaluated for ion transmission, and ion mobility separations with different RF, TW parameters and SLIM surface gaps in conjunction with mass spectrometry. In this work TWs were created by the transient and dynamic application of DC potentials. The TW-SLIM module demonstrated highly robust performance and the ion mobility resolution achieved even with sixteen close spaced turns was comparable to a similar straight path TW-SLIM module. We found an ion mobility peak capacity of ~ 31 and peak generation rate of 780 s-1 for TW speeds of <210 m/s using the current multi-turn TW-SLIM module. The separations achieved for isomers of peptides and tetrasaccharides were found to be comparable to those from a ~ 0.9-m drift tube-based IMS-MS platform operated at the same pressure (4 torr). The combined attributes of flexible design, low voltage requirements and lossless ion transmission through multiple turns for the present TW-SLIM module provides a basis for SLIM devices capable of achieving much greater ion mobility resolutions via greatly extended ion path lengths and compact serpentine designs that do not significantly impact the instrumentation profile, a direction described in a companion manuscript.

  7. Ion mobility spectrometry and its applications in detection of chemical warfare agents.

    Science.gov (United States)

    Mäkinen, Marko A; Anttalainen, Osmo A; Sillanpää, Mika E T

    2010-12-01

    When fast detection of chemical warfare agents in the field is required, the ion mobility spectrometer may be the only suitable option. This article provides an essential survey of the different ion mobility spectrometry detection technologies. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

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

    Science.gov (United States)

    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.

  9. Li mobility in fast ion conductors followed by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, J.

    2010-07-01

    Structural features that enhance Li mobility in fast ion conductors with perovskite (Li{sub 3}xLa{sub 2}/3-xTiO{sub 3} series) and Nasicon structure (Li{sub 1}+xTi{sub 2}-xAl{sub x} (PO{sub 4}){sub 3} series) have been investigated. From the analysis of quadrupolar interactions, the local symmetry and exchange processes between structural sites occupied by lithium have been deduced to investigate local motions of lithium in conduction paths of analyzed compounds. The study of spin-lattice (T{sub 1}) and spin-spin (T{sub 2}) relaxation times made possible the analysis of the temperature dependence of Li residence times at structural sites. The comparison of these values with those deduced from conductivity (ac and dc-measurements) allowed the study of Li-motion mechanisms. The onset of long range motions requires the analysis of low frequency measurements (T{sub 2} relaxation and dc-conductivity). The non- Arrhenius behaviour, often observed in fast ion conductors, has been ascribed to order/disorder transitions. At increasing temperatures, Li motions become less correlated, producing the decrement of activation energy. In analyzed compounds, a direct measurement of diffusion coefficients has been obtained from NMR experiments performed with the pulse field gradient (PFG) technique. Finally, it is emphasized the importance of the vacancy percolation in conductivity processes. (Author)

  10. Ion mobilities in Xe/Ne and other rare-gas mixtures.

    Science.gov (United States)

    Piscitelli, D; Phelps, A V; de Urquijo, J; Basurto, E; Pitchford, L C

    2003-10-01

    The ion mobility or drift velocity data important for modeling glow discharges in rare gas mixtures are not generally available, nor are the ion-neutral scattering cross sections needed to calculate these data. In this paper we propose a set of cross sections for Xe+ and Ne+ collisions with Xe and Ne atoms. Ion mobilities at 300 K calculated using this cross section set in a Monte Carlo simulation are reported for reduced field strengths, E/N, up to 1500 x 10(-21) V m(2), in pure gases and in Xe/Ne mixtures containing 5% and 20% Xe/Ne, which are mixtures of interest for plasma display panels (PDPs). The calculated Xe+ mobilities depend strongly on the mixture composition, but the Ne+ mobility varies only slightly with increasing Xe in the mixture over the range studied here. The mobilities in pure gases compare well with available experimental values, and mobilities in gas mixtures at low E/N compare well with our recent measurements which will be published separately. Results from these calculations of ion mobilities are used to evaluate the predictions of Blanc's law and of the mixture rule proposed by Mason and Hahn [Phys. Rev. A 5, 438 (1972)] for determining the ion mobilities in mixtures from a knowledge of the mobilities in each of the pure gases. The mixture rule of Mason and Hahn is accurate to better than 10% at high field strengths over a wide range of conditions of interest for modeling PDPs. We conclude that a good estimate of ion mobilities at high E/N in Xe/Ne and other binary rare gas mixtures can be obtained using this mixture rule combined with known values of mobilities in parent gases and with the Langevin form for mobility of rare gas ions ion in other gases. This conclusion is supported by results in Ar/Ne mixtures which are also presented here.

  11. Combined corona discharge and UV photoionization source for ion mobility spectrometry.

    Science.gov (United States)

    Bahrami, Hamed; Tabrizchi, Mahmoud

    2012-08-15

    An ion mobility spectrometer is described which is equipped with two non-radioactive ion sources, namely an atmospheric pressure photoionization and a corona discharge ionization source. The two sources cannot only run individually but are additionally capable of operating simultaneously. For photoionization, a UV lamp was mounted parallel to the axis of the ion mobility cell. The corona discharge electrode was mounted perpendicular to the UV radiation. The total ion current from the photoionization source was verified as a function of lamp current, sample flow rate, and drift field. Simultaneous operation of the two ionization sources was investigated by recording ion mobility spectra of selected samples. The design allows one to observe peaks from either the corona discharge or photoionization individually or simultaneously. This makes it possible to accurately compare peaks in the ion mobility spectra from each individual source. Finally, the instrument's capability for discriminating two peaks appearing in approximately identical drift times using each individual ionization source is demonstrated.

  12. Ion Mobility Studies on the Negative Ion-Molecule Chemistry of Isoflurane and Enflurane

    Science.gov (United States)

    González-Méndez, Ramón; Watts, Peter; Howse, David C.; Procino, Immacolata; McIntyre, Henry; Mayhew, Chris A.

    2017-02-01

    In the present work we present an investigation of the negative ion-molecule chemistry of the anaesthetics isoflurane, ISOF, and enflurane, ENF, in an ion mobility spectrometry/mass spectrometry (IMS/MS), in both air and nitrogen. Hexachloroethane (HCE) was introduced in both air and nitrogen to produce Cl- as a reactant ion. This study was undertaken owing to uncertainties in the chemical processes, which lead to the cluster ions reported in other work (Eiceman et al. Anal. Chem. 61, 1093-1099, 1). In particular for ISOF the product ion observed was ISOF.Cl-, and it was suggested that the Cl- was formed by dissociative electron attachment (DEA) although there was mention of a chlorine containing contaminant. We show in this study that ISOF and ENF do not produce Cl- in an IMS system either by capture of free electrons or reaction with O2 -. This demonstrates that the Cl- containing ions, reported in the earlier study, must have been the result of a chlorine containing contaminant as suggested. The failure of ISOF and ENF to undergo DEA was initially surprising given the high calculated electron affinities, but further calculations showed that this was a result of the large positive vertical attachment energies (VAEs). This experimental work has been supported by electronic structure calculations at the B3LYP level, and is consistent with those obtained in a crossed electron-molecular beam two sector field mass spectrometer. An unusual observation is that the monomer complexes of ISOF and ENF with O2 - are relatively unstable compared with the dimer complexes.

  13. First observation and mobility measurements of negative ions in superfluid 4He

    NARCIS (Netherlands)

    Kasimov, Aziz; Zühlke, Christiane; Jungmann, Klaus; Zu Putlitz, Gisbert

    2003-01-01

    We present the results of the first mobility measurements in superfluid helium for negative ions of different elements. Various negative ions like Cl-, F- and I- were produced by laser ablation from targets consisting of NaCl, NaF, NaI, LiF and KCl immersed in a 4He bath. In addition to negative ion

  14. Dividing to unveil protein microheterogeneities: traveling wave ion mobility study.

    Science.gov (United States)

    Halgand, F; Habchi, Johnny; Cravello, Laetitia; Martinho, Marlène; Guigliarelli, Bruno; Longhi, Sonia

    2011-10-01

    Overexpression of a protein in a foreign host is often the only route toward an exhaustive characterization, especially when purification from the natural source(s) is hardly achievable. The key issue in these studies relies on quality control of the purified recombinant protein to precisely determining its identity as well as any undesirable microheterogeneities. While standard proteomics approaches preclude unbiased search for modifications, the optional technique of top-down tandem mass spectrometry (MSMS) requires the use of highly accurate and highly resolved experiments to reveal subtle sequence modifications. In the present study, the top-down MSMS approach combined with traveling wave ion mobility (TWIM) separation was evaluated for its ability to achieve high sequence coverage and to reveal subtle microheterogeneities that were hitherto only accessible with Fourier-transform ion cyclotron resonance-MS instruments. The power of this approach is herein illustrated in an in-depth analysis of both the wild type and K496C variant of the recombinant X domain (XD; aa's 459-507) of the measles virus phosphoprotein expressed in Escherichia coli . Using top-down MSMS combined with TWIM, we show that XD samples occasionally exhibit a microheterogeneity that could not be anticipated from the nucleotide sequence of the encoding constructs and that likely reflects a genetic drift, neutral or not, occurring during expression. In addition, a 1-oxyl-2,2,5,5-tetramethyl-δ3-pyrroline-3-methyl methanethiosulfonate nitroxide probe that was grafted onto the K496C XD variant was shown to undergo oxidation and/or protonation in the electrospray ionization source, leading to artifactual mass increases.

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

    Science.gov (United States)

    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.

  16. Thin layer chromatography-ion mobility spectrometry (TLC-IMS).

    Science.gov (United States)

    Ilbeigi, Vahideh; Tabrizchi, Mahmoud

    2015-01-06

    Ion mobility spectrometry (IMS) is a fast and sensitive analytical method which operates at the atmospheric pressure. To enhance the capability of IMS for the analysis of mixtures, it is often used with preseparation techniques, such as GC or HPLC. Here, we report for the first time the coupling of the thin-layer chromatography and IMS. A variety of coupling schemes were tried that included direct electrospray from the TLC strip tip, indirect electrospray from a needle connected to the TLC strip, introducing the moving solvent into the injection port, and, the simplest way, offline introduction of scratched or cut pieces of strips into the IMS injection port. In this study a special solvent tank was designed and the TLC strip was mounted horizontally where the solvent would flow down. A very small funnel right below the TLC tip collected the solvent and transferred it to a needle via a capillary tubing. Using the TLC-ESI-IMS technique, acceptable separations were achieved for two component mixtures of morphine-papaverine and acridine-papaverine. A special injection port was designed to host the pieces cut off the TLC. The method was successfully used to identify each spot on the TLC by IMS in a few seconds.

  17. Immobilized aptamer paper spray ionization source for ion mobility spectrometry.

    Science.gov (United States)

    Zargar, Tahereh; Khayamian, Taghi; Jafari, Mohammad T

    2017-01-05

    A selective thin-film microextraction based on aptamer immobilized on cellulose paper was used as a paper spray ionization source for ion mobility spectrometry (PSI-IMS), for the first time. In this method, the paper is not only used as an ionization source but also it is utilized for the selective extraction of analyte, based on immobilized aptamer. This combination integrates both sample preparation and analyte ionization in a Whatman paper. To that end, an appropriate sample introduction system with a novel design was constructed for the paper spray ionization source. Using this system, a continuous solvent flow works as an elution and spray solvent simultaneously. In this method, analyte is adsorbed on a triangular paper with immobilized aptamer and then it is desorbed and ionized by elution solvent and applied high voltage on paper, respectively. The effects of different experimental parameters such as applied voltage, angle of paper tip, distance between paper tip and counter electrode, elution solvent type, and solvent flow rate were optimized. The proposed method was exhaustively validated in terms of sensitivity and reproducibility by analyzing the standard solutions of codeine and acetamiprid. The analytical results obtained are promising enough to ensure the use of immobilized aptamer paper-spray as both the extraction and ionization techniques in IMS for direct analysis of biomedicine. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. An online peak extraction algorithm for ion mobility spectrometry data.

    Science.gov (United States)

    Kopczynski, Dominik; Rahmann, Sven

    2015-01-01

    Ion mobility (IM) spectrometry (IMS), coupled with multi-capillary columns (MCCs), has been gaining importance for biotechnological and medical applications because of its ability to detect and quantify volatile organic compounds (VOC) at low concentrations in the air or in exhaled breath at ambient pressure and temperature. Ongoing miniaturization of spectrometers creates the need for reliable data analysis on-the-fly in small embedded low-power devices. We present the first fully automated online peak extraction method for MCC/IMS measurements consisting of several thousand individual spectra. Each individual spectrum is processed as it arrives, removing the need to store the measurement before starting the analysis, as is currently the state of the art. Thus the analysis device can be an inexpensive low-power system such as the Raspberry Pi. The key idea is to extract one-dimensional peak models (with four parameters) from each spectrum and then merge these into peak chains and finally two-dimensional peak models. We describe the different algorithmic steps in detail and evaluate the online method against state-of-the-art peak extraction methods.

  19. Towards metals analysis using corona discharge ionization ion mobility spectrometry.

    Science.gov (United States)

    Jafari, Mohammad T; Saraji, Mohammad; Sherafatmand, Hossein

    2016-02-25

    For the first time, the capability of corona discharge ionization ion mobility spectrometry (CD-IMS) in the determination of metal complex was evaluated. The extreme simplicity of dispersive liquid-liquid microextraction (DLLME) coupled to the high sensitivity of CD-IMS measurement could make this combination really useful for simple, rapid, and sensitive determination of metals in different samples. In this regard, mercury, as a model metal, was complexed with diethyldithiocarbamate (DEDTC), and then extracted into the carbon tetrachloride using DLLME. Some parameters affecting the extraction efficiency, including the type and volume of the extraction solvent, the type and volume of the disperser solvent, the concentration of the chelating agent, salt addition and, pH were exhaustively investigated. Under the optimized condition, the enrichment factor was obtained to be 142. The linear range of 0.035-10.0 μg mL(-1) with r(2) = 0.997 and the detection limit of 0.010 μg mL(-1) were obtained. The relative standard deviation values were calculated to be lower than 4% and 8% for intra-day and inter-day, respectively. Finally, the developed method was successfully applied for the extraction and determination of mercury in various real samples. The satisfactory results revealed the capability of the proposed method in trace analysis without tedious derivatization or hydride generation.

  20. QconCAT standard for calibration of ion mobility-mass spectrometry systems.

    Science.gov (United States)

    Chawner, Ross; McCullough, Bryan; Giles, Kevin; Barran, Perdita E; Gaskell, Simon J; Eyers, Claire E

    2012-11-01

    Ion mobility-mass spectrometry (IM-MS) is a useful technique for determining information about analyte ion conformation in addition to mass/charge ratio. The physical principles that govern the mobility of an ion through a gas in the presence of a uniform electric field are well understood, enabling rotationally averaged collision cross sections (Ω) to be directly calculated from measured drift times under well-defined experimental conditions. However, such "first principle" calculations are not straightforward for Traveling Wave (T-Wave) mobility separations due to the range of factors that influence ion motion through the mobility cell. If collision cross section information is required from T-Wave mobility separations, then calibration of the instruments using known standards is essential for each set of experimental conditions. To facilitate such calibration, we have designed and generated an artificial protein based on the QconCAT technology, QCAL-IM, which upon proteolysis can be used as a universal ion mobility calibration standard. This single unique standard enables empirical calculation of peptide ion collision cross sections from the drift time on a T-Wave mobility instrument.

  1. Comparison of the mobilities of negative and positive ions in nonpolar solutions.

    Science.gov (United States)

    Ivanishko, Irina S; Borovkov, Vsevolod I

    2010-08-01

    The mobilities of organic radical ions of different molecular volumes have been determined in squalane and hexane solutions to study the influence of the ion charge sign on the ionic mobility in a weakly polar liquid. The relative mobility of geminate radical ions was measured using the method of time-resolved electric field effect in the recombination fluorescence. To determine the mobility of cations and anions separately, a trend in the value of the relative mobility was analyzed by varying the mobility of one of the geminate partners. The ratios between the mobilities of the anion and the cation of the same molecules were found to be about 1.1. It was shown that in liquid alkanes, the solvent electrostriction was the main factor determining a decrease in the mobility of an ion as compared to the parent neutral molecule. The strong dependence of the electrostrictive effect on the radius of the ionic solvation shell allows the observed difference between negative and positive charge carriers by a small but systematic difference in the effective radii of the ions to be explained.

  2. Ion mobility-mass spectrometry of phosphorylase B ions generated with supercharging reagents but in charge-reducing buffer.

    Science.gov (United States)

    Hogan, Christopher J; Ogorzalek Loo, Rachel R; Loo, Joseph A; de la Mora, Juan Fernandez

    2010-11-01

    We investigate whether "supercharging" reagents able to shift the charge state distributions (CSDs) of electrosprayed protein ions upward also influence gas-phase protein structure. A differential mobility analyzer and a mass spectrometer are combined in series (DMA-MS) to measure the mass and mobility of monomer and multimeric phosphorylase B ions (monomer molecular weight ∼97 kDa) in atmospheric pressure air. Proteins are electrosprayed from charge-reducing triethylammonium formate in water (pH = 6.8) with and without the addition of the supercharging reagent tetramethylene sulfone (sulfolane). Because the DMA measures ion mobility prior to collisional heating or declustering, it probes the structure of supercharged protein ions immediately following solvent (water) evaporation. As in prior studies, the addition of sulfolane is found to drastically increase both the mean and maximum charge state of phosphorylase B ions. Ions from all protein n-mers were found to yield mobilities that, for a given charge state, were ∼6-10% higher in the absence of sulfolane. We find that the mobility decrease which arises with sulfolane is substantially smaller than that typically observed for folded-to-unfolded transitions in protein ions (where a ∼60% decrease in mobility is typical), suggesting that supercharging reagents do not cause structural protein modifications in solution as large as noted recently by Williams and colleagues [E. R. Williams et al., J. Am. Soc. Mass Spectrom., 2010, 21, 1762-1774]. In fact, the measurements described here indicate that the modest mobility decrease observed can be partly attributed to sulfolane trapping within the protein ions during DMA measurements, and probably also in solution. As the most abundant peaks in measured mass-mobility spectra for ions produced with and without sulfolane correspond to non-covalently bound phosphorylase B dimers, we find that in spite of a change in mobility/cross section, sulfolane addition does not

  3. Compression Ratio Ion Mobility Programming (CRIMP) Accumulation and Compression of Billions of Ions for Ion Mobility-Mass Spectrometry Using Traveling Waves in Structures for Lossless Ion Manipulations (SLIM).

    Science.gov (United States)

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

    2017-06-20

    We report on the implementation of a traveling wave (TW) based compression ratio ion mobility programming (CRIMP) approach within structures for lossless ion manipulations (SLIM) that enables both greatly enlarged trapped ion charge capacities and also efficient ion population compression for use in ion mobility (IM) separations. Ion accumulation is conducted in a SLIM serpentine ultralong path with extended routing (SUPER) region after which CRIMP compression allows the large ion populations to be "squeezed". The SLIM SUPER IM module has two regions, one operating with conventional traveling waves (i.e., traveling trap; TT region) and the second having an intermittently pausing or "stuttering" TW (i.e., stuttering trap; ST region). When a stationary voltage profile was used in the ST region, ions are blocked at the TT-ST interface and accumulated in the TT region and then can be released by resuming a conventional TW in the ST region. The population can also be compressed using CRIMP by the repetitive merging of ions distributed over multiple TW bins in the TT region into a single TW bin in the ST region. Ion accumulation followed by CRIMP compression provides the basis for the use of larger ion populations for IM separations. We show that over 10(9) ions can be accumulated with high efficiency in the present device and that the extent of subsequent compression is only limited by the space charge capacity of the trapping region. Approximately 5 × 10(9) charges introduced from an electrospray ionization source were trapped for a 40 s accumulation period, more than 2 orders of magnitude greater than the previously reported charge capacity of an ion funnel trap. Importantly, we show that extended ion accumulation in conjunction with CRIMP compression and multiple passes through the serpentine path provides the basis for a highly desirable combination of ultrahigh sensitivity and SLIM SUPER high-resolution IM separations.

  4. Ion mobility studies of carbohydrates as group I adducts: isomer specific collisional cross section dependence on metal ion radius.

    Science.gov (United States)

    Huang, Yuting; Dodds, Eric D

    2013-10-15

    Carbohydrates play numerous critical roles in biological systems. Characterization of oligosaccharide structures is essential to a complete understanding of their functions in biological processes; nevertheless, their structural determination remains challenging in part due to isomerism. Ion mobility spectrometry provides the means to resolve gas phase ions on the basis of their shape-to-charge ratios, thus providing significant potential for separation and differentiation of carbohydrate isomers. Here, we report on the determination of collisional cross sections for four groups of isomeric carbohydrates (including five isomeric disaccharides, four isomeric trisaccharides, two isomeric pentasaccharides, and two isomeric hexasaccharides) as their group I metal ion adducts (i.e., [M + Li](+), [M + Na](+), [M + K](+), [M + Rb](+), and [M + Cs](+)). In all, 65 collisional cross sections were measured, the great majority of which have not been previously reported. As anticipated, the collisional cross sections of the carbohydrate metal ion adducts generally increase with increasing metal ion radius; however, the collisional cross sections were found to scale with the group I cation size in isomer specific manners. Such measurements are of substantial analytical value, as they illustrate how the selection of charge carrier influences carbohydrate ion mobility determinations. For example, certain pairs of isomeric carbohydrates assume unique collisional cross sections upon binding one metal ion, but not another. On the whole, these data suggest a role for the charge carrier as a probe of carbohydrate structure and thus have significant implications for the continued development and application of ion mobility spectrometry for the distinction and resolution of isomeric carbohydrates.

  5. Effective Ion Mobility Peak Width as a New Isomeric Descriptor for the Untargeted Analysis of Complex Mixtures Using Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Farenc, Mathilde; Paupy, Benoit; Marceau, Sabrina; Riches, Eleanor; Afonso, Carlos; Giusti, Pierre

    2017-07-01

    Ion mobility coupled with mass spectrometry was proven to be an efficient way to characterize complex mixtures such as petroleum samples. However, the identification of isomeric species is difficult owing to the molecular complexity of petroleum and no availability of standard molecules. This paper proposes a new simple indicator to estimate the isomeric content of highly complex mixtures. This indicator is based on the full width at half maximum (FWHM) of the extracted ion mobility peak measured in millisecond or square angstrom that is corrected for instrumental factors such as ion diffusion. This value can be easily obtained without precisely identifying the number of isomeric species under the ion mobility peaks. Considering the Boduszynski model, the ion mobility profile for a particular elemental composition is expected to be a continuum of various isomeric species. The drift time-dependent fragmentation profile was studied and confirmed this hypothesis, a continuous evolution of the fragmentation profile showing that the larger alkyl chain species were detected at higher drift time values. This new indicator was proven to be a fast and efficient method to compare vacuum gas oils for which no difference was found using other analytical techniques.

  6. Ancient Pb and Ti mobilization revealed by Scanning Ion Imaging

    Science.gov (United States)

    Kusiak, Monika A.; Whitehouse, Martin J.; Wilde, Simon A.

    2014-05-01

    Zircons from strongly layered early Archean ortho- and paragneisses in ultra-high temperature (UHT) metamorphic rocks of the Napier Complex, Enderby Land, East Antarctica are characterized by complex U-Th-Pb systematics [1,2,3]. A large number of zircons from three samples, Gage Ridge, Mount Sones and Dallwitz Nunatak, are reversely discordant (U/Pb ages older than 207Pb/206Pb ages) with the oldest date of 3.9 Ga [4] (for the grain from Gage Ridge orthogneiss). To further investigate this process, we utilized a novel high spatial resolution Scanning Ion Imaging technique on the CAMECA IMS 1280 at the Natural History Museum in Stockholm. Areas of 70 μm x 70 μm were selected for imaging in mono- and multicollection modes using a ~2 μm rastered primary beam to map out the distribution of 48Ti, 89Y, 180Hf, 232Th, 238U, 204Pb, 206Pb and 207Pb. The ion maps reveal variable distribution of certain elements within analysed grains that can be compared to their CL response. Yttrium, together with U and Th, exhibits zonation visible on the CL images, Hf shows expected minimal variation. Unusual patchiness is visible in the map for Ti and Pb distribution. The bright patches with enhanced signal do not correspond to any zones or to crystal imperfections (e.g. cracks). The presence of patchy titanium is likely to affect Ti-in-zircon thermometry, and patchy Pb affecting 207Pb/206Pb ages, usually considered as more robust for Archean zircons. Using the WinImage program, we produced 207Pb/206Pb ratio maps that allow calculation of 207Pb/206Pb ages for spots of any size within the frame of the picture and at any time after data collection. This provides a new and unique method for obtaining age information from zircon. These maps show areas of enhanced brightness where the 207Pb/206Pb ratio is higher and demonstrate that within these small areas (μm scale) the apparent 207Pb/206Pb age is older, in some of these patches even > 4 Ga. These data are a result of ancient Pb

  7. Detection of emissions from surfaces using ion mobility spectrometry.

    Science.gov (United States)

    Vautz, Wolfgang; Baumbach, Jörg Ingo; Uhde, Erik

    2006-02-01

    Emissions from surfaces (from furniture, wall paintings or floor coverings for instance) significantly influence indoor air quality and therefore the wellbeing or even the health of the occupants. Together with metabolites from mold they are responsible for the well-known "sick building syndrome". Therefore, it is in the interest of the manufacturer as well as of the occupants to have a fast and accurate method for the detection of substances relevant to this syndrome in order to be able to monitor and control product quality and indoor air quality. The use of small and easy-to-transport ion mobility spectrometers that use UV light as the ionization source enables rapid in situ detection of such substances with high selectivity and sensitivity (detection limits in the lower ppb range). If a multicapillary column is used for preseparation as well, the selectivity is increased and the unwanted influence of humidity on the spectra can be eliminated, thus enabling the use of the instruments under normal ambient conditions. Furthermore, the use of air as carrier gas avoids the need for other sources of high-purity gas. An emission cell with a homogeneous and constant air flow over the surface to be investigated was developed in order to ensure reproducible results. Investigations of emissions from wooden surfaces with and without additional contamination as well as from complex mixtures are presented. The results demonstrate that relevant emissions can be identified and quantified with high sensitivity and selectivity in under five minutes. Therefore, the method is useful for indoor air quality monitoring, especially when miniaturized instruments are applied.

  8. Measurement of ion swarm distribution functions in miniature low-temperature co-fired ceramic ion mobility spectrometer drift tubes.

    Science.gov (United States)

    Pfeifer, Kent B; Rumpf, Arthur N

    2005-08-15

    Measurements of the performance of a miniature, portable 12-mm-diameter, 57-mm-length low-temperature cofired ceramic (LTCC) ion mobility spectrometer drift tube were undertaken to verify models of ion transport and determine the physical shape of the ion "swarms" in the LTCC tube. Simplified two-dimensional Gaussian models of ion swarm shape were fit to measured data to extract geometrical shape parameters. Results indicate that tube-transfer function effects that produce asymmetric ion swarms are minimized in the tube reducing temporal dispersion. Data are presented that illustrate the swarm shape as a function of gate time, electric field magnitude, and total charge in the ion swarm. Characterization and understanding of the ion transport mechanisms and effects that limit the resolution and other performance parameters of miniature IMS drift tubes is essential to the development of practical, robust, portable systems for "first responder" and homeland security missions.

  9. Compression Ratio Ion Mobility Programming (CRIMP) Accumulation and Compression of Billions of Ions for Ion Mobility-Mass Spectrometry Using Traveling Waves in Structures for Lossless Ion Manipulations (SLIM)

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-05-25

    We report on the implementation of a traveling wave (TW) based compression ratio ion mobility programming (CRIMP) approach within Structures for Lossless Ion Manipulations (SLIM) that enables both greatly enlarged trapped ion charge capacities and also their subsequent efficient compression for use in ion mobility (IM) separations. Ion accumulation is conducted in a long serpentine path TW SLIM region after which CRIMP allows the large ion populations to be ‘squeezed’. The compression process occurs at an interface between two SLIM regions, one operating conventionally and the second having an intermittently pausing or ‘stuttering’ TW, allowing the contents of multiple bins of ions from the first region to be merged into a single bin in the second region. In this initial work stationary voltages in the second region were used to block ions from exiting the first (trapping) region, and the resumption of TWs in the second region allows ions to exit, and the population to also be compressed if CRIMP is applied. In our initial evaluation we show that the number of charges trapped for a 40 s accumulation period was ~5×109, more than two orders of magnitude greater than the previously reported charge capacity using an ion funnel trap. We also show that over 1×109 ions can be accumulated with high efficiency in the present device, and that the extent of subsequent compression is only limited by the space charge capacity of the trapping region. Lower compression ratios allow increased IM peak heights without significant loss of signal, while excessively large compression ratios can lead to ion losses and other artifacts. Importantly, we show that extended ion accumulation in conjunction with CRIMP and multiple passes provides the basis for a highly desirable combination of ultra-high sensitivity and ultra-high resolution IM separations using SLIM.

  10. Relating chromatographic retention and electrophoretic mobility to the ion distribution within electrosprayed droplets.

    Science.gov (United States)

    Bökman, C Fredrik; Bylund, Dan; Markides, Karin E; Sjöberg, Per J R

    2006-03-01

    Ions that are observed in a mass spectrum obtained with electrospray mass spectrometry can be assumed to originate preferentially from ions that have a high distribution to the surface of the charged droplets. In this study, a relation between chromatographic retention and electrophoretic mobility to the ion distribution (derived from measured signal intensities in mass spectra and electrospray current) within electrosprayed droplets for a series of tetraalkylammonium ions, ranging from tetramethyl to tetrapentyl, is presented. Chromatographic retention in a reversed-phase system was taken as a measure of the analyte's surface activity, which was found to have a large influence on the ion distribution within electrosprayed droplets. In addition, different transport mechanisms such as electrophoretic migration and diffusion can influence the surface partitioning coefficient. The viscosity of the solvent system is affected by the methanol content and will influence both diffusion and ion mobility. However, as diffusion and ion mobility are proportional to each other, we have, in this study, chosen to focus on the ion mobility parameter. It was found that the influence of ion mobility relative to surface activity on the droplet surface partitioning of analyte ions decreases with increasing methanol content. This effect is most probably coupled to the decrease in droplet size caused by the decreased surface tension at increasing methanol content. The same observation was made upon increasing the ionic strength of the solvent system, which is also known to give rise to a decreased initial droplet size. The observed effect of ionic strength on the droplet surface partitioning of analyte ions could also be explained by the fact that at higher ionic strength, a larger number of ions are initially closer to the droplet surface and, thus, the contribution of ionic transport from the bulk liquid to the liquid/air surface interface (jet and droplet surface), attributable to

  11. Experimental research on benzene detection using ion mobility spectrometer with a laser ionization source

    Institute of Scientific and Technical Information of China (English)

    LIU Xian-yun; KONG Xiang-he; JI Ren-dong; ZHANG Shu-dong

    2006-01-01

    An ion mobility spectrometer equipped with a laser ionization source is used for the sensitive detection of benzene.Mobility spectra of the benzene are presented.We also discussed the mobility spectra at various concentrations and drift voltages.Detection limits are determined to be in the upper ppbv range.In the end,the advantages and possibilities of this technique are briefly discussed.

  12. Study and optimization of key parameters of a laser ablation ion mobility spectrometer

    Science.gov (United States)

    Ni, Kai; Li, Jianan; Tang, Binchao; Shi, Yuan; Yu, Quan; Qian, Xiang; Wang, Xiaohao

    2016-11-01

    Ion Mobility Spectrometry (IMS), having an advantage in real-time and on-line detection, is an atmospheric pressure detecting technique. LA-IMS (Laser Ablation Ion Mobility Spectrometry) uses Nd-YAG laser as ionization source, whose energy is high enough to ionize metal. In this work, we tested the signal in different electric field intensity by a home-made ion mobility spectrometer, using silicon wafers the sample. The transportation of metal ions was match with the formula: Td = d/K • 1/E, when the electric field intensity is greater than 350v/cm. The relationship between signal intensity and collection angle (the angle between drift tube and the surface of the sample) was studied. With the increasing of the collection angle, signal intensity had a significant increase; while the variation of incident angle of the laser had no significant influence. The signal intensity had a 140% increase when the collection angle varied from 0 to 45 degree, while the angle between the drift tube and incident laser beam keeping the same as 90 degree. The position of ion gate in LA-IMS(Laser Ablation Ion Mobility Spectrometry) is different from the traditional ones for the kinetic energy of the ions is too big, if the distance between ion gate and sampling points less than 2.5cm the ion gate will not work, the ions could go through ion gate when it closed. The SNR had been improved by define the signal when the ion gate is closed as background signal, the signal noise including shock wave and electrical field perturbation produced during the interaction between laser beam and samples is eliminated when the signal that the ion gate opened minus the background signal.

  13. First observation and mobility measurements of negative ions in superfluid He-4

    NARCIS (Netherlands)

    Kasimova, A; Zuhlke, C; Jungmann, K; Putlitz, GZ

    2003-01-01

    We present the results of the first mobility measurements in superfluid helium for negative ions of different elements. Various negative ions like Cl-, F- and I- were produced by laser ablation from targets consisting of NaCl, NaF, NaI, LiF and KCl immersed in a He-4 bath. In addition to negative io

  14. First observation and mobility measurements of negative ions in superfluid He-4

    NARCIS (Netherlands)

    Kasimova, A; Zuhlke, C; Jungmann, K; Putlitz, GZ

    We present the results of the first mobility measurements in superfluid helium for negative ions of different elements. Various negative ions like Cl-, F- and I- were produced by laser ablation from targets consisting of NaCl, NaF, NaI, LiF and KCl immersed in a He-4 bath. In addition to negative

  15. Greatly Increasing Trapped Ion Populations for Mobility Separations Using Traveling Waves in Structures for Lossless Ion Manipulations

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-10-18

    The initial use of traveling waves (TW) for ion mobility (IM) separations using a structures for lossless ion manipulations (SLIM) employed an ion funnel trap (IFT) to accumulate ions from a continuous electrospray ionization source, and limited to injected ion populations of ~106 charges due to the onset of space charge effects in the trapping region. Additional limitations arise due to the loss of resolution for the injection of ions over longer periods (e.g. in extended pulses). In this work a new SLIM ‘flat funnel’ (FF) module has been developed and demonstrated to enable the accumulation of much larger ion populations and their injection for IM separations. Ion current measurements indicate a capacity of ~3.2×108 charges for the extended trapping volume, over an order of magnitude greater than the IFT. The orthogonal ion injection into a funnel shaped separation region can greatly reduce space charge effects during the initial IM separation stage, and the gradually reduced width of the path allows the ion packet to be increasingly compressed in the lateral dimension as the separation progresses, allowing e.g. efficient transmission through conductance limits or compatibility with subsequent ion manipulations. This work examined the TW, RF, and DC confining field SLIM parameters involved in ion accumulation, injection, transmission and separation in the FF IM module using both direct ion current and MS measurements. Wide m/z range ion transmission is demonstrated, along with significant increases in signal to noise (S/N) ratios due to the larger ion populations injected. Additionally, we observed a reduction in the chemical background, which was attributed to more efficient desolvation of solvent related clusters over the extended ion accumulation periods. The TW SLIM FF IM module is anticipated to be especially effective as a front end for long path SLIM IM separation modules.

  16. Greatly Increasing Trapped Ion Populations for Mobility Separations Using Traveling Waves in Structures for Lossless Ion Manipulations.

    Science.gov (United States)

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

    2016-10-07

    The initial use of traveling waves (TW) for ion mobility (IM) separations using structures for lossless ion manipulations (SLIM) employed an ion funnel trap (IFT) to accumulate ions from a continuous electrospray ionization source and was limited to injected ion populations of ∼10(6) charges due to the onset of space charge effects in the trapping region. Additional limitations arise due to the loss of resolution for the injection of ions over longer periods, such as in extended pulses. In this work a new SLIM "flat funnel" (FF) module has been developed and demonstrated to enable the accumulation of much larger ion populations and their injection for IM separations. Ion current measurements indicate a capacity of ∼3.2 × 10(8) charges for the extended trapping volume, over an order of magnitude greater than that of the IFT. The orthogonal ion injection into a funnel shaped separation region can greatly reduce space charge effects during the initial IM separation stage, and the gradually reduced width of the path allows the ion packet to be increasingly compressed in the lateral dimension as the separation progresses, allowing efficient transmission through conductance limits or compatibility with subsequent ion manipulations. This work examined the TW, rf, and dc confining field SLIM parameters involved in ion accumulation, injection, transmission, and IM separation in the FF module using both direct ion current and MS measurements. Wide m/z range ion transmission is demonstrated, along with significant increases in the signal-to-noise ratios (S/N) due to the larger ion populations injected. Additionally, we observed a reduction in the chemical background, which was attributed to more efficient desolvation of solvent related clusters over the extended ion accumulation periods. The TW SLIM FF IM module is anticipated to be especially effective as a front end for long path SLIM IM separation modules.

  17. Data for Users of Handheld Ion Mobility Spectrometers

    Energy Technology Data Exchange (ETDEWEB)

    Keith A. Daum; Sandra L. Fox

    2008-05-01

    Chemical detection technology end-user surveys conducted by Idaho National Laboratory (INL) in 2005 and 2007 indicated that first responders believed manufacturers’ claims for instruments sometimes were not supported in field applications, and instruments sometimes did not meet their actual needs. Based on these findings, the Department of Homeland Security (DHS) asked INL to conduct a similar survey for handheld ion mobility spectrometers (IMS), which are used by a broad community of first responders as well as for other applications. To better access this broad community, the INL used the Center for Technology Commercialization, Inc. (CTC), Public Safety Technology Center (PSTC) to set up an online framework to gather information from users of handheld IMS units. This framework (Survey Monkey) was then used to perform an online Internet survey, augmented by e-mail prompts, to get information from first responders and personnel from various agencies about their direct experience with handheld IMS units. Overall, 478 individuals responded to the survey. Of these, 174 respondents actually owned a handheld IMS. Performance and satisfaction data from these 174 respondents are captured in this report. The survey identified the following observations: • The most common IMS unit used by respondents was the Advanced Portable Detector (APD 2000), followed by ChemRae, Sabre 4000, Sabre 2000, Draeger Multi IMS, Chemical Agent Monitor-2, Chemical Agent Monitor, Vapor Tracer, and Vapor Tracer 2. • The primary owners were HazMat teams (20%), fire services (14%), local police (12%), and sheriffs’ departments (9%). • IMS units are seldom used as part of an integrated system for detecting and identifying chemicals but instead are used independently. • Respondents are generally confused about the capabilities of their IMS unit. This is probably a result of lack of training. • Respondents who had no training or fewer than 8 hours were not satisfied with the overall

  18. Extending the dynamic range of the ion trap by differential mobility filtration.

    Science.gov (United States)

    Hall, Adam B; Coy, Stephen L; Kafle, Amol; Glick, James; Nazarov, Erkinjon; Vouros, Paul

    2013-09-01

    A miniature, planar, differential ion mobility spectrometer (DMS) was interfaced to an LCQ classic ion trap to conduct selective ion filtration prior to mass analysis in order to extend the dynamic range of the trap. Space charge effects are known to limit the functional ion storage capacity of ion trap mass analyzers and this, in turn, can affect the quality of the mass spectral data generated. This problem is further exacerbated in the analysis of mixtures where the indiscriminate introduction of matrix ions results in premature trap saturation with non-targeted species, thereby reducing the number of parent ions that may be used to conduct MS/MS experiments for quantitation or other diagnostic studies. We show that conducting differential mobility-based separations prior to mass analysis allows the isolation of targeted analytes from electrosprayed mixtures preventing the indiscriminate introduction of matrix ions and premature trap saturation with analytically unrelated species. Coupling these two analytical techniques is shown to enhance the detection of a targeted drug metabolite from a biological matrix. In its capacity as a selective ion filter, the DMS can improve the analytical performance of analyzers such as quadrupole (3D or linear) and ion cyclotron resonance (FT-ICR) ion traps that depend on ion accumulation.

  19. Extending the Dynamic Range of the Ion Trap by Differential Mobility Filtration

    Science.gov (United States)

    Hall, Adam B.; Coy, Stephen L.; Kafle, Amol; Glick, James; Nazarov, Erkinjon

    2013-01-01

    A miniature, planar, differential ion mobility spectrometer (DMS) was interfaced to an LCQ classic ion trap to conduct selective ion filtration prior to mass analysis in order to extend the dynamic range of the trap. Space charge effects are known to limit the functional ion storage capacity of ion trap mass analyzers and this, in turn, can affect the quality of the mass spectral data generated. This problem is further exacerbated in the analysis of mixtures where the indiscriminate introduction of matrix ions results in premature trap saturation with non-targeted species, thereby reducing the number of parent ions that may be used to conduct MS/MS experiments for quantitation or other diagnostic studies. We show that conducting differential mobility-based separations prior to mass analysis allows the isolation of targeted analytes from electrosprayed mixtures preventing the indiscriminate introduction of matrix ions and premature trap saturation with analytically unrelated species. Coupling these two analytical techniques is shown to enhance the detection of a targeted drug metabolite from a biological matrix. In its capacity as a selective ion filter, the DMS can improve the analytical performance of analyzers such as quadrupole (3-D or linear) and ion cyclotron resonance (FT-ICR) ion traps that depend on ion accumulation. PMID:23797861

  20. Mobility of O$_2^-$ ions in supercritical Ar: Experiment and Molecular Dynamics Simulations

    CERN Document Server

    Borghesani, A F

    2008-01-01

    A new analysis and new Molecular Dynamics (MD) simulations of the measurements of the mobility $\\mu_{i}$ of O$_{2}^{-} $ ions in dense supercritical Ar gas are reported. $\\mu_{i}$ shows a marked dependence on the distance from the critical temperature $T_{c}.$ A mobility defect appears as a function of the gas density and its maximum value occurs below the critical density. The locus of points of maximum mobility defect in the $P-T$ plane appears on the extrapolation of the coexistence curve into the single-phase region. MD simulations quantitatively reproduce the mobility defect near $T_{c}.$

  1. Adjusting mobility scales of ion mobility spectrometers using 2,6-DtBP as a reference compound.

    Science.gov (United States)

    Viitanen, A-K; Mauriala, T; Mattila, T; Adamov, A; Pedersen, C S; Mäkelä, J M; Marjamäki, M; Sysoev, A; Keskinen, J; Kotiaho, T

    2008-09-15

    Performance of several time-of-flight (TOF) type ion mobility spectrometers (IMS) was compared in a joint measurement campaign and their mobility scales were adjusted based on the measurements. A standard reference compound 2,6-di-tert butylpyridine (2,6-DtBP) was used to create a single peak ion mobility distribution with a known mobility value. The effective length of the drift tube of each device, considered here as an instrument constant, was determined based on the measurements. Sequentially, two multi-peaked test compounds, DMMP and DIMP, were used to verify the performance of the adjustment procedure in a wider mobility scale. By determining the effective drift tube lengths using 2,6-DtBP, agreement between the devices was achieved. The determination of effective drift tube lengths according to standard reference compound was found to be a good method for instrument inter-comparison. The comparison procedure, its benefits and shortcomings as well as dependency on accuracy of literature value are discussed along with the results.

  2. Artificial neural networks for the prediction of peptide drift time in ion mobility mass spectrometry

    Directory of Open Access Journals (Sweden)

    Plasencia Manolo

    2010-04-01

    Full Text Available Abstract Background There is an increasing usage of ion mobility-mass spectrometry (IMMS in proteomics. IMMS combines the features of ion mobility spectrometry (IMS and mass spectrometry (MS. It separates and detects peptide ions on a millisecond time-scale. IMS separates peptide ions based on drift time that is determined by the collision cross-section of each peptide ion in a given experiment condition. A peptide ion's collision cross-section is related to the ion size and shape resulted from the peptide amino acid sequence and their modifications. This inherent relation between the drift time of peptide ion and peptide sequence indicates that the drift time of peptide ions can be used to infer peptide sequence and therefore, for peptide identification. Results This paper describes an artificial neural networks (ANNs regression model for the prediction of peptide ion drift time in IMMS. Each peptide in this work was represented using three descriptors (i.e., molecular weight, sequence length and a two-dimensional sequence index. An ANN predictor consisting of four input nodes, three hidden nodes and one output node was constructed for peptide ion drift time prediction. For the model training and testing, a 10-fold cross-validation strategy was employed for three datasets each containing different charge states. Dataset one contains 212 singly-charged peptide ions, dataset two has 306 doubly-charged peptide ions, and dataset three has 77 triply-charged peptide ions. Our proposed method achieved 94.4%, 93.6% and 74.2% prediction accuracy for singly-, doubly- and triply-charged peptide ions, respectively. Conclusions An ANN-based method has been developed for predicting the drift time of peptide ions in IMMS. The results achieved here demonstrate the effectiveness and efficiency of the prediction model. This work can enhance the confidence of protein identification by combining with current database search approaches for protein identification.

  3. Performance, resolving power, and radial ion distributions of a prototype nanoelectrospray ionization resistive glass atmospheric pressure ion mobility spectrometer.

    Science.gov (United States)

    Kwasnik, Mark; Fuhrer, Katrin; Gonin, Marc; Barbeau, Katherine; Fernandez, Facundo M

    2007-10-15

    In this article, we describe and characterize a novel ion mobility spectrometer constructed with monolithic resistive glass desolvation and drift regions. This instrument is equipped with switchable corona discharge and nanoelectrospray ionization sources and a Faraday plate detector. Following description of the instrument, pulsing electronics, and data acquisition system, we examine the effects of drift gas flow rate and temperature, and of the aperture grid to anode distance on the observed resolving power and sensitivity. Once optimum experimental parameters are identified, different ion gate pulse lengths, and their effect on the temporal spread of the ion packet were investigated. Resolving power ranged from an average value of 50 ms/ms for a 400-micros ion gate pulse, up to an average value of 68 ms/ms for a 100-micros ion gate pulse, and a 26-cm drift tube operated at 383 V cm(-1). Following these experiments, the radial distribution of ions in the drift region of the spectrometer was studied by using anodes of varying sizes, showing that the highest ionic density was located at the center of the drift tube. Finally, we demonstrate the applicability of this instrument to the study of small molecules of environmental relevance by analyzing a commercially available siderophore, deferoxamine mesylate, in both the free ligand and Fe-bound forms. Ion mobility experiments showed a dramatic shift to shorter drift times caused by conformational changes upon metal binding, in agreement with previous reversed-phase liquid chromatography observations.

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

    Science.gov (United States)

    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.

  5. Collisional Cross-Sections with T-Wave Ion Mobility Spectrometry without Experimental Calibration

    Science.gov (United States)

    Mortensen, Daniel N.; Susa, Anna C.; Williams, Evan R.

    2017-07-01

    A method for relating traveling-wave ion mobility spectrometry (TWIMS) drift times with collisional cross-sections using computational simulations is presented. This method is developed using SIMION modeling of the TWIMS potential wave and equations that describe the velocity of ions in gases induced by electric fields. The accuracy of this method is assessed by comparing the collisional cross-sections of 70 different reference ions obtained using this method with those obtained from static drift tube ion mobility measurements. The cross-sections obtained here with low wave velocities are very similar to those obtained using static drift (average difference = 0.3%) for ions formed from both denaturing and buffered aqueous solutions. In contrast, the cross-sections obtained with high wave velocities are significantly greater, especially for ions formed from buffered aqueous solutions. These higher cross-sections at high wave velocities may result from high-order factors not accounted for in the model presented here or from the protein ions unfolding during TWIMS. Results from this study demonstrate that collisional cross-sections can be obtained from single TWIMS drift time measurements, but that low wave velocities and gentle instrument conditions should be used in order to minimize any uncertainties resulting from high-order effects not accounted for in the present model and from any protein unfolding that might occur. Thus, the method presented here eliminates the need to calibrate TWIMS drift times with collisional cross-sections measured using other ion mobility devices.

  6. Effects of ion mobility and positron fraction on solitary waves in weak relativistic electron-positron-ion plasma

    CERN Document Server

    Lu, Ding; Xie, Bai-Song

    2013-01-01

    Effects of ion mobility and positron fraction on solitary waves of envelop of laser field and potential of electrostatic field in weak relativistic electron-positron-ion plasma are investigated. The parameter region for the existence of solitary waves is obtained analytically, and the reasonable choice of parameters is clarified. Both cases of mobile and immobile ions are considered. It is found that the amplitudes of solitary waves in the former case are larger compared to the latter case. For small plasma density, the localized solitary wave solutions in terms of approximate perturbation analytical method are consistent well with that by exact numerical calculations. However as the plasma density increases the analytical method loses its validity more and more. The influence of the positron fraction on the amplitudes of solitary waves shows a monotonous increasing relation. Implication of our results to the particle acceleration is also discussed briefly.

  7. Effects of ion mobility and positron fraction on solitary waves in weak relativistic electron-positron-ion plasma

    Science.gov (United States)

    Lu, Ding; Li, Zi-Liang; Xie, Bai-Song

    2013-09-01

    The effects of ion mobility and positron fraction on the solitary waves of the laser field envelope and the potential of the electrostatic field in weak relativistic electron-positron-ion plasma are investigated. The parameter region for the existence of solitary waves is obtained analytically, and a reasonable choice of parameters is clarified. Both cases of mobile and immobile ions are considered. It is found that the amplitudes of solitary waves in the former case are larger compared to the latter case. For small plasma density, the localized solitary wave solutions in terms of the approximate perturbation analytical method are very consistent with those by exact numerical calculations. However, as the plasma density increases the analytical method loses its validity more and more. The influence of the positron fraction on the amplitudes of solitary waves shows a monotonous increasing relation. The implications of our results to particle acceleration are also discussed briefly.

  8. Ion Mobility Separations of Isomers based upon Long Path Length Structures for Lossless Ion Manipulations Combined with Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Liulin [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Ibrahim, Yehia M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Baker, Erin S. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Aly, Noor A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Hamid, Ahmed M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zhang, Xing [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zheng, Xueyun [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Garimella, Sandilya V. B. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Webb, Ian K. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Prost, Spencer A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Sandoval, Jeremy A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Norheim, Randolph V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Anderson, Gordon A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Tolmachev, Aleksey V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Smith, Richard D. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA

    2016-07-01

    Mass spectrometry (MS)-based multi-omic measurements, including proteomics, metabolomics, lipidomics, and glycomics, are increasingly transforming our ability to characterize and understand biological systems, but, presently have limitations due to the chemical diversity and range of abundances of biomolecules in complex samples. Advances addressing these challenges increasingly are based upon the ability to quickly separate, react and otherwise manipulate sample components for analysis by MS. Here we report on a new approach using Structures for Lossless Ion Manipulations (SLIM) to enable long serpentine path ion mobility spectrometry (IMS) separations followed by MS analyses. This approach provides previously unachieved mobility biomolecule isomer separations for biomolecular species, in conjunction with more effective ion utilization, and producing a basis for the improved characterization of very small samples.

  9. The investigation of ionization conditions in the trace amounts detection of heterocyclic compounds by ion mobility spectrometry and mass spectrometry

    Science.gov (United States)

    Shaltaeva, Y. R.; Sysoev, A. A.; Poteshin, S. S.; Negru, K. I.; Grishin, S. S.; Trefilova, V. V.; Zuev, M. I.; Baberkina, E. P.

    2016-10-01

    The first part of paper is devoted to the detection of New Psychoactive Substances by ion mobility mass spectrometry study. In the second part of the paper presents a promising approach to prevent the spread of narcotic substances, consisting in the use of field-portable ion mobility spectrometers and finding the correlation between the peaks of the spectrograms of ion mobility and the chemical structure of the compound.

  10. Identity Efficiency for High-Performance Ambient Pressure Ion Mobility Spectrometry.

    Science.gov (United States)

    Kanu, A Bakarr; Leal, Anne

    2016-03-15

    A new approach to reduce the false-positive responses commonly encountered in the field when drugs and explosives are detected is reported for an electrospray ionization high-performance ion mobility spectrometry (ESI-HPIMS). In this article, we report on the combination of reduced mobility and the width-at-half-height of a peak to give a new parameter called conditional reduced mobility (CRM). It was found that the CRM was capable of differentiating between real drugs peaks from that of a false-positive peak and may help to reduce false-positive rates. This effect was demonstrated using 11 drugs (amphetamine, cannabidiol, cocaine, codeine, heroine, methamphetamine, morphine, phentermine, L-phenylepherine, proglitazone, and rosiglitazone) and seven interferences chosen from off-the-shelf products. This report determined and compared CRM, resolving power (R(m)), and diffusion-limited conditional theoretical reduced mobility (DLCTRM) for ESI-HPIMS. The most important parameters for determining CRM are reduced mobility and width-at-half-height of a peak. There is a specific optimum voltage, gate pulse width, resolving power, and now CRM for each ion. DLCTRM indicate the optimum reduced mobility that is not normally possible under field conditions. CRM predicts the condition at which a target compound can be differentiated from a false-positive response. This was possible because different ions exhibits different drifting patterns and hence a different peak broadening phenomenon inside an ion mobility tube. Reduced mobility for target compounds reported were reproducible to within 2% for ESI-HPIMS. The estimated resolving power for the ESI-HPIMS used in this study was 61 ± 0.22. Conditional reduced mobility introduced in this paper show differences between target compounds and false-positive peaks as high as 74%, as was the case for cannabidiol and interference #1 at 70 μs gate pulse width.

  11. Secondary electrospray ionization ion mobility spectrometry/mass spectrometry of illicit drugs.

    Science.gov (United States)

    Wu, C; Siems, W F; Hill, H H

    2000-01-15

    A secondary electrospray ionization (SESI) method was developed as a nonradioactive ionization source for ion mobility spectrometry (IMS). This SESI method relied on the gas-phase interaction between charged particles created by electrospray ionization (ESI) and neutral gaseous sample molecules. Mass spectrometry (MS) was used as the detection method after ion mobility separation for ion identification. Preliminary investigations focussed on understanding the ionization process of SESI. The performance of ESI-IMS and SESI-IMS for illicit drug detection was evaluated by determining the analytical figures of merit. In general, SESI had a higher ionization efficiency for small volatile molecules compared with the electrospray method. The potential of developing a universal interface for both GC- and LC-MS with an addition stage of mobility separation was demonstrated.

  12. Interfacing an ion mobility spectrometry based explosive trace detector to a triple quadrupole mass spectrometer.

    Science.gov (United States)

    Kozole, Joseph; Stairs, Jason R; Cho, Inho; Harper, Jason D; Lukow, Stefan R; Lareau, Richard T; DeBono, Reno; Kuja, Frank

    2011-11-15

    Hardware from a commercial-off-the-shelf (COTS) ion mobility spectrometry (IMS) based explosive trace detector (ETD) has been interfaced to an AB/SCIEX API 2000 triple quadrupole mass spectrometer. To interface the COTS IMS based ETD to the API 2000, the faraday plate of the IMS instrument and the curtain plate of the mass spectrometer were removed from their respective systems and replaced by a custom faraday plate, which was fabricated with a hole for passing the ion beam to the mass spectrometer, and a custom interface flange, which was designed to attach the IMS instrument onto the mass spectrometer. Additionally, the mass spectrometer was modified to increase the electric field strength and decrease the pressure in the differentially pumped interface, causing a decrease in the effect of collisional focusing and permitting a mobility spectrum to be measured using the mass spectrometer. The utility of the COTS-ETD/API 2000 configuration for the characterization of the gas phase ion chemistry of COTS-ETD equipment was established by obtaining mass and tandem mass spectra in the continuous ion flow and selected mobility monitoring operating modes and by obtaining mass-selected ion mobility spectra for the explosive standard 2,4,6 trinitrotoluene (TNT). This analysis confirmed that the product ion for TNT is [TNT - H](-), the predominant collision-induced dissociation pathway for [TNT- H](-) is the loss of NO and NO(2), and the reduced mobility value for [TNT - H](-) is 1.54 cm(2)V(-1) s(-1). Moreover, this analysis was attained for sample amounts of 1 ng and with a resolving power of 37. The objective of the research is to advance the operational effectiveness of COTS IMS based ETD equipment by developing a platform that can facilitate the understanding of the ion chemistry intrinsic to the equipment.

  13. Determining the mobility of ions by transient current measurements at high voltages.

    Science.gov (United States)

    Kohn, Peter; Schröter, Klaus; Thurn-Albrecht, Thomas

    2007-08-24

    We present polarization and transient current experiments that allow an independent determination of the charge carrier density and the mobility of ions in polymer electrolytes at low charge carrier density. The method relies on a complete depletion of ions in the bulk electrolyte achieved by applying high voltages. Based on a qualitative model for the charge dynamics in this nonlinear regime, the method is exemplarily applied to a system of polymethylmethacrylate doped with small amounts of a lithium salt. The independently obtained values for the ionic mobility, the charge carrier density, and the conductivity are consistent for all salt concentrations studied. Criteria for the applicability of the method are discussed.

  14. Photo and Collision Induced Isomerization of a Cyclic Retinal Derivative: An Ion Mobility Study.

    Science.gov (United States)

    Coughlan, Neville J A; Scholz, Michael S; Hansen, Christopher S; Trevitt, Adam J; Adamson, Brian D; Bieske, Evan J

    2016-09-01

    A cationic degradation product, formed in solution from retinal Schiff base (RSB), is examined in the gas phase using ion mobility spectrometry, photoisomerization action spectroscopy, and collision induced dissociation (CID). The degradation product is found to be N-n-butyl-2-(β-ionylidene)-4-methylpyridinium (BIP) produced through 6π electrocyclization of RSB followed by protonation and loss of dihydrogen. Ion mobility measurements show that BIP exists as trans and cis isomers that can be interconverted through buffer gas collisions and by exposure to light, with a maximum response at λ = 420 nm.Graphical Abstract.

  15. Electron attachment rate constant measurement by photoemission electron attachment ion mobility spectrometry (PE-EA-IMS)

    Science.gov (United States)

    Su, Desheng; Niu, Wenqi; Liu, Sheng; Shen, Chengyin; Huang, Chaoqun; Wang, Hongmei; Jiang, Haihe; Chu, Yannan

    2012-12-01

    Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS), with a source of photoelectrons induced by vacuum ultraviolet radiation on a metal surface, has been developed to study electron attachment reaction at atmospheric pressure using nitrogen as the buffer gas. Based on the negative ion mobility spectra, the rate constants for electron attachment to tetrachloromethane and chloroform were measured at ambient temperature as a function of the average electron energy in the range from 0.29 to 0.96 eV. The experimental results are in good agreement with the data reported in the literature.

  16. IR-MALDI-LDI combined with ion mobility orthogonal time-of-flight mass spectrometry.

    Science.gov (United States)

    Woods, Amina S; Ugarov, Michael; Jackson, Shelley N; Egan, Thomas; Wang, Hay-Yan J; Murray, Kermit K; Schultz, J Albert

    2006-06-01

    Most MALDI instrumentation uses UV lasers. We have designed a MALDI-IM-oTOF-MS which employs both a Nd:YAG laser pumped optical parametric oscillator (OPOTEK, lambda = 2.8-3.2 microm at 20 Hz) to perform IR-LDI or IR-MALDI and a Nd:YLF laser (Crystalaser, lambda = 249 nm at 200 Hz) for the UV. Ion mobility (IM) gives a fast separation and analysis of biomolecules from complex mixtures in which ions of similar chemical type fall along well-defined "trend lines". Our data shows that ion mobility allows multiply charged monomers and multimers to be resolved; thus, yielding pure spectra of the singly charged protein ion which are virtually devoid of chemical noise. In addition, we have demonstrated that IR-LDI produced similar results as IR-MALDI for the direct tissue analysis of phospholipids from rat brain.

  17. Measurements of ion mobility in argon and neon based gas mixtures

    Science.gov (United States)

    Deisting, Alexander; Garabatos, Chilo; Szabo, Alexander; Vranic, Danilo

    2017-02-01

    As gaseous detectors are operated at high rates of primary ionisation, ions created in the detector have a considerable impact on the performance of the detector. The upgraded ALICE Time Projection Chamber (TPC) will operate during LHC Run 3 with a substantial space charge density of positive ions in the drift volume. In order to properly simulate such space charges, knowledge of the ion mobility K is necessary. To this end, a small gaseous detector was constructed and the ion mobility of various gas mixtures was measured. To validate the corresponding signal analysis, simulations were performed. Results are shown for several argon and neon based mixtures with different CO2 fractions. A decrease of K was measured for increasing water content.

  18. Measurements of ion mobility in argon and neon based gas mixtures

    CERN Document Server

    Deisting, Alexander; Szabo, Alexander; Vranic, Danilo

    2016-01-01

    As gaseous detectors are operated at high rates of primary ionisation, ions created in the detector have a considerable impact on the performance of the detector. The upgraded ALICE Time Projection Chamber (TPC) will operate during LHC Run$\\,3$ with a substantial space charge density of positive ions in the drift volume. In order to properly simulate such space charges, knowledge of the ion mobility $K$ is necessary. To this end, a small gaseous detector was constructed and the ion mobility of various gas mixtures was measured. To validate the corresponding signal analysis, simulations were performed. Results are shown for several argon and neon based mixtures with different $\\textrm{CO}_2$ fractions. A decrease of $K$ was measured for increasing water content.

  19. Atmospheric Pressure Chemical Ionization Sources Used in The Detection of Explosives by Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Waltman, Melanie J. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States)

    2010-05-01

    Explosives detection is a necessary and wide spread field of research. From large shipping containers to airline luggage, numerous items are tested for explosives every day. In the area of trace explosives detection, ion mobility spectrometry (IMS) is the technique employed most often because it is a quick, simple, and accurate way to test many items in a short amount of time. Detection by IMS is based on the difference in drift times of product ions through the drift region of an IMS instrument. The product ions are created when the explosive compounds, introduced to the instrument, are chemically ionized through interactions with the reactant ions. The identity of the reactant ions determines the outcomes of the ionization process. This research investigated the reactant ions created by various ionization sources and looked into ways to manipulate the chemistry occurring in the sources.

  20. Modulation of electrical mobility in Au ion irradiated titanium oxide with crystal field splitting

    Science.gov (United States)

    Park, Hyun-Woo; Jun, Byung-Hyuk; Choi, Dukhyun; Chung, Kwun-Bum

    2016-11-01

    Electrical modulation of radio frequency (RF) sputtered TiO2- x films were investigated as a function of Au swift heavy ion irradiation dose at room temperature. The prepared TiO2- x films were irradiated with 130 MeV Au swift heavy ion in the range from 1 × 1011 to 5 × 1012 ions/cm2. As the Au ion irradiation dose increased up to 1 × 1012 ions/cm2, the electrical mobility of TiO2- x films were dramatically increased 3.07 × 102 cm2 V-1 s-1 without the change of carrier concentration. These changes in electrical properties of Au irradiated TiO2- x film, are related to the modification of electronic structure such as crystal field splitting of Ti 3d orbital hybridization and sub-band edge states below the conduction band as a function of Au swift heavy ion irradiation dose.

  1. Lithium-ion battery electrolyte mobility at nano-confined graphene interfaces

    OpenAIRE

    Moeremans, Boaz; Cheng, Hsiu-Wei; Hu, Qingyun; Garces, Hector F.; Padture, Nitin P.; Renner, Frank Uwe; Valtiner, Markus

    2016-01-01

    Interfaces are essential in electrochemical processes, providing a critical nanoscopic design feature for composite electrodes used in Li-ion batteries. Understanding the structure, wetting and mobility at nano-confined interfaces is important for improving the efficiency and lifetime of electrochemical devices. Here we use a Surface Forces Apparatus to quantify the initial wetting of nanometre-confined graphene, gold and mica surfaces by Li-ion battery electrolytes. Our results indicate pref...

  2. Pharmaceutical metabolite profiling using quadrupole/ion mobility spectrometry/time-of-flight mass spectrometry.

    Science.gov (United States)

    Chan, Eric C Y; New, Lee Sun; Yap, Chun Wei; Goh, Lin Tang

    2009-02-01

    The use of hybrid quadrupole ion mobility spectrometry time-of-flight mass spectrometry (Q/IMS/TOFMS) in the metabolite profiling of leflunomide (LEF) and acetaminophen (APAP) is presented. The IMS drift times (T(d)) of the drugs and their metabolites were determined in the IMS/TOFMS experiments and correlated with their exact monoisotopic masses and other in silico generated structural properties, such as connolly molecular area (CMA), connolly solvent-excluded volume (CSEV), principal moments of inertia along the X, Y and Z Cartesian coordinates (MI-X, MI-Y and MI-Z), inverse mobility and collision cross-section (CCS). The correlation of T(d) with these parameters is presented and discussed. IMS/TOF tandem mass spectrometry experiments (MS(2) and MS(3)) were successfully performed on the N-acetyl-p-benzoquinoneimine glutathione (NAPQI-GSH) adduct derived from the in vitro microsomal metabolism of APAP. As comparison, similar experiments were also performed using hybrid triple quadrupole linear ion trap mass spectrometry (QTRAPMS) and quadrupole time-of-flight mass spectrometry (QTOFMS). The abilities to resolve the product ions of the metabolite within the drift tube and fragment the ion mobility resolved product ions in the transfer travelling wave-enabled stacked ring ion guide (TWIG) demonstrated the potential applicability of the Q/IMS/TOFMS technique in pharmaceutical metabolite profiling.

  3. On-tissue protein identification and imaging by MALDI-ion mobility mass spectrometry.

    Science.gov (United States)

    Stauber, Jonathan; MacAleese, Luke; Franck, Julien; Claude, Emmanuelle; Snel, Marten; Kaletas, Basak Kükrer; Wiel, Ingrid M V D; Wisztorski, Maxence; Fournier, Isabelle; Heeren, Ron M A

    2010-03-01

    MALDI imaging mass spectrometry (MALDI-IMS) has become a powerful tool for the detection and localization of drugs, proteins, and lipids on-tissue. Nevertheless, this approach can only perform identification of low mass molecules as lipids, pharmaceuticals, and peptides. In this article, a combination of approaches for the detection and imaging of proteins and their identification directly on-tissue is described after tryptic digestion. Enzymatic digestion protocols for different kinds of tissues--formalin fixed paraffin embedded (FFPE) and frozen tissues--are combined with MALDI-ion mobility mass spectrometry (IM-MS). This combination enables localization and identification of proteins via their related digested peptides. In a number of cases, ion mobility separates isobaric ions that cannot be identified by conventional MALDI time-of-flight (TOF) mass spectrometry. The amount of detected peaks per measurement increases (versus conventional MALDI-TOF), which enables mass and time selected ion images and the identification of separated ions. These experiments demonstrate the feasibility of direct proteins identification by ion-mobility-TOF IMS from tissue. The tissue digestion combined with MALDI-IM-TOF-IMS approach allows a proteomics "bottom-up" strategy with different kinds of tissue samples, especially FFPE tissues conserved for a long time in hospital sample banks. The combination of IM with IMS marks the development of IMS approaches as real proteomic tools, which brings new perspectives to biological studies.

  4. Direct classification of olive oils by using two types of ion mobility spectrometers

    Energy Technology Data Exchange (ETDEWEB)

    Garrido-Delgado, Rocio [Department of Analytical Chemistry, University of Cordoba, Annex C3 Building, Campus of Rabanales, E-14071 Cordoba (Spain); Mercader-Trejo, Flora [Department of Analytical Chemistry, University of Cordoba, Annex C3 Building, Campus of Rabanales, E-14071 Cordoba (Spain); Metrologia de Materiales, Centro Nacional de Metrologia, km. 4.5 Carretera a Los Cues, El Marques, Queretaro (Mexico); Sielemann, Stefanie; Bruyn, Wolfgang de [G.A.S. Gesellschaft fuer analytische Sensorsysteme mbH, BioMedizinZentrumDortmund, Otto-Hahn-Str. 15, 44227 Dortmund (Germany); Arce, Lourdes [Department of Analytical Chemistry, University of Cordoba, Annex C3 Building, Campus of Rabanales, E-14071 Cordoba (Spain); Valcarcel, Miguel, E-mail: qa1meobj@uco.es [Department of Analytical Chemistry, University of Cordoba, Annex C3 Building, Campus of Rabanales, E-14071 Cordoba (Spain)

    2011-06-24

    Graphical abstract: Highlights: > We explore the use of Ion Mobility Spectrometers for classification of olive oils. > Three types of olive oils were analyzed with both devices coupled to headspace system. > The ion mobility data were processed using chemometric to obtain global information. > The classification rate was better using tritium source and separation step prior IMS. - Abstract: In this work, we explored the use of an Ion Mobility Spectrometry (IMS) device with an ultraviolet (UV) source, and of a Gas Chromatographic (GC) column coupled to an IM Spectrometer with a tritium source, for the discrimination of three grades of olive oil, namely: extra virgin olive oil (EVOO), olive oil (OO) and pomace olive oil (POO). The three types of oil were analyzed with both equipment combinations as coupled to a headspace system and the obtained ion mobility data were consecutively processed with various chemometric tools. The classification rate for an independent validation set was 86.1% (confidence interval at 95% [83.4%, 88.5%]) with an UV-IMS and 100% (confidence interval at 95% [87%, 100%]) using a GC-IMS system. The classification rate was improved by using a more suitable ionization source and a pre-separation step prior to the IM analysis.

  5. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 1. Peptides to Proteins

    Science.gov (United States)

    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.

  6. Determining the isomeric heterogeneity of neutral oligosaccharide-alditols of bovine submaxillary mucin using negative ion traveling wave ion mobility mass spectrometry.

    Science.gov (United States)

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

    2015-02-17

    Negative ions produced by electrospray ionization were used to evaluate the isomeric heterogeneity of neutral oligosaccharide-alditols isolated from bovine submaxillary mucin (BSM). The oligosaccharide-alditol mixture was preseparated on an off-line high-performance liquid chromatography (HPLC) column, and the structural homogeneity of individual LC fractions was investigated using a Synapt G2 traveling wave ion mobility spectrometer coupled between quadupole and time-of-flight mass spectrometers. Mixtures of isomers separated by both chromatography and ion mobility spectrometry were studied. Tandem mass spectrometry (MS/MS) of multiple mobility peaks having the same mass-to-charge ratio (m/z) demonstrated the presence of different structural isomers and not differences in ion conformations due to charge site location. Although the oligosaccharide-alditol mixture was originally separated by HPLC, multiple ion mobility peaks due to structural isomers were observed for a number of oligosaccharide-alditols from single LC fractions. The collision-induced dissociation cells located in front of and after the ion mobility separation device enabled oligosaccharide precursor or product ions to be separated by ion mobility and independent fragmentation spectra to be acquired for isomeric carbohydrate precursor or product ions. MS/MS spectra so obtained for independent mobility peaks at a single m/z demonstrated the presence of structural variants or stereochemical isomers having the same molecular formula. This was observed both for oligosaccharide precursor and product ions. In addition, mobilities of both [M - H](-) and [M + Cl](-) ions, formed by adding NH4OH or NH4Cl to the electrospray solvent, were examined and compared for selected oligosaccharide-alditols. Better separation among structural isomers appeared to be achieved for some [M + Cl](-) anions.

  7. Effect of the difference in ion mobilities on traveling-wave electro-osmosis

    CERN Document Server

    Gonzalez, Antonio; Garcia-Sanchez, Pablo; Castellanos, Antonio

    2008-01-01

    We analyze the AC electro-osmotic motion of a 1:1 aqueous solution, taking into account the difference in mobilities and diffusion coefficients between positive and negative ions. This model serves to understand the behavior of common systems as a solution of NaCl in water. We pay special attention to two cases. First, the case of slightly different mobilities, that can model a KCl solution. Second, the case of a strongly asymmetric solution, with an almost vanishing mobility, applicable to the case of a salt where the negative ion is much more massive than the positive one. For all the cases, we perform the mathematical description and linear analysis of the problem, in order to establish the dependence of the induced velocity with the frequency, wavelength and amplitude of the applied voltage.

  8. Collision Cross Sections for 20 Protonated Amino Acids: Fourier Transform Ion Cyclotron Resonance and Ion Mobility Results

    Science.gov (United States)

    Anupriya; Jones, Chad A.; Dearden, David V.

    2016-08-01

    We report relative dephasing cross sections for the 20 biogenic protonated amino acids measured using the cross sectional areas by Fourier transform ion cyclotron resonance (CRAFTI) technique at 1.9 keV in the laboratory reference frame, as well as momentum transfer cross sections for the same ions computed from Boltzmann-weighted structures determined using molecular mechanics. Cross sections generally increase with increasing molecular weight. Cross sections for aliphatic and aromatic protonated amino acids are larger than the average trend, suggesting these side chains do not fold efficiently. Sulfur-containing protonated amino acids have smaller than average cross sections, reflecting the mass of the S atom. Protonated amino acids that can internally hydrogen-bond have smaller than average cross sections, reflecting more extensive folding. The CRAFTI measurements correlate well with results from drift ion mobility (IMS) and traveling wave ion mobility (TWIMS) spectrometric measurements; CRAFTI results correlate with IMS values approximately as well as IMS and TWIMS values from independent measurements correlate with each other. Both CRAFTI and IMS results correlate well with the computed momentum transfer cross sections, suggesting both techniques provide accurate molecular structural information. Absolute values obtained using the various methods differ significantly; in the case of CRAFTI, this may be due to errors in measurements of collision gas pressure, measurement of excitation voltage, and/or dependence of cross sections on kinetic energy.

  9. High-Voltage, Asymmetric-Waveform Generator

    Science.gov (United States)

    Beegle, Luther W.; Duong, Tuan A.; Duong, Vu A.; Kanik, Isik

    2008-01-01

    The shapes of waveforms generated by commercially available analytical separation devices, such as some types of mass spectrometers and differential mobility spectrometers are, in general, inadequate and result in resolution degradation in output spectra. A waveform generator was designed that would be able to circumvent these shortcomings. It is capable of generating an asymmetric waveform, having a peak amplitude as large as 2 kV and frequency of several megahertz, which can be applied to a capacitive load. In the original intended application, the capacitive load would consist of the drift plates in a differential-mobility spectrometer. The main advantage to be gained by developing the proposed generator is that the shape of the waveform is made nearly optimum for various analytical devices requiring asymmetric-waveform such as differential-mobility spectrometers. In addition, this waveform generator could easily be adjusted to modify the waveform in accordance with changed operational requirements for differential-mobility spectrometers. The capacitive nature of the load is an important consideration in the design of the proposed waveform generator. For example, the design provision for shaping the output waveform is based partly on the principle that (1) the potential (V) on a capacitor is given by V=q/C, where C is the capacitance and q is the charge stored in the capacitor; and, hence (2) the rate of increase or decrease of the potential is similarly proportional to the charging or discharging current. The proposed waveform generator would comprise four functional blocks: a sine-wave generator, a buffer, a voltage shifter, and a high-voltage switch (see Figure 1). The sine-wave generator would include a pair of operational amplifiers in a feedback configuration, the parameters of which would be chosen to obtain a sinusoidal timing signal of the desired frequency. The buffer would introduce a slight delay (approximately equal to 20 ns) but would otherwise

  10. Desorption electrospray ionization (DESI) with atmospheric pressure ion mobility spectrometry for drug detection.

    Science.gov (United States)

    Roscioli, Kristyn M; Tufariello, Jessica A; Zhang, Xing; Li, Shelly X; Goetz, Gilles H; Cheng, Guilong; Siems, William F; Hill, Herbert H

    2014-04-01

    Desorption electrospray ionization (DESI) was coupled to an ambient pressure drift tube ion mobility time-of-flight mass spectrometer (IM-TOFMS) for the direct analysis of active ingredients in pharmaceutical samples. The DESI source was also coupled with a standalone IMS demonstrating potential of portable and inexpensive drug-quality testing platforms. The DESI-IMS required no sample pretreatment as ions were generated directly from tablets and cream formulations. The analysis of a range of over-the-counter and prescription tablet formations was demonstrated for amphetamine (methylphenidate), antidepressant (venlafaxine), barbiturate (Barbituric acid), depressant (alprazolam), narcotic (3-methylmorphine) and sympatholytic (propranolol) drugs. Active ingredients from soft and liquid formulations, such as Icy Hot cream (methyl salicylate) and Nyquil cold medicine (acetaminophen, dextromethorphan, doxylamine) were also detected. Increased sensitivity for selective drug responses was demonstrated through the formation of sodiated adduct ions by introducing small quantities of NaCl into the DESI solvent. Of the drugs and pharmaceuticals tested in this study, 68% (22 total samples) provided a clear ion mobility response at characteristic mobilities either as (M + H)(+), (M - H)(-), or (M + Na)(+) ions.

  11. Ion Mobility Separations of Isomers based upon Long Path Length Structures for Lossless Ion Manipulations Combined with Mass Spectrometry.

    Science.gov (United States)

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

    2016-07-01

    Mass spectrometry (MS)-based multi-omic measurements, including proteomics, metabolomics, lipidomics, and glycomics, are increasingly transforming our ability to characterize and understand biological systems. Multi-omic analyses and the desire for comprehensive measurement coverage presently have limitations due to the chemical diversity and range of abundances of biomolecules in complex samples. Advances addressing these challenges increasingly are based upon the ability to quickly separate, react and otherwise manipulate sample components for analysis by MS. Here we report on a new approach using Structures for Lossless Ion Manipulations (SLIM) to enable long serpentine path ion mobility spectrometry (IMS) separations followed by MS analyses. This approach provides previously unachieved resolution for biomolecular species, in conjunction with more effective ion utilization, and a basis for greatly improved characterization of very small sample sizes.

  12. Achieving High Resolution Ion Mobility Separations Using Traveling Waves in Compact Multiturn Structures for Lossless Ion Manipulations.

    Science.gov (United States)

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

    2016-09-20

    We report on ion mobility (IM) separations achievable using traveling waves (TW) in a Structures for Lossless Ion Manipulations (SLIM) module having a 44 cm path length and 16 90° turns. The performance of the TW-SLIM module was evaluated for ion transmission and IM separations with different RF, TW parameters, and SLIM surface gaps in conjunction with mass spectrometry. In this work, TWs were created by the transient and dynamic application of DC potentials. The module demonstrated highly robust performance and, even with 16 closely spaced turns, achieving IM resolution performance and ion transmission comparable to a similar straight path module. We found an IM peak capacity of ∼31 and peak generation rate of 780 s(-1) for TW speeds of ∼80 m/s using the current multi-turn TW-SLIM module. The separations achieved for isomers of peptides and tetrasaccharides were found to be comparable to those from a ∼0.9-m drift tube-based IM-MS platform operated at the same pressure (4 Torr). The combined attributes of flexible design, low voltage requirements and lossless ion transmission through multiple turns for the present TW-SLIM module provides a basis for SLIM devices capable of achieving much greater IM resolution via greatly extended ion path lengths and using compact serpentine designs.

  13. Misfolded Amyloid Ion Channels Present Mobile β-Sheet Subunits in Contrast to Conventional Ion Channels

    OpenAIRE

    Jang, Hyunbum; Arce, Fernando Teran; Capone, Ricardo; Ramachandran, Srinivasan; Lal, Ratnesh; Nussinov, Ruth

    2009-01-01

    In Alzheimer's disease, calcium permeability through cellular membranes appears to underlie neuronal cell death. It is increasingly accepted that calcium permeability involves toxic ion channels. We modeled Alzheimer's disease ion channels of different sizes (12-mer to 36-mer) in the lipid bilayer using molecular dynamics simulations. Our Aβ channels consist of the solid-state NMR-based U-shaped β-strand-turn-β-strand motif. In the simulations we obtain ion-permeable channels whose subunit mo...

  14. Shift reagents in ion mobility spectrometry: the effect of the number of interaction sites, size and interaction energies on the mobilities of valinol and ethanolamine.

    Science.gov (United States)

    Fernández-Maestre, Roberto; Meza-Morelos, Dairo; Wu, Ching

    2016-05-01

    Overlapping peaks interfere in ion mobility spectrometry (IMS), but they are separated introducing mobility shift reagents (SR) in the buffer gas forming adducts with different collision cross-sections (size). IMS separations using SR depend on the ion mobility shifts which are governed by adduct's size and interaction energies (stabilities). Mobility shifts of valinol and ethanolamine ions were measured by electrospray-ionization ion mobility-mass spectrometry (MS). Methyl-chloro propionate (M) was used as SR; 2-butanol (B) and nitrobenzene (N) were used for comparison. Density functional theory was used for calculations. B produced the smallest mobility shifts because of its small size. M and N have two strong interaction sites (oxygen atoms) and similar molecular mass, and they should produce similar shifts. For both ethanolamine and valinol ions, stabilities were larger for N adducts than those of M. With ethanolamine, M produced a 68% shift, large compared to that using N, 61%, because M has a third weak interaction site on the chlorine atom and, therefore, M has more interaction possibilities than N. This third site overrode the oxygen atoms' interaction energy that favored the adduction of ethanolamine with N over that with M. On the contrary, with valinol mobility shifts were larger with N than with M (21 vs 18%) because interaction energy favored even more adduction of valinol with N than with M; that is, the interaction energy difference between adducts of valinol with M and N was larger than that between those adducts with ethanolamine, and the third M interaction could not override this larger difference. Mobility shifts were explained based on the number of SR's interaction sites, size of ions and SR, and SR-ion interaction energies. This is the first time that the number of interaction sites is used to explain mobility shifts in SR-assisted IMS. Copyright © 2016 John Wiley & Sons, Ltd.

  15. Simple Waveforms, Simply Described

    Science.gov (United States)

    Baker, John G.

    2008-01-01

    Since the first Lazarus Project calculations, it has been frequently noted that binary black hole merger waveforms are 'simple.' In this talk we examine some of the simple features of coalescence and merger waveforms from a variety of binary configurations. We suggest an interpretation of the waveforms in terms of an implicit rotating source. This allows a coherent description, of both the inspiral waveforms, derivable from post-Newtonian(PN) calculations, and the numerically determined merger-ringdown. We focus particularly on similarities in the features of various Multipolar waveform components Generated by various systems. The late-time phase evolution of most L these waveform components are accurately described with a sinple analytic fit. We also discuss apparent relationships among phase and amplitude evolution. Taken together with PN information, the features we describe can provide an approximate analytic description full coalescence wavefoRms. complementary to other analytic waveforns approaches.

  16. T-wave ion mobility-mass spectrometry: basic experimental procedures for protein complex analysis.

    Science.gov (United States)

    Michaelevski, Izhak; Kirshenbaum, Noam; Sharon, Michal

    2010-07-31

    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 N(2;)) 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 (Omega). 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 Omega is related to the overall shape and topology of the ion. The correlation between the measured drift time values and Omega is calculated using a calibration curve generated from calibrant proteins with defined cross-sections(1). 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 conditions(1). Several recent IM studies of both individual proteins(2,3) and non-covalent protein complexes(4-9), 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

  17. Influence of the coupling between an atmospheric pressure ion mobility spectrometer and the low pressure ion inlet of a mass spectrometer on the mobility measurement

    Directory of Open Access Journals (Sweden)

    Gunzer Frank

    2016-01-01

    Full Text Available Ion mobility spectrometers (IMS are versatile gas analyzers. Due to their small size and robustness, combined with a very high sensitivity, they are often used in gas sensing applications such as environmental monitoring. In order to improve the selectivity, they are typically combined with a mass spectrometer (MS. Since IMS works at atmospheric pressure, and MS works at vacuum, a special interface reducing the pressure over normally two stages has to be used. In this paper the influence of this coupling of different pressure areas on the IMS signal will be analyzed with help of finite elements method simulations.

  18. Affecting proton mobility in activated peptide and whole protein ions via lysine guanidination.

    Science.gov (United States)

    Pitteri, Sharon J; Reid, Gavin E; McLuckey, Scott A

    2004-01-01

    We have evaluated the effect of lysine guanidination in peptides and proteins on the dissociation of protonated ions in the gas phase. The dissociation of guanidinated model peptide ions compared to their unmodified forms showed behavior consistent with concepts of proton mobility as a major factor in determining favored fragmentation channels. Reduction of proton mobility associated with lysine guanidination was reflected by a relative increase in cleavages occurring C-terminal to aspartic acid residues as well as increases in small molecule losses. To evaluate the effect of guanidination on the dissociation behavior of whole protein ions, bovine ubiquitin was selected as a model. Essentially, all of the amide bond cleavages associated with the +10 charge state of fully guanidinated ubiquitin were observed to occur C-terminal to aspartic acid residues, unlike the dissociation behavior of the +10 ion of the unmodified protein, where competing cleavage N-terminal to proline and nonspecific amide bond cleavages were also observed. The +8 and lower charge states of the guanidinated protein showed prominent losses of small neutral molecules. This overall fragmentation behavior is consistent with current hypotheses regarding whole protein dissociation that consider proton mobility and intramolecular charge solvation as important factors in determining favored dissociation channels, and are also consistent with the fragmentation behaviors observed for the guanidinated model peptide ions. Further evaluation of the utility of condensed phase guanidination of whole proteins is necessary but the results described here confirm that guanidination can be an effective strategy for enhancing C-terminal aspartic acid cleavages. Gas phase dissociation exclusively at aspartic acid residues, especially for whole protein ions, could be useful in identifying and characterizing proteins via tandem mass spectrometry of whole protein ions.

  19. Atmospheric pressure ionization and gas phase ion mobility studies of isomeric dihalogenated benzenes using different ionization techniques

    Science.gov (United States)

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

    2004-03-01

    Ion mobility spectrometry (IMS) featuring different ionization techniques was used to analyze isomeric ortho-, meta- and para-dihalogenated benzenes in order to assess how structural features affect ion formation and drift behavior. The structure of the product ions formed was investigated by atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and IMS-MS coupling. Photoionization provided [M]+ ions for chlorinated and fluorinated compounds while bromine was cleaved from isomers of dibromobenzene and bromofluorobenzene. This ionization technique does not permit the different isomers to be distinguished. Comparable ions and additional clustered ions were obtained using 63Ni ionization. Depending on the chemical constitution, different clustered ions were observed in ion mobility spectra for the separate isomers of dichlorobenzene and dibromobenzene. Corona discharge ionization permits the most sensitive detection of dihalogenated compounds. Only clustered product ions were obtained. Corona discharge ionization enables the classification of different structural isomers of dichlorobenzene, dibromobenzene and bromofluorobenzene.

  20. Development of an ion mobility spectrometer with UV ionization source to detect ketones and BTX

    Science.gov (United States)

    Ni, Kai; Guo, Jingran; Ou, Guangli; Lei, Yu; Wang, Xiaohao

    2014-11-01

    Ion mobility spectrometry (IMS) is an attractive material analysis technology for developing a miniaturized volatile organic compounds (VOCs) on-site monitoring sensor. Having simple instrumentation, IMS is especially suitable when portability and sensitivity are required. In this work, we designed an ion mobility spectrometer with UV ionization. The geometric parameters of the UV-IMS were optimized based on a numerical simulation. The simulation results demonstrated that the drift electric field in the drift region was approximately homogenous and in the reaction region had an ion focusing effect, which could improve the sensitivity and resolving power of the IMS. The UV-IMS has been constructed and used to detect VOCs, such as acetone, benzene, toluene and m-xylene (BTX). The resolution of these substance measured from the UV-IMS in the atmospheric conditions are about 30 and the limit of detection (LOD) is low to ppmv. The ion mobility module and electric circuit are integrated in a main PCB, which can facilitate mass production and miniaturization. The present UV-IMS is expected to become a tool of choice for the on-site monitoring for VOCs.

  1. Travelling-wave ion mobility mass spectrometry and negative ion fragmentation of hybrid and complex N-glycans.

    Science.gov (United States)

    Harvey, David J; Scarff, Charlotte A; Edgeworth, Matthew; Pagel, Kevin; Thalassinos, Konstantinos; Struwe, Weston B; Crispin, Max; Scrivens, James H

    2016-11-01

    Nitrogen collisional cross sections (CCSs) of hybrid and complex glycans released from the glycoproteins IgG, gp120 (from human immunodeficiency virus), ovalbumin, α1-acid glycoprotein and thyroglobulin were measured with a travelling-wave ion mobility mass spectrometer using dextran as the calibrant. The utility of this instrument for isomer separation was also investigated. Some isomers, such as Man3 GlcNAc3 from chicken ovalbumin and Man3 GlcNAc3 Fuc1 from thyroglobulin could be partially resolved and identified by their negative ion fragmentation spectra obtained by collision-induced decomposition (CID). Several other larger glycans, however, although existing as isomers, produced only asymmetric rather than separated arrival time distributions (ATDs). Nevertheless, in these cases, isomers could often be detected by plotting extracted fragment ATDs of diagnostic fragment ions from the negative ion CID spectra obtained in the transfer cell of the Waters Synapt mass spectrometer. Coincidence in the drift times of all fragment ions with an asymmetric ATD profile in this work, and in the related earlier paper on high-mannose glycans, usually suggested that separations were because of conformers or anomers, whereas symmetrical ATDs of fragments showing differences in drift times indicated isomer separation. Although some significant differences in CCSs were found for the smaller isomeric glycans, the differences found for the larger compounds were usually too small to be analytically useful. Possible correlations between CCSs and structural types were also investigated, and it was found that complex glycans tended to have slightly smaller CCSs than high-mannose glycans of comparable molecular weight. In addition, biantennary glycans containing a core fucose and/or a bisecting GlcNAc residue fell on different mobility-m/z trend lines to those glycans not so substituted with both of these substituents contributing to larger CCSs. Copyright © 2016 John Wiley & Sons

  2. Lifetimes and stabilities of familiar explosives molecular adduct complexes during ion mobility measurements

    Science.gov (United States)

    McKenzie, Alan; DeBord, John Daniel; Ridgeway, Mark; Park, Melvin; Eiceman, Gary; Fernandez-Lima, Francisco

    2015-01-01

    Trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) was utilized for the separation and identification of familiar explosives in complex mixtures. For the first time, molecular adduct complex lifetimes, relative stability, binding energies and candidate structures are reported for familiar explosives. Experimental and theoretical results showed that the adduct size and reactivity, complex binding energy and the explosive structure tailors the stability of the molecular adduct complex. TIMS flexibility to adapt the mobility separation as a function of the molecular adduct complex stability (i.e., short or long IMS experiments / low or high IMS resolution) permits targeted measurements of explosives in complex mixtures with higher confidence levels. PMID:26153567

  3. Unfolding of Hydrated Alkyl Diammonium Cations Revealed by Cryogenic Ion Mobility-Mass Spectrometry.

    Science.gov (United States)

    Servage, Kelly A; Fort, Kyle L; Silveira, Joshua A; Shi, Liuqing; Clemmer, David E; Russell, David H

    2015-07-22

    Hydration of the ammonium ion plays a key role in determining the biomolecular structure as well as local structure of water in aqueous environments. Experimental data obtained by cryogenic ion mobility-mass spectrometry (cryo-IM-MS) show that dehydration of alkyl diammonium cations induces a distinct unfolding transition at a critical number of water molecules, n = 21 to 23, n = 24 to 26, and n = 27 to 29, for 1,7-diaminoheptane, 1,8-diaminooctane, and 1,10-diaminodecane, respectively. Results are also presented that reveal compelling evidence for unique structural transitions of hydrated ammonium ions associated with the development of the hydrogen-bond network around individual charged groups. The ability to track the evolution of structure upon stepwise dehydration provides direct insight into the intricate interplay between solvent-molecule interactions that are responsible for defining conformations. Such insights are potentially valuable in understanding how ammonium ion solvation influences conformation(s) of larger biomolecules.

  4. Reactant ion chemistry for detection of TNT, RDX, and PETN using an ion mobility spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Klassen, S.E.; Rodacy, P.; Silva, R.

    1997-09-01

    This report describes the responses of three energetic materials (TNT, RDX, and PETN) to varying reactant ion chemistries and IMS cell temperatures. The following reactant ion chemistries were evaluated; air-dry; air-wet; methylene chloride-dry; methylene chloride-wet; methylene bromide-dry; nitrogen dioxide-wet; sulfur dioxide-wet. The temperature was varied between 160 - 220{degrees}C.

  5. Prediction of peptide drift time in ion mobility mass spectrometry from sequence-based features

    KAUST Repository

    Wang, Bing

    2013-05-09

    Background: Ion mobility-mass spectrometry (IMMS), an analytical technique which combines the features of ion mobility spectrometry (IMS) and mass spectrometry (MS), can rapidly separates ions on a millisecond time-scale. IMMS becomes a powerful tool to analyzing complex mixtures, especially for the analysis of peptides in proteomics. The high-throughput nature of this technique provides a challenge for the identification of peptides in complex biological samples. As an important parameter, peptide drift time can be used for enhancing downstream data analysis in IMMS-based proteomics.Results: In this paper, a model is presented based on least square support vectors regression (LS-SVR) method to predict peptide ion drift time in IMMS from the sequence-based features of peptide. Four descriptors were extracted from peptide sequence to represent peptide ions by a 34-component vector. The parameters of LS-SVR were selected by a grid searching strategy, and a 10-fold cross-validation approach was employed for the model training and testing. Our proposed method was tested on three datasets with different charge states. The high prediction performance achieve demonstrate the effectiveness and efficiency of the prediction model.Conclusions: Our proposed LS-SVR model can predict peptide drift time from sequence information in relative high prediction accuracy by a test on a dataset of 595 peptides. This work can enhance the confidence of protein identification by combining with current protein searching techniques. 2013 Wang et al.; licensee BioMed Central Ltd.

  6. Analysis of explosives using corona discharge ionization combined with ion mobility spectrometry-mass spectrometry.

    Science.gov (United States)

    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). © 2013 Elsevier B.V. All rights reserved.

  7. Investigation of the lithium ion mobility in cyclic model compounds and their ion conduction properties

    Energy Technology Data Exchange (ETDEWEB)

    Thielen, Joerg

    2011-07-27

    In view of both, energy density and energy drain, rechargeable lithium ion batteries outperform other present accumulator systems. However, despite great efforts over the last decades, the ideal electrolyte in terms of key characteristics such as capacity, cycle life, and most important reliable safety, has not yet been identified. Steps ahead in lithium ion battery technology require a fundamental understanding of lithium ion transport, salt association, and ion solvation within the electrolyte. Indeed, well defined model compounds allow for systematic studies of molecular ion transport. Thus, in the present work, based on the concept of immobilizing ion solvents, three main series with a cyclotriphosphazene (CTP), hexaphenylbenzene (HBP), and tetramethylcyclotetrasiloxane (TMS) scaffold were prepared. Lithium ion solvents, among others ethylene carbonate (EC), which has proven to fulfill together with propylene carbonate safety and market concerns in commercial lithium ion batteries, were attached to the different cores via alkyl spacers of variable length. All model compounds were fully characterized, pure and thermally stable up to at least 235 C, covering the requested broad range of glass transition temperatures from -78.1 C up to +6.2 C. While the CTP models tend to rearrange at elevated temperatures over time, which questions the general stability of alkoxide related (poly)phosphazenes, both, the HPB and CTP based models show no evidence of core stacking. In particular the CTP derivatives represent good solvents for various lithium salts, exhibiting no significant differences in the ionic conductivity {sigma}{sub dc} and thus indicating comparable salt dissociation and rather independent motion of cations and ions. In general, temperature-dependent bulk ionic conductivities investigated via impedance spectroscopy follow a William-Landel-Ferry (WLF) type behavior. Modifications of the alkyl spacer length were shown to influence ionic conductivities only in

  8. Lithium-ion battery electrolyte mobility at nano-confined graphene interfaces

    Science.gov (United States)

    Moeremans, Boaz; Cheng, Hsiu-Wei; Hu, Qingyun; Garces, Hector F.; Padture, Nitin P.; Renner, Frank Uwe; Valtiner, Markus

    2016-08-01

    Interfaces are essential in electrochemical processes, providing a critical nanoscopic design feature for composite electrodes used in Li-ion batteries. Understanding the structure, wetting and mobility at nano-confined interfaces is important for improving the efficiency and lifetime of electrochemical devices. Here we use a Surface Forces Apparatus to quantify the initial wetting of nanometre-confined graphene, gold and mica surfaces by Li-ion battery electrolytes. Our results indicate preferential wetting of confined graphene in comparison with gold or mica surfaces because of specific interactions of the electrolyte with the graphene surface. In addition, wetting of a confined pore proceeds via a profoundly different mechanism compared with wetting of a macroscopic surface. We further reveal the existence of molecularly layered structures of the confined electrolyte. Nanoscopic confinement of less than 4-5 nm and the presence of water decrease the mobility of the electrolyte. These results suggest a lower limit for the pore diameter in nanostructured electrodes.

  9. Advancing the High Throughput Identification of Liver Fibrosis Protein Signatures Using Multiplexed Ion Mobility Spectrometry*

    Science.gov (United States)

    Baker, Erin Shammel; Burnum-Johnson, Kristin E.; Jacobs, Jon M.; Diamond, Deborah L.; Brown, Roslyn N.; Ibrahim, Yehia M.; Orton, Daniel J.; Piehowski, Paul D.; Purdy, David E.; Moore, Ronald J.; Danielson, William F.; Monroe, Matthew E.; Crowell, Kevin L.; Slysz, Gordon W.; Gritsenko, Marina A.; Sandoval, John D.; LaMarche, Brian L.; Matzke, Melissa M.; Webb-Robertson, Bobbie-Jo M.; Simons, Brenna C.; McMahon, Brian J.; Bhattacharya, Renuka; Perkins, James D.; Carithers, Robert L.; Strom, Susan; Self, Steven G.; Katze, Michael G.; Anderson, Gordon A.; Smith, Richard D.

    2014-01-01

    Rapid diagnosis of disease states using less invasive, safer, and more clinically acceptable approaches than presently employed is a crucial direction for the field of medicine. While MS-based proteomics approaches have attempted to meet these objectives, challenges such as the enormous dynamic range of protein concentrations in clinically relevant biofluid samples coupled with the need to address human biodiversity have slowed their employment. Herein, we report on the use of a new instrumental platform that addresses these challenges by coupling technical advances in rapid gas phase multiplexed ion mobility spectrometry separations with liquid chromatography and MS to dramatically increase measurement sensitivity and throughput, further enabling future high throughput MS-based clinical applications. An initial application of the liquid chromatography - ion mobility spectrometry-MS platform analyzing blood serum samples from 60 postliver transplant patients with recurrent fibrosis progression and 60 nontransplant patients illustrates its potential utility for disease characterization. PMID:24403597

  10. Advancing the high throughput identification of liver fibrosis protein signatures using multiplexed ion mobility spectrometry.

    Science.gov (United States)

    Baker, Erin Shammel; Burnum-Johnson, Kristin E; Jacobs, Jon M; Diamond, Deborah L; Brown, Roslyn N; Ibrahim, Yehia M; Orton, Daniel J; Piehowski, Paul D; Purdy, David E; Moore, Ronald J; Danielson, William F; Monroe, Matthew E; Crowell, Kevin L; Slysz, Gordon W; Gritsenko, Marina A; Sandoval, John D; Lamarche, Brian L; Matzke, Melissa M; Webb-Robertson, Bobbie-Jo M; Simons, Brenna C; McMahon, Brian J; Bhattacharya, Renuka; Perkins, James D; Carithers, Robert L; Strom, Susan; Self, Steven G; Katze, Michael G; Anderson, Gordon A; Smith, Richard D

    2014-04-01

    Rapid diagnosis of disease states using less invasive, safer, and more clinically acceptable approaches than presently employed is a crucial direction for the field of medicine. While MS-based proteomics approaches have attempted to meet these objectives, challenges such as the enormous dynamic range of protein concentrations in clinically relevant biofluid samples coupled with the need to address human biodiversity have slowed their employment. Herein, we report on the use of a new instrumental platform that addresses these challenges by coupling technical advances in rapid gas phase multiplexed ion mobility spectrometry separations with liquid chromatography and MS to dramatically increase measurement sensitivity and throughput, further enabling future high throughput MS-based clinical applications. An initial application of the liquid chromatography--ion mobility spectrometry-MS platform analyzing blood serum samples from 60 postliver transplant patients with recurrent fibrosis progression and 60 nontransplant patients illustrates its potential utility for disease characterization.

  11. EM∩IM: software for relating ion mobility mass spectrometry and electron microscopy data.

    Science.gov (United States)

    Degiacomi, Matteo T; Benesch, Justin L P

    2016-01-07

    We present EM∩IM, software that allows the calculation of collision cross-sections from electron density maps obtained for example by means of transmission electron microscopy. This allows the assessment of structures other than those described by atomic coordinates with ion mobility mass spectrometry data, and provides a new means for contouring and validating electron density maps. EM∩IM thereby facilitates the use of data obtained in the gas phase within structural biology studies employing diverse experimental methodologies.

  12. Multi-Capillary Column-Ion Mobility Spectrometry of Volatile Metabolites Emitted by Saccharomyces Cerevisiae

    OpenAIRE

    Christoph Halbfeld; Ebert, Birgitta E.; Blank, Lars M.

    2014-01-01

    Volatile organic compounds (VOCs) produced during microbial fermentations determine the flavor of fermented food and are of interest for the production of fragrances or food additives. However, the microbial synthesis of these compounds from simple carbon sources has not been well investigated so far. Here, we analyzed the headspace over glucose minimal salt medium cultures of Saccharomyces cerevisiae using multi-capillary column-ion mobility spectrometry (MCC-IMS). The high sensitivity and f...

  13. Analyses of mouse breath with ion mobility spectrometry: a feasibility study.

    Science.gov (United States)

    Vautz, Wolfgang; Nolte, Jürgen; Bufe, Albrecht; Baumbach, Jörg I; Peters, Marcus

    2010-03-01

    Exhaled breath can provide comprehensive information about the metabolic state of the subject. Breath analysis carried out during animal experiments promises to increase the information obtained from a particular experiment significantly. This feasibility study should demonstrate the potential of ion mobility spectrometry for animal breath analysis, even for mice. In the framework of the feasibility study, an ion mobility spectrometer coupled with a multicapillary column for rapid preseparation was used to analyze the breath of orotracheally intubated spontaneously breathing mice during anesthesia for the very first time. The sampling procedure was validated successfully. Furthermore, the breath of four mice (2 healthy control mice, 2 with allergic airway inflammation) was analyzed. Twelve peaks were identified directly by comparison with a database. Additional mass spectrometric analyses were carried out for validation and for identification of unknown signals. Significantly different patterns of metabolites were detected in healthy mice compared with asthmatic mice, thus demonstrating the feasibility of analyzing mouse breath with ion mobility spectrometry. However, further investigations including a higher animal number for validation and identification of unknown signals are needed. Nevertheless, the results of the study demonstrate that the method is capable of rapid analyses of the breath of mice, thus significantly increasing the information obtained from each particular animal experiment.

  14. A compact high-resolution X-ray ion mobility spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Reinecke, T.; Kirk, A. T.; Heptner, A.; Niebuhr, D.; Böttger, S.; Zimmermann, S. [Department of Sensors and Measurement Technology, Institute of Electrical Engineering and Measurement Technology, Leibniz Universität Hannover, Appelstr. 9A, 30167 Hannover (Germany)

    2016-05-15

    For the ionization of gaseous samples, most ion mobility spectrometers employ radioactive ionization sources, e.g., containing {sup 63}Ni or {sup 3}H. Besides legal restrictions, radioactive materials have the disadvantage of a constant radiation with predetermined intensity. In this work, we replaced the {sup 3}H source of our previously described high-resolution ion mobility spectrometer with 75 mm drift tube length with a commercially available X-ray source. It is shown that the current configuration maintains the resolving power of R = 100 which was reported for the original setup containing a {sup 3}H source. The main advantage of an X-ray source is that the intensity of the radiation can be adjusted by varying its operating parameters, i.e., filament current and acceleration voltage. At the expense of reduced resolving power, the sensitivity of the setup can be increased by increasing the activity of the source. Therefore, the performance of the setup can be adjusted to the specific requirements of any application. To investigate the relation between operating parameters of the X-Ray source and the performance of the ion mobility spectrometer, parametric studies of filament current and acceleration voltage are performed and the influence on resolving power, peak height, and noise is analyzed.

  15. Differential Ion Mobility Separations in up to 100% Helium Using Microchips

    Energy Technology Data Exchange (ETDEWEB)

    Shvartsburg, Alexandre A.; Ibrahim, Yehia M.; Smith, Richard D.

    2014-01-09

    The performance of differential IMS (FAIMS) analyzers is much enhanced by gases comprising He, especially He/N2 buffers. However, electrical breakdown has limited the He fraction in those mixtures to ~50 - 75%, depending on the field strength. By Paschen law, the threshold field for breakdown increases at shorter distances. This allows FAIMS using chips with microscopic channels to utilize much stronger field intensities (E) than “full-size” analyzers with wider gaps. Here we show that those chips can employ higher He fractions up to 100%. Use of He-rich gases improves the resolution and resolution/sensitivity balance substantially, although less than for full-size analyzers. The optimum He fraction is ~80%, in line with first-principles theory. Hence one can now measure the dependences of ion mobility on E in pure He, where ion-molecule cross section calculations are much more tractable than in other gases that form deeper and more complex interaction potentials. This capability may facilitate quantitative modeling of high-field ion mobility behavior and thus FAIMS separation properties, which would enable a priori extraction of structural information about the ions from FAIMS data.

  16. Differential ion mobility separations in up to 100% helium using microchips.

    Science.gov (United States)

    Shvartsburg, Alexandre A; Ibrahim, Yehia M; Smith, Richard D

    2014-03-01

    The performance of differential IMS (FAIMS) analyzers is much enhanced by gases comprising He, especially He/N2 mixtures. However, electrical breakdown has limited the He fraction to ~50%-75%, depending on the field strength. By the Paschen law, the threshold field for breakdown increases at shorter distances. This allows FAIMS using chips with microscopic channels to utilize much stronger field intensities (E) than "full-size" analyzers with wider gaps. Here we show that those chips can employ higher He fractions up to 100%. Use of He-rich gases improves the resolution and resolution/sensitivity balance substantially, although less than for full-size analyzers. The optimum He fraction is ~80%, in line with first-principles theory. Hence, one can now measure the dependences of ion mobility on E in pure He, where ion-molecule cross section calculations are much more tractable than in other gases that form deeper and more complex interaction potentials. This capability may facilitate quantitative modeling of high-field ion mobility behavior and, thus, FAIMS separation properties, which would enable a priori extraction of structural information about the ions.

  17. Characterization of Polylactides with Different Stereoregularity Using Electrospray Ionization Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Kim, Kihyun; Lee, Jong Wha; Chang, Taihyun; Kim, Hugh I.

    2014-10-01

    We investigated the effect of stereoregularity on the gas-phase conformations of linear and cyclic polylactides (PLA) using electrospray ionization ion mobility mass spectrometry (ESI-IM-MS) combined with molecular dynamics simulations. IM-MS analysis of PLA ions shows intriguing difference between the collision cross section (ΩD) value of poly-L-lactide (PLLA) and poly-LD-lactide (PLDLA) ions with respect to their chain architecture and stereoregularity. In the singly sodiated linear PLA ( l-PLA•Na+) case, both l-PLLA and l-PLDLA up to 11mer have very similar ΩD values, but the ΩD values of l-PLLA are greater than that of l-PLDLA ions for larger ions. In the case of cyclic PLA ( c-PLA), c-PLLA•Na+ is more compact than c-PLDLA•Na+ for short PLA ions. However, c-PLLA exhibits larger ΩD value than c-PLDLA for PLA ions longer than 13mer. The origin of difference in the ΩD values was investigated using theoretical investigation of PLAs in the gas phase. The gas-phase conformation of PLA ions is influenced by Na+-oxygen coordination and the weak intramolecular hydrogen bond interaction, which are more effectively formed in more flexible chains. Therefore, the less flexible PLLA has a larger ΩD value than PLDLA. However, for short c-PLA, concomitant maximization of both Na+-oxygen coordination and hydrogen bond interaction is difficult due to the constricted chain freedom, which makes the ΩD value of PLAs in this range show a different trend compared with other PLA ions. Our study facilitates the understanding of correlation between stereoregularity of PLAs and their structure, providing potential utility of IM-MS to characterize stereoisomers of polymers.

  18. An MSK Radar Waveform

    Science.gov (United States)

    Quirk, Kevin J.; Srinivasan, Meera

    2012-01-01

    The minimum-shift-keying (MSK) radar waveform is formed by periodically extending a waveform that separately modulates the in-phase and quadrature- phase components of the carrier with offset pulse-shaped pseudo noise (PN) sequences. To generate this waveform, a pair of periodic PN sequences is each passed through a pulse-shaping filter with a half sinusoid impulse response. These shaped PN waveforms are then offset by half a chip time and are separately modulated on the in-phase and quadrature phase components of an RF carrier. This new radar waveform allows an increase in radar resolution without the need for additional spectrum. In addition, it provides self-interference suppression and configurable peak sidelobes. Compared strictly on the basis of the expressions for delay resolution, main-lobe bandwidth, effective Doppler bandwidth, and peak ambiguity sidelobe, it appears that bi-phase coded (BPC) outperforms the new MSK waveform. However, a radar waveform must meet certain constraints imposed by the transmission and reception of the modulation, as well as criteria dictated by the observation. In particular, the phase discontinuity of the BPC waveform presents a significant impediment to the achievement of finer resolutions in radar measurements a limitation that is overcome by using the continuous phase MSK waveform. The phase continuity, and the lower fractional out-of-band power of MSK, increases the allowable bandwidth compared with BPC, resulting in a factor of two increase in the range resolution of the radar. The MSK waveform also has been demonstrated to have an ambiguity sidelobe structure very similar to BPC, where the sidelobe levels can be decreased by increasing the length of the m-sequence used in its generation. This ability to set the peak sidelobe level is advantageous as it allows the system to be configured to a variety of targets, including those with a larger dynamic range. Other conventionally used waveforms that possess an even greater

  19. Isomer separation and gas-phase configurations of organoruthenium anticancer complexes: ion mobility mass spectrometry and modeling.

    Science.gov (United States)

    Williams, Jonathan P; Bugarcic, Tijana; Habtemariam, Abraha; Giles, Kevin; Campuzano, Iain; Rodger, P Mark; Sadler, Peter J

    2009-06-01

    We have used ion mobility-mass spectrometry combined with molecular modeling for the separation and configurational analysis of three low-molecular-weight isomeric organoruthenium anticancer complexes containing ortho-, meta-, or para-terphenyl arene ligands. The isomers were separated using ion mobility based on traveling-wave technology and the experimentally determined collision cross sections were compared to theoretical calculations. Excellent agreement was observed between the experimentally and theoretically derived measurements.

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

    Science.gov (United States)

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

    2011-02-01

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

  1. Analysis of antibiotics from liquid sample using electrospray ionization-ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Li Shu; Jia Jian; Gao Xiaoguang; He Xiuli [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China); Li Jianping, E-mail: jpli@mail.ie.ac.cn [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer The reduced mobilities of 18 antibiotics are determined. Black-Right-Pointing-Pointer Establishing antibiotic mass-mobility correlation using (12,4) potential model. Black-Right-Pointing-Pointer Multi-component characteristics of antibiotics can be revealed using ESI-IMS. Black-Right-Pointing-Pointer Most mixtures of antibiotics can be analyzed using ESI-IMS. Black-Right-Pointing-Pointer The detection limit of amoxicillin is 70 pg. - Abstract: The recent findings of antibiotic residues in aquatic environment at trace level have gained much concern for the detrimental effect on ecological and human health due to bacterial resistance. Here, the feasibility of using electrospray ionization ion mobility spectrometry (ESI-IMS) for analysis antibiotics in liquid sample is demonstrated. Reduced mobilities and collision cross sections of 18 antibiotics are experimentally measured and compared with theoretical values according to mass-mobility correlation. Gentamicin is used as an example to investigate the capability of ESI-IMS for multi-component analysis of antibiotics. Mixtures of antibiotics at different concentrations are analyzed. The estimated detection limit for amoxicillin is 0.7 mg L{sup -1} (70 pg) and the linear range of response maintains over two orders. This method will be a potential technique for the analysis of antibiotics in aquatic environment.

  2. A comparison of the ion chemistry for mono-substituted toluenes and anilines by three methods of atmospheric pressure ionization with ion mobility spectrometry.

    Science.gov (United States)

    Borsdorf, H; Neitsch, K; Eiceman, G A; Stone, J A

    2009-06-15

    Ion mobility spectra for a series of mono-substituted toluenes and a series of mono-substituted anilines were obtained using three different methods of atmospheric pressure ionization including photoionization, chemical ionization from a (63)Ni source, and chemical ionization from a corona discharge source. The product ion peak intensities were measured as functions of analyte concentration at 323 K in a purified air atmosphere. Two, and sometimes three, product ion peaks were observed in spectra from chemical ionization with the (63)Ni source and it is suggested that the major peak, due to the protonated molecule, arose in both series by proton transfer from H3O+(H2O)n. The second peak with diminished intensity and longer drift time than the protonated molecule can be seen with the toluenes and was understood to be the NO+ adduct, formed from the reactant ion NO+(H2O)n. Electron transfer from the anilines to the latter ion yields the molecular ions, identified by having the same reduced mobility coefficients as the molecular ions produced by photoionization. The structure of these product ions was determined by investigations using the coupling of ion mobility spectrometry with atmospheric pressure photoionization and mass spectrometry (APPI-IMS-MS). The relative abundances of both the NO+ adducts with the toluenes and the molecular ions with the anilines are enhanced with a corona discharge source where relatively more NO+(H2O)n is produced than in a (63)Ni source. Ab initio calculations show that only the protonated anilines of all the product ions are significantly hydrated with 1 ppm(v) of moisture in the supporting atmosphere of the ion mobility spectrometer.

  3. Combined Use of Post-Ion Mobility/Collision-Induced Dissociation and Chemometrics for b Fragment Ion Analysis

    Science.gov (United States)

    Zekavat, Behrooz; Miladi, Mahsan; Becker, Christopher; Munisamy, Sharon M.; Solouki, Touradj

    2013-09-01

    Although structural isomers may yield indistinguishable ion mobility (IM) arrival times and similar fragment ions in tandem mass spectrometry (MS), it is demonstrated that post-IM/collision-induced dissociation MS (post-IM/CID MS) combined with chemometrics can enable independent study of the IM-overlapped isomers. The new approach allowed us to investigate the propensity of selected b type fragment ions from AlaAlaAlaHisAlaAlaAla-NH2 (AAA(His)AAA) heptapeptide to form different isomers. Principle component analysis (PCA) of the unresolved post-IM/CID profiles indicated the presence of two different isomer types for b4 +, b5 +, and b6 + and a single isomer type for b7 + fragments of AAA(His)AAA. We employed a simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) to calculate the total IM profiles and CID mass spectra of b fragment isomers. The deconvoluted CID mass spectra showed discernible fragmentation patterns for the two isomers of b4 +, b5 +, and b6 + fragments. Under our experimental conditions, calculated percentages of the "cyclic" isomers (at the 95 % confidence level for n = 3) for b4 +, b5 +, and b6 + were 61 (± 5) %, 36 (± 5) %, and 48 (± 2) %, respectively. Results from the SIMPLISMA deconvolution of b5 + species resembled the CID MS patterns of fully resolved IM profiles for the two b5 + isomers. The "cyclic" isomers for each of the two-component b fragment ions were less susceptible to ion fragmentation than their "linear" counterparts.

  4. Ion mobility spectrometry-mass spectrometry studies of ion processes in air at atmospheric pressure and their application to thermal desorption of 2,4,6-trinitrotoluene

    Science.gov (United States)

    Sabo, Martin; Malásková, Michaela; Matejčík, Štefan

    2014-02-01

    In this study we have investigated the negative reactant ion formation in a negative corona discharge (CD) using the corona discharge ion mobility spectrometry orthogonal acceleration time-of-flight (CD-IMS-oaTOF) technique. The reactant ions were formed in the CD operating in the reverse gas flow mode at an elevated temperature of 363.5 K in synthetic and ambient air. Under these conditions mainly O_{2}^{-} and their clusters were formed. We have also studied the influence of CCl4 admixture to air (dopant gas) on the composition of the reactant ions, which resulted in the formation of Cl- and its clusters with a reduced ion mobility of 3.05 cm2 V-1 s-1 as a major reactant ion peak. Additional IMS peaks with reduced ion mobilities of 2.49, 2.25 and 2.03 cm2 V-1 s-1 were detected, and Cl- · (NO2) and Cl- · (NO)n(n = 2, 3) anions were identified. The negative reactant ions were used to detect 2,4,6 trinitrotoluene (TNT) using the thermal desorption (TD) technique using a CD-IMS instrument. Using TD sampling and a negative CD ion source doped by CCl4 we have achieved a limit of detection of 350 pg for direct surface analysis of TNT.

  5. Enhancing glycan isomer separations with metal ions and positive and negative polarity ion mobility spectrometry-mass spectrometry analyses

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun; Zhang, Xing; Schocker, Nathaniel S.; Renslow, Ryan S.; Orton, Daniel J.; Khamsi, Jamal; Ashmus, Roger A.; Almeida, Igor C.; Tang, Keqi; Costello, Catherine E.; Smith, Richard D.; Michael, Katja; Baker, Erin S.

    2016-09-07

    Glycomics has become an increasingly important field of research since glycans play critical roles in biology processes ranging from molecular recognition and signaling to cellular communication. Glycans often conjugate with other biomolecules such as proteins and lipids, and alter their properties and functions, so understanding the effect glycans have on cellular systems is essential. However the analysis of glycans is extremely difficult due to their complexity and structural diversity (i.e., the number and identity of monomer units, and configuration of their glycosidic linkages and connectivities). In this work, we coupled ion mobility spectrometry with mass spectrometry (IMS-MS) to characterize glycan standards and biologically important isomers of synthetic αGal-containing O-glycans including glycotopes of the protozoan parasite Trypanosoma cruzi, which is the causative agent of Chagas disease. IMS-MS results showed significant differences for the glycan structural isomers when analyzed in positive and negative polarity and complexed with different metal cations. These results suggest specific metal ions or ion polarities could be used to target and baseline separate glycan isomers of interest with IMS-MS.

  6. Dopant-assisted negative photoionization ion mobility spectrometry for sensitive detection of explosives.

    Science.gov (United States)

    Cheng, Shasha; Dou, Jian; Wang, Weiguo; Chen, Chuang; Hua, Lei; Zhou, Qinghua; Hou, Keyong; Li, Jinghua; Li, Haiyang

    2013-01-02

    Ion mobility spectrometry (IMS) is a key trace detection technique for explosives and the development of a simple, stable, and efficient nonradioactive ionization source is highly demanded. A dopant-assisted negative photoionization (DANP) source has been developed for IMS, which uses a commercial VUV krypton lamp to ionize acetone as the source of electrons to produce negative reactant ions in air. With 20 ppm of acetone as the dopant, a stable current of reactant ions of 1.35 nA was achieved. The reactant ions were identified to be CO(3)(-)(H(2)O)(n) (K(0) = 2.44 cm(2) V(-1) s(-1)) by atmospheric pressure time-of-flight mass spectrometry, while the reactant ions in (63)Ni source were O(2)(-)(H(2)O)(n) (K(0) = 2.30 cm(2) V(-1) s(-1)). Finally, its capabilities for detection of common explosives including ammonium nitrate fuel oil (ANFO), 2,4,6-trinitrotoluene (TNT), N-nitrobis(2-hydroxyethyl)amine dinitrate (DINA), and pentaerythritol tetranitrate (PETN) were evaluated, and the limits of detection of 10 pg (ANFO), 80 pg (TNT), and 100 pg (DINA) with a linear range of 2 orders of magnitude were achieved. The time-of-flight mass spectra obtained with use of DANP source clearly indicated that PETN and DINA can be directly ionized by the ion-association reaction of CO(3)(-) to form PETN·CO(3)(-) and DINA·CO(3)(-) adduct ions, which result in good sensitivity for the DANP source. The excellent stability, good sensitivity, and especially the better separation between the reactant and product ion peaks make the DANP a potential nonradioactive ionization source for IMS.

  7. Dopant titrating ion mobility spectrometry for trace exhaled nitric oxide detection.

    Science.gov (United States)

    Peng, Liying; Hua, Lei; Li, Enyou; Wang, Weiguo; Zhou, Qinghua; Wang, Xin; Wang, Changsong; Li, Jinghua; Li, Haiyang

    2015-01-05

    Ion mobility spectrometry (IMS) is a promising non-invasive tool for the analysis of exhaled gas and exhaled nitric oxide (NO), a biomarker for diagnosis of respiratory diseases. However, the high moisture in exhaled gas always brings about extra overlapping ion peaks and results in poor identification ability. In this paper, p-benzoquinone (PBQ) was introduced into IMS to eliminate the interference of overlapping ion peaks and realize the selective identification of NO. The overlapping ions caused by moisture were titrated by PBQ and then converted to hydrated PBQ anions (C6H4[Formula: see text](H2O)n). The NO concentration could be determined by quantifying gas phase hydrated nitrite anions (N[Formula: see text](H2O)n), product ions of NO. Under optimized conditions, a limit of detection (LOD) of about 1.4 ppbv and a linear range of 10-200 ppbv were obtained for NO even in 100% relative humidity (RH) purified air. Furthermore, this established method was applied to measure hourly the exhaled NO of eight healthy volunteers, and real-time monitoring the exhaled NO of an esophageal carcinoma patient during radical surgery. These results revealed the potential of the current dopant titrating IMS method in the measurement of exhaled NO for medical disease diagnosis.

  8. Experimental Ion Mobility measurements in Ne-CO$_2$ and CO$_2$-N$_2$ mixtures

    CERN Document Server

    Encarnação, P.M.C.C.; Veenhof, R.; Neves, P.N.B.; Santos, F.P.; Trindade, A.M.F.; Borges, F.I.G.M.; Conde, C.A.N.

    2016-01-01

    In this paper we present the experimental results for the mobility, K0, of ions in neon-carbon dioxide (Ne-CO2) and carbon dioxide-nitrogen (CO2-N2) gaseous mixtures for total pressures ranging from 8–12 Torr, reduced electric fields in the 10–25 Td range, at room temperature. Regarding the Ne-CO2 mixture only one peak was observed for CO2 concentrations above 25%, which has been identified as an ion originated in CO2, while below 25% of CO2 a second-small peak appears at the left side of the main peak, which has been attributed to impurities. The mobility values for the main peak range between 3.51 ± 0.05 and 1.07 ± 0.01 cm2V−1s−1 in the 10%-99% interval of CO2, and from 4.61 ± 0.19 to 3.00 ± 0.09 cm2V−1s−1 for the second peak observed (10%–25% of CO2). For the CO2-N2, the time-of-arrival spectra displayed only one peak for CO2 concentrations above 10%, which was attributed to ions originated in CO2, namely CO2+(CO2), with a second peak appearing for CO2 concentrations below 10%. This secon...

  9. Monitoring the Effect of Metal Ions on the Mobility of Artemia salina Nauplii.

    Science.gov (United States)

    Kokkali, Varvara; Katramados, Ioannis; Newman, Jeffrey D

    2011-03-28

    This study aims to measure the effect of toxic aqueous solutions of metals on the mobility of Artemia salina nauplii by using digital image processing. The instrument consists of a camera with a macro lens, a dark chamber, a light source and a laptop computer. Four nauplii were inserted into a macro cuvette, which contained copper, cadmium, iron and zinc ions at various concentrations. The nauplii were then filmed inside the dark chamber for two minutes and the video sequence was processed by a motion tracking algorithm that estimated their mobility. The results obtained by this system were compared to the mortality assay of the Artemia salina nauplii. Despite the small number of tested organisms, this system demonstrates great sensitivity in quantifying the mobility of the nauplii, which leads to significantly lower EC50 values than those of the mortality assay. Furthermore, concentrations of parts per trillion of toxic compounds could be detected for some of the metals. The main novelty of this instrument relies in the sub-pixel accuracy of the tracking algorithm that enables robust measurement of the deterioration of the mobility of Artemia salina even at very low concentrations of toxic metals.

  10. Lifetimes and stabilities of familiar explosive molecular adduct complexes during ion mobility measurements.

    Science.gov (United States)

    McKenzie-Coe, Alan; DeBord, John Daniel; Ridgeway, Mark; Park, Melvin; Eiceman, Gary; Fernandez-Lima, Francisco

    2015-08-21

    Trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) was utilized for the separation and identification of familiar explosives in complex mixtures. For the first time, molecular adduct complex lifetimes, relative stability, binding energies and candidate structures are reported for familiar explosives. Experimental and theoretical results showed that the adduct size and reactivity, complex binding energy and the explosive structure tailor the stability of the molecular adduct complex. The flexibility of TIMS to adapt the mobility separation as a function of the molecular adduct complex stability (i.e., short or long IMS experiments/low or high IMS resolution) permits targeted measurements of explosives in complex mixtures with high confidence levels.

  11. Size Exclusion Chromatography-Ion Mobility-Mass Spectrometry Coupling: a Step Toward Structural Biology.

    Science.gov (United States)

    Van der Rest, Guillaume; Halgand, Frédéric

    2017-09-20

    Noncovalent interactions are essential for the structural organization of biomacromolecules in cells. For this reason, the study of the biophysical, dynamic, and architectural interactions among biomacromolecules is essential. Since mass spectrometry requires compatible solutions while preserving the noncovalent bonding network, we envisioned that size exclusion chromatography coupled with ion mobility and mass spectrometry would be a valuable technique to desalt the initial sample and provide solution and gas-phase structural information in a single stage experiment. Such coupling allowed obtaining information on solution protein complex composition with SEC separation and on authenticity and purity with IMS-MS. Our study demonstrated that such coupling is compatible, useful, as well as suitable for a routine analysis, in pharmaceutical industry, for example. Mobility data were reliable and injected standards allowed calibrating the collision cross-section scale. Graphical Abstract ᅟ.

  12. High Precision Measurements of Carbon Disulfide Negative Ion Mobility and Diffusion

    CERN Document Server

    Snowden-Ifft, D P

    2013-01-01

    High precision measurements were made of mobility, lateral and longitudinal diffusion of CS2 negative ions in 40 Torr CS2 and 30 - 10 Torr CS2 - CF4. The mobility was found to be be 363.1 +/- 0.5 Torr cm2 / s V in CS2 and 408.0 +/- 0.8 Torr cm2 / s V in the CS2 - CF4 gas mixture. The lateral diffusion temperatures for these two gases (295 +/- 15 K and 297 +/- 6 K) were found to be in good agreement with room temperature. By contrast longitudinal diffusion temperature was found to be slightly elevated (319 +/- 10 (stat) +/- 8 (sys) K and 310 +/- 20 (stat) +/- 6 (sys) K) though given the errors, room temperature diffusion can not be ruled out. For lateral diffusion significant capture distances (0.21 +/- 0.07 mm and 0.15 +/- 0.03 mm) were measured while for longitudinal diffusion the results were not conclusive.

  13. Applicability of ion mobility spectrometry for detection of quarantine pests in wood

    Science.gov (United States)

    Ewing, K. J.; Sanghera, J.; Myers, S. W.; Ervin, A. M.; Carey, C.; Gleason, G.; Mosser, L.; Levy, L.; Hennessey, M. K.; Bulluck, R.

    2016-05-01

    Visual inspection is the most commonly used method for detecting quarantine pests in agricultural cargo items at ports. For example, solid wood packing material (SWPM) at ports may be a pathway for wood pests and is a frequent item of inspection at ports. The inspection process includes examination of the external surface of the item and often destructive sampling to detect internal pest targets. There are few tools available to inspectors to increase the efficiency of inspection and reduce the labor involved. Ion mobility spectrometry (IMS) has promise as an aid for inspection. Because pests emit volatile organic compounds (VOCs) such as hormone like substances, Ion Mobility Spectrometry (IMS) was investigated for possible utility for detecting pests during inspection. SWPM is a major pest pathway in trade, and fumigation of many kinds of wood, including SWPM, with methyl bromide (MeBr) following a published schedule1 is regularly conducted for phytosanitary reasons prior to shipment to the United States. However, the question remains as to how long the methyl bromide remains in the wood samples after fumigation such that it could act as an interferent to the detection of pest related VOC emissions. This work investigates the capability of ion mobility spectrometry to detect the presence of residual methyl bromide in fumigated maple and poplar wood samples at different times post fumigation up to 118 days after fumigation. Data show that MeBr can be detected in the less dense poplar wood up to 118 days after fumigation while MeBr can be detected in the denser maple wood 55 days after fumigation.

  14. Mixed mobile ion effect on a.c. conductivity of boroarsenate glasses

    Indian Academy of Sciences (India)

    M Purnima; Shashidhar Bale; Ch Srinivasu; M A Samee; Syed Rahman

    2012-06-01

    In this article we report the study of mixed mobile ion effect (MMIE) in boroarsenate glasses. DSC and a.c. electrical conductivity studies have been carried out for MgO–(25−)Li2O–50B2O3–25As2O3 glasses. It is observed that strength of MMIE in a.c. conductivity is less pronounced with increase in temperature and frequency. The results were explained on the basis of structural model (SM) proposed by Swenson and his co-workers supporting molecular dynamic results.

  15. Development of a portable preconcentrator/ion mobility spectrometer system for the trace detection of narcotics

    Energy Technology Data Exchange (ETDEWEB)

    Parmeter, J.E.; Custer, C.A.

    1997-08-01

    This project was supported by LDRD funding for the development and preliminary testing of a portable narcotics detection system. The system developed combines a commercial trace detector known as an ion mobility spectrometer (IMS) with a preconcentrator originally designed by Department 5848 for the collection of explosives molecules. The detector and preconcentrator were combined along with all necessary accessories onto a push cart, thus yielding a fully portable detection unit. Preliminary testing with both explosives and narcotics molecules shown that the system is operational, and that it can successfully detect drugs as marijuana, methamphetamine (speed), and cocaine based on their characteristics IMS signatures.

  16. Application of Ion Mobility Spectrometry (IMS) in forensic chemistry and toxicology with focus on biological matrices

    Science.gov (United States)

    Bernhard, Werner; Keller, Thomas; Regenscheit, Priska

    1995-01-01

    The IMS (Ion Mobility Spectroscopy) instrument 'Ionscan' takes advantage of the fact that trace quantities of illicit drugs are adsorbed on dust particles on clothes, in cars and on other items of evidence. The dust particles are collected on a membrane filter by a special attachment on a vacuum cleaner. The sample is then directly inserted into the spectrometer and can be analyzed immediately. We show casework applications of a forensic chemistry and toxicology laboratory. One new application of IMS in forensic chemistry is the detection of psilocybin in dried mushrooms without any further sample preparation.

  17. DSP Based Waveform Generator

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The DSP Based Waveform Generator is used for CSR Control system to control special controlled objects, such as the pulsed power supply for magnets, RF system, injection and extraction synchronization, global CSR synchronization etc. This intelligent controller based on 4800 MIPS DSP and 256M SDRAM technology will supply highly stable and highly accurate reference waveform used by the power supply of magnets. The specifications are as follows:

  18. Enhancing bottom-up and top-down proteomic measurements with ion mobility separations.

    Science.gov (United States)

    Baker, Erin Shammel; Burnum-Johnson, Kristin E; Ibrahim, Yehia M; Orton, Daniel J; Monroe, Matthew E; Kelly, Ryan T; Moore, Ronald J; Zhang, Xing; Théberge, Roger; Costello, Catherine E; Smith, Richard D

    2015-08-01

    Proteomic measurements with greater throughput, sensitivity, and structural information are essential for improving both in-depth characterization of complex mixtures and targeted studies. While LC separation coupled with MS (LC-MS) measurements have provided information on thousands of proteins in different sample types, the introduction of a separation stage that provides further component resolution and rapid structural information has many benefits in proteomic analyses. Technical advances in ion transmission and data acquisition have made ion mobility separations an opportune technology to be easily and effectively incorporated into LC-MS proteomic measurements for enhancing their information content. Herein, we report on applications illustrating increased sensitivity, throughput, and structural information by utilizing IMS-MS and LC-IMS-MS measurements for both bottom-up and top-down proteomics measurements.

  19. Formation of oxides and segregation of mobile atoms during SIMS profiling of Si with oxygen ions

    Energy Technology Data Exchange (ETDEWEB)

    Petravic, M.; Williams, J.S.; Svensson, B.G.; Conway, M. [Australian National Univ., Canberra, ACT (Australia). Research School of Physical Sciences

    1993-12-31

    An oxygen beam is commonly used in secondary ion mass spectroscopy (SIMS) analysis to enhance the ionization probability for positive secondary ions. It has been observed, however, that this technique produces in some cases a great degradation of depth resolution. The most pronounced effects have been found for impurities in silicon under oxygen bombardment at angles of incidence smaller than {approx} 30 deg from the surface normal. A new approach is described which involved broadening of SIMS profiles for some mobile atoms, such as Cu, Ni and Au, implanted into silicon. The anomalously large broadening is explained in terms of segregation at a SiO{sub 2}/Si interface formed during bombardment with oxygen at impact angles less than 30 deg. 2 refs., 1 tab., 4 figs.

  20. Ion Mobility-Mass Spectrometry Differentiates Protein Quaternary Structures Formed in Solution and in Electrospray Droplets.

    Science.gov (United States)

    Han, Linjie; Ruotolo, Brandon T

    2015-07-01

    Electrospray ionization coupled to mass spectrometry is a key technology for determining the stoichiometries of multiprotein complexes. Despite highly accurate results for many assemblies, challenging samples can generate signals for artifact protein-protein binding born of the crowding forces present within drying electrospray droplets. Here, for the first time, we study the formation of preferred protein quaternary structures within such rapidly evaporating nanodroplets. We use ion mobility and tandem mass spectrometry to investigate glutamate dehydrogenase dodecamers and serum amyloid P decamers as a function of protein concentration, along with control experiments using carefully chosen protein analogues, to both establish the formation of operative mechanisms and assign the bimodal conformer populations observed. Further, we identify an unprecedented symmetric collision-induced dissociation pathway that we link directly to the quaternary structures of the precursor ions selected.

  1. Ion mobility spectrometry: A personal view of its development at UCSB.

    Science.gov (United States)

    Bowers, Michael T

    2014-09-15

    Ion mobility is not a newly discovered phenomenon. It has roots going back to Langevin at the beginning of the 20th century. Our group initially got involved by accident around 1990 and this paper is a brief account of what has transpired here at UCSB the past 25 years in response to this happy accident. We started small, literally, with transition metal atomic ions and transitioned to carbon clusters, synthetic polymers, most types of biological molecules and eventually peptide and protein oligomeric assembly. Along the way we designed and built several generations of instruments, a process that is still ongoing. And perhaps most importantly we have incorporated theory with experiment from the beginning; a necessary wedding that allows an atomistic face to be put on the otherwise interesting but not fully informative cross section measurements.

  2. Arbitrary waveform generator

    Science.gov (United States)

    Griffin, Maurice; Sugawara, Glen

    1995-02-01

    A system for storing an arbitrary waveform on nonvolatile random access memory (NVRAM) device and generating an analog signal using the NVRAM device is described. A central processing unit is used to synthesize an arbitrary waveform and create a digital representation of the waveform and transfer the digital representation to a microprocessor which, in turn, writes the digital data into an NVRAM device which has been mapped into a portion of the microprocessor address space. The NVRAM device is removed from address space and placed into an independent waveform generation unit. In the waveform generation unit, an address clock provides an address timing signal and a cycle clock provides a transmit signal. Both signals are applied to an address generator. When both signals are present, the address generator generates and transmits to the NVRAM device a new address for each cycle of the address timing signal. In response to each new address generated, the NVRAM devices provides a digital output which is applied to a digital to analog converter. The converter produces a continuous analog output which is smoothed by a filter to produce the arbitrary waveform.

  3. Arterial waveform analysis.

    Science.gov (United States)

    Esper, Stephen A; Pinsky, Michael R

    2014-12-01

    The bedside measurement of continuous arterial pressure values from waveform analysis has been routinely available via indwelling arterial catheterization for >50 years. Invasive blood pressure monitoring has been utilized in critically ill patients, in both the operating room and critical care units, to facilitate rapid diagnoses of cardiovascular insufficiency and monitor response to treatments aimed at correcting abnormalities before the consequences of either hypo- or hypertension are seen. Minimally invasive techniques to estimate cardiac output (CO) have gained increased appeal. This has led to the increased interest in arterial waveform analysis to provide this important information, as it is measured continuously in many operating rooms and intensive care units. Arterial waveform analysis also allows for the calculation of many so-called derived parameters intrinsically created by this pulse pressure profile. These include estimates of left ventricular stroke volume (SV), CO, vascular resistance, and during positive-pressure breathing, SV variation, and pulse pressure variation. This article focuses on the principles of arterial waveform analysis and their determinants, components of the arterial system, and arterial pulse contour. It will also address the advantage of measuring real-time CO by the arterial waveform and the benefits to measuring SV variation. Arterial waveform analysis has gained a large interest in the overall assessment and management of the critically ill and those at a risk of hemodynamic deterioration.

  4. Characterization of Membrane Protein-Lipid Interactions by Mass Spectrometry Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Liu, Yang; Cong, Xiao; Liu, Wen; Laganowsky, Arthur

    2016-12-01

    Lipids in the biological membrane can modulate the structure and function of integral and peripheral membrane proteins. Distinguishing individual lipids that bind selectively to membrane protein complexes from an ensemble of lipid-bound species remains a daunting task. Recently, ion mobility mass spectrometry (IM-MS) has proven to be invaluable for interrogating the interactions between protein and individual lipids, where the complex undergoes collision induced unfolding followed by quantification of the unfolding pathway to assess the effect of these interactions. However, gas-phase unfolding experiments for membrane proteins are typically performed on the entire ensemble (apo and lipid bound species), raising uncertainty to the contribution of individual lipids and the species that are ejected in the unfolding process. Here, we describe the application of mass spectrometry ion mobility mass spectrometry (MS-IM-MS) for isolating ions corresponding to lipid-bound states of a model integral membrane protein, ammonia channel (AmtB) from Escherichia coli. Free of ensemble effects, MS-IM-MS reveals that bound lipids are ejected as neutral species; however, no correlation was found between the lipid-induced stabilization of complex and their equilibrium binding constants. In comparison to data obtained by IM-MS, there are surprisingly limited differences in stability measurements from IM-MS and MS-IM-MS. The approach described here to isolate ions of membrane protein complexes will be useful for other MS methods, such as surface induced dissociation or collision induced dissociation to determine the stoichiometry of hetero-oligomeric membrane protein complexes.

  5. Ion Mobility Measurements of Nondenatured 12-150 kDa Proteins and Protein Multimers by Tandem Differential Mobility Analysis-Mass Spectrometry (DMA-MS)

    Science.gov (United States)

    Hogan, Christopher J.; de la Mora, Juan Fernández

    2011-01-01

    The mobilities of electrosprayed proteins and protein multimers with molecular weights ranging from 12.4 kDa (cytochrome C monomers) to 154 kDa (nonspecific concanavalin A hexamers) were measured in dry air by a planar differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer (TOF-MS). The DMA determines true mobility at atmospheric pressure, without perturbing ion structure from that delivered by the electrospray. A nondenaturing aqueous 20 mM triethylammonium formate buffer yields compact ions with low charge states, moderating polarization effects on ion mobility. Conversion of mobilities into cross-sections involves a reduction factor ξ for the actual mobility relative to that associated with elastic specular collisions with smooth surfaces. ξ is known to be 1.36 in air from Millikan's oil drop experiments. A similar enhancement effect ascribed to atomic-scale surface roughness has been found in numerical simulations. Adopting Millikan's value ξ = 1.36 and assuming a spherical geometry yields a gas-phase protein density ρ p = 0.949 ± 0.053 g cm-3 for all our protein data. This is substantially higher than the 0.67 g cm-3 found in recent low-resolution DMA measurements of singly charged proteins. DMA-MS can distinguish nonspecific protein aggregates formed during the electrospray process from those formed preferentially in solution. The observed charge versus diameter relation is compatible with a protein charge reduction mechanism based on the evaporation of triethylammonium ions from electrosprayed drops.

  6. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger

    Science.gov (United States)

    Horeh, N. Bahaloo; Mousavi, S. M.; Shojaosadati, S. A.

    2016-07-01

    In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.

  7. Lithium-ion battery electrolyte mobility at nano-confined graphene interfaces

    Science.gov (United States)

    Moeremans, Boaz; Cheng, Hsiu-Wei; Hu, Qingyun; Garces, Hector F.; Padture, Nitin P.; Renner, Frank Uwe; Valtiner, Markus

    2016-01-01

    Interfaces are essential in electrochemical processes, providing a critical nanoscopic design feature for composite electrodes used in Li-ion batteries. Understanding the structure, wetting and mobility at nano-confined interfaces is important for improving the efficiency and lifetime of electrochemical devices. Here we use a Surface Forces Apparatus to quantify the initial wetting of nanometre-confined graphene, gold and mica surfaces by Li-ion battery electrolytes. Our results indicate preferential wetting of confined graphene in comparison with gold or mica surfaces because of specific interactions of the electrolyte with the graphene surface. In addition, wetting of a confined pore proceeds via a profoundly different mechanism compared with wetting of a macroscopic surface. We further reveal the existence of molecularly layered structures of the confined electrolyte. Nanoscopic confinement of less than 4–5 nm and the presence of water decrease the mobility of the electrolyte. These results suggest a lower limit for the pore diameter in nanostructured electrodes. PMID:27562148

  8. An Effective Approach for Coupling Direct Analysis in Real Time with Atmospheric Pressure Drift Tube Ion Mobility Spectrometry

    Science.gov (United States)

    Keelor, Joel D.; Dwivedi, Prabha; Fernández, Facundo M.

    2014-09-01

    Drift tube ion mobility spectrometry (DTIMS) has evolved as a robust analytical platform routinely used for screening small molecules across a broad suite of chemistries ranging from food and pharmaceuticals to explosives and environmental toxins. Most modern atmospheric pressure IM detectors employ corona discharge, photoionization, radioactive, or electrospray ion sources for efficient ion production. Coupling standalone DTIMS with ambient plasma-based techniques, however, has proven to be an exceptional challenge. Device sensitivity with near-ground ambient plasma sources is hindered by poor ion transmission at the source-instrument interface, where ion repulsion is caused by the strong electric field barrier of the high potential ion mobility spectrometry (IMS) inlet. To overcome this shortfall, we introduce a new ion source design incorporating a repeller point electrode used to shape the electric field profile and enable ion transmission from a direct analysis in real time (DART) plasma ion source. Parameter space characterization studies of the DART DTIMS setup were performed to ascertain the optimal configuration for the source assembly favoring ion transport. Preliminary system capabilities for the direct screening of solid pharmaceuticals are briefly demonstrated.

  9. Method for selective detection of explosives in mass spectrometer or ion mobility spectrometer at parts-per-quadrillion level

    Science.gov (United States)

    Ewing, Robert G.; Atkinson, David A.; Clowers, Brian H.

    2015-09-01

    A method for selective detection of volatile and non-volatile explosives in a mass spectrometer or ion mobility spectrometer at a parts-per-quadrillion level without preconcentration is disclosed. The method comprises the steps of ionizing a carrier gas with an ionization source to form reactant ions or reactant adduct ions comprising nitrate ions (NO.sub.3.sup.-); selectively reacting the reactant ions or reactant adduct ions with at least one volatile or non-volatile explosive analyte at a carrier gas pressure of at least about 100 Ton in a reaction region disposed between the ionization source and an ion detector, the reaction region having a length which provides a residence time (tr) for reactant ions therein of at least about 0.10 seconds, wherein the selective reaction yields product ions comprising reactant ions or reactant adduct ions that are selectively bound to the at least one explosive analyte when present therein; and detecting product ions with the ion detector to determine presence or absence of the at least one explosive analyte.

  10. Ion mobility spectrometry for the rapid analysis of over-the-counter drugs and beverages

    Science.gov (United States)

    Fernández-Maestre, Roberto

    2009-01-01

    In the pharmaceutical industry, there are increasing requirements for analytical methods in quality assessment for the production of drugs. In this investigation, ion mobility spectrometry (IMS) was used for the rapid qualitative separation and identification of active ingredients in generic over-the-counter drugs and food additives in beverages. The active ingredients determined in drugs were acetaminophen, aspartame, bisacodyl, caffeine, dextromethorphan, diphenhydramine, famotidine, glucosamine, guaifenesin, loratadine, niacin, phenylephrine, pyridoxine, thiamin, and tetrahydrozoline. Aspartame and caffeine were determined in beverages. Fourteen over-the-counter drugs and beverages were analyzed. Analysis times below 10 s were obtained for IMS, and reduced mobilities were reported for the first time for 12 compounds. A quadrupole mass spectrometer coupled to a mobility spectrometer was used to assure a correct peak assignation. The combination of fast analysis, low cost, and inexpensive maintenance of IMS instruments makes IMS an attractive technique for the qualitative determination of the active ingredients in over-the-counter drugs and food additives in manufacture quality control and cleaning verification for the drug and food industries. PMID:20835390

  11. Experimental and Theoretical Investigation of Sodiated Multimers of Steroid Epimers with Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Chouinard, Christopher D.; Cruzeiro, Vinícius Wilian D.; Roitberg, Adrian E.; Yost, Richard A.

    2017-02-01

    Ion mobility-mass spectrometry (IM-MS) has recently seen increased use in the analysis of small molecules, especially in the field of metabolomics, for increased breadth of information and improved separation of isomers. In this study, steroid epimers androsterone and trans-androsterone were analyzed with IM-MS to investigate differences in their relative mobilities. Although sodiated monomers exhibited very similar collision cross-sections (CCS), baseline separation was observed for the sodiated dimer species (RS = 1.81), with measured CCS of 242.6 and 256.3 Å2, respectively. Theoretical modeling was performed to determine the most energetically stable structures of solution-phase and gas-phase monomer and dimer structures. It was revealed that these epimers differ in their preferred dimer binding mode in solution phase: androsterone adopts a R=O - Na+ - OH—R' configuration, whereas trans-androsterone adopts a R=O - Na+ - O=R' configuration. This difference contributes to a significant structural variation, and subsequent CCS calculations based on these structures relaxed in the gas phase were in agreement with experimentally measured values (ΔCCS 5%). Additionally, these calculations accurately predicted the relative difference in mobility between the epimers. This study illustrates the power of combining experimental and theoretical results to better elucidate gas-phase structures.

  12. Comparison of the performance of three ion mobility spectrometers for measurement of biogenic amines

    Energy Technology Data Exchange (ETDEWEB)

    Karpas, Zeev, E-mail: karpas4@netvision.net.il [3QBD, Arad (Israel); Chemistry Department, Nuclear Research Center, Negev, Beer-Sheva 84190 (Israel); Guaman, Ana V., E-mail: aguaman@ibecbarcelona.eu [Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Artificial Olfaction Lab, Institute for Bioengineering of Catalonia, Baldiri i Rexach, 4-8, 08028 Barcelona (Spain); Pardo, Antonio, E-mail: apardo@el.ub.edu [Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Marco, Santiago, E-mail: smarco@ibecbarcelona.eu [Departament d' Electronica, Universitat de Barcelona, Marti i Franques 1, 08028 Barcelona (Spain); Artificial Olfaction Lab, Institute for Bioengineering of Catalonia, Baldiri i Rexach, 4-8, 08028 Barcelona (Spain)

    2013-01-03

    Graphical abstract: The response to different amounts of TMA (in {mu}g) that were placed in a headspace vial as a function of time for the VG-Test (top) and the GDA (bottom). Note that the ratio [TMA/(TMA + TEP)] (top) and [TMA/(TMA + RIP)] (bottom) and the clearance time increase with the amount of TMA deposited in the vial. Highlights: Black-Right-Pointing-Pointer First comparison of performance of IMS devices. Black-Right-Pointing-Pointer Gas-phase ion chemistry affected by operational parameters. Black-Right-Pointing-Pointer Limits of detection quite similar despite differences in devices. Black-Right-Pointing-Pointer LODs determined in controlled continuous flow and in headspace vapor. Black-Right-Pointing-Pointer Exponential dilution of headspace studies. - Abstract: The performance of three different types of ion mobility spectrometer (IMS) devices: GDA2 with a radioactive ion source (Airsense, Germany), UV-IMS with a photo-ionization source (G.A.S. Germany) and VG-Test with a corona discharge source (3QBD, Israel) was studied. The gas-phase ion chemistry in the IMS devices affected the species formed and their measured reduced mobility values. The sensitivity and limit of detection for trimethylamine (TMA), putrescine and cadaverine were compared by continuous monitoring of a stream of air with a given concentration of the analyte and by measurement of headspace vapors of TMA in a sealed vial. Preprocessing of the mobility spectra and the effectiveness of multivariate curve resolution techniques (MCR-LASSO) improved the accuracy of the measurements by correcting baseline effects and adjusting for variations in drift time as well as enhancing the signal to noise ratio and deconvolution of the complex data matrix to their pure components. The limit of detection for measurement of the biogenic amines by the three IMS devices was between 0.1 and 1.2 ppm (for TMA with the VG-Test and GDA, respectively) and between 0.2 and 0.7 ppm for putrescine and cadaverine

  13. Full Waveform Inversion Using Waveform Sensitivity Kernels

    Science.gov (United States)

    Schumacher, Florian; Friederich, Wolfgang

    2013-04-01

    We present a full waveform inversion concept for applications ranging from seismological to enineering contexts, in which the steps of forward simulation, computation of sensitivity kernels, and the actual inversion are kept separate of each other. We derive waveform sensitivity kernels from Born scattering theory, which for unit material perturbations are identical to the Born integrand for the considered path between source and receiver. The evaluation of such a kernel requires the calculation of Green functions and their strains for single forces at the receiver position, as well as displacement fields and strains originating at the seismic source. We compute these quantities in the frequency domain using the 3D spectral element code SPECFEM3D (Tromp, Komatitsch and Liu, 2008) and the 1D semi-analytical code GEMINI (Friederich and Dalkolmo, 1995) in both, Cartesian and spherical framework. We developed and implemented the modularized software package ASKI (Analysis of Sensitivity and Kernel Inversion) to compute waveform sensitivity kernels from wavefields generated by any of the above methods (support for more methods is planned), where some examples will be shown. As the kernels can be computed independently from any data values, this approach allows to do a sensitivity and resolution analysis first without inverting any data. In the context of active seismic experiments, this property may be used to investigate optimal acquisition geometry and expectable resolution before actually collecting any data, assuming the background model is known sufficiently well. The actual inversion step then, can be repeated at relatively low costs with different (sub)sets of data, adding different smoothing conditions. Using the sensitivity kernels, we expect the waveform inversion to have better convergence properties compared with strategies that use gradients of a misfit function. Also the propagation of the forward wavefield and the backward propagation from the receiver

  14. Analysis of Bacterial Lipooligosaccharides by MALDI-TOF MS with Traveling Wave Ion Mobility.

    Science.gov (United States)

    Phillips, Nancy J; John, Constance M; Jarvis, Gary A

    2016-07-01

    Lipooligosaccharides (LOS) are major microbial virulence factors displayed on the outer membrane of rough-type Gram-negative bacteria. These amphipathic glycolipids are comprised of two domains, a core oligosaccharide linked to a lipid A moiety. Isolated LOS samples are generally heterogeneous mixtures of glycoforms, with structural variability in both domains. Traditionally, the oligosaccharide and lipid A components of LOS have been analyzed separately following mild acid hydrolysis, although important acid-labile moieties can be cleaved. Recently, an improved method was introduced for analysis of intact LOS by MALDI-TOF MS using a thin layer matrix composed of 2,4,6-trihydroxyacetophenone (THAP) and nitrocellulose. In addition to molecular ions, the spectra show in-source "prompt" fragments arising from regiospecific cleavage between the lipid A and oligosaccharide domains. Here, we demonstrate the use of traveling wave ion mobility spectrometry (TWIMS) for IMS-MS and IMS-MS/MS analyses of intact LOS from Neisseria spp. ionized by MALDI. Using IMS, the singly charged prompt fragments for the oligosaccharide and lipid A domains of LOS were readily separated into resolved ion plumes, permitting the extraction of specific subspectra, which led to increased confidence in assigning compositions and improved detection of less abundant ions. Moreover, IMS separation of precursor ions prior to collision-induced dissociation (CID) generated time-aligned, clean MS/MS spectra devoid of fragments from interfering species. Incorporating IMS into the profiling of intact LOS by MALDI-TOF MS exploits the unique domain structure of the molecule and offers a new means of extracting more detailed information from the analysis. Graphical Abstract ᅟ.

  15. Analysis of Bacterial Lipooligosaccharides by MALDI-TOF MS with Traveling Wave Ion Mobility

    Science.gov (United States)

    Phillips, Nancy J.; John, Constance M.; Jarvis, Gary A.

    2016-07-01

    Lipooligosaccharides (LOS) are major microbial virulence factors displayed on the outer membrane of rough-type Gram-negative bacteria. These amphipathic glycolipids are comprised of two domains, a core oligosaccharide linked to a lipid A moiety. Isolated LOS samples are generally heterogeneous mixtures of glycoforms, with structural variability in both domains. Traditionally, the oligosaccharide and lipid A components of LOS have been analyzed separately following mild acid hydrolysis, although important acid-labile moieties can be cleaved. Recently, an improved method was introduced for analysis of intact LOS by MALDI-TOF MS using a thin layer matrix composed of 2,4,6-trihydroxyacetophenone (THAP) and nitrocellulose. In addition to molecular ions, the spectra show in-source "prompt" fragments arising from regiospecific cleavage between the lipid A and oligosaccharide domains. Here, we demonstrate the use of traveling wave ion mobility spectrometry (TWIMS) for IMS-MS and IMS-MS/MS analyses of intact LOS from Neisseria spp. ionized by MALDI. Using IMS, the singly charged prompt fragments for the oligosaccharide and lipid A domains of LOS were readily separated into resolved ion plumes, permitting the extraction of specific subspectra, which led to increased confidence in assigning compositions and improved detection of less abundant ions. Moreover, IMS separation of precursor ions prior to collision-induced dissociation (CID) generated time-aligned, clean MS/MS spectra devoid of fragments from interfering species. Incorporating IMS into the profiling of intact LOS by MALDI-TOF MS exploits the unique domain structure of the molecule and offers a new means of extracting more detailed information from the analysis.

  16. Gas-phase metalloprotein complexes interrogated by ion mobility-mass spectrometry

    Science.gov (United States)

    Faull, Peter A.; Korkeila, Karoliina E.; Kalapothakis, Jason M.; Gray, Andrew; McCullough, Bryan J.; Barran, Perdita E.

    2009-06-01

    Gas-phase biomolecular structure may be explored through a number of analytical techniques. Ion mobility-mass spectrometry (IM-MS) continues to prove itself as a sensitive and reliable bioanalytical tool for gas-phase structure determination due to intense study and development over the past 15 years. A vast amount of research interest, especially in protein and peptide conformational studies has generated a wealth of structural information for biological systems from small peptides to megadalton-sized biomolecules. In this work, linear low field IM-MS has been used to study gas-phase conformations and determine rotationally averaged collision cross-sections of three metalloproteins--cytochrome c, haemoglobin and calmodulin. Measurements have been performed on the MoQToF, a modified QToF 1 instrument (Micromass UK Ltd., Manchester, UK) modified in house. Gas-phase conformations and cross-sections of multimeric cytochrome c ions of the form [xM + nH+]n+ for x = 1-3 (monomer to trimer) have been successfully characterised and measured. We believe these to be the first reported collision cross-sections of higher order multimeric cytochrome c. Haemoglobin is investigated to obtain structural information on the associative mechanism of tetramer formation. Haemoglobin molecules, comprising apo- and holo-monomer chains, dimer and tetramer are transferred to the gas phase under a range of solution conditions. Structural information on the proposed critical intermediate, semi-haemoglobin, is reported. Cross-sections of the calcium binding protein calmodulin have been obtained under a range of calcium-bound conditions. Metalloprotein collision cross-sections from ion mobility measurements are compared with computationally derived values from published NMR and X-ray crystallography structural data. Finally we consider the change in the density of the experimentally measured rotationally averaged collision cross-section for compact geometries of the electrosprayed proteins.

  17. Biomedical applications of ion mobility-enhanced data-independent acquisition-based label-free quantitative proteomics.

    Science.gov (United States)

    Distler, Ute; Kuharev, Jörg; Tenzer, Stefan

    2014-12-01

    Mass spectrometry-based proteomics greatly benefited from recent improvements in instrument performance and the development of bioinformatics solutions facilitating the high-throughput quantification of proteins in complex biological samples. In addition to quantification approaches using stable isotope labeling, label-free quantification has emerged as the method of choice for many laboratories. Over the last years, data-independent acquisition approaches have gained increasing popularity. The integration of ion mobility separation into commercial instruments enabled researchers to achieve deep proteome coverage from limiting sample amounts. Additionally, ion mobility provides a new dimension of separation for the quantitative assessment of complex proteomes, facilitating precise label-free quantification even of highly complex samples. The present work provides a thorough overview of the combination of ion mobility and data-independent acquisition-based label-free quantification LC-MS and its applications in biomedical research.

  18. Atomistic insight into adsorption, mobility, and vibration of water in ion-exchanged zeolite-like metal-organic frameworks.

    Science.gov (United States)

    Nalaparaju, A; Babarao, R; Zhao, X S; Jiang, J W

    2009-09-22

    The adsorption, mobility, and vibration of water in ion-exchanged rho-zeolite-like metal-organic frameworks (ZMOFs) are investigated using atomistic simulations. Because of the high affinity for the ionic framework and nonframework ions, water is strongly adsorbed in rho-ZMOFs with a three-step adsorption mechanism. At low pressures, water is preferentially adsorbed onto Na(+) ions, particularly at site II; with increasing pressure, adsorption occurs near the framework and finally in the large cage. Upon water adsorption, Na(+) ions are observed to redistribute from site I to site II and gradually hydrated with increasing pressure. In Li-, Na-, and Cs-exchanged rho-ZMOFs, the adsorption capacity and isosteric heat decrease with increasing ionic radius attributed to the reduced electrostatic interaction and free volume. The mobility of water in Na-rho-ZMOF increases at low pressures but decreases upon approaching saturation. With sufficient amount of water present, the mobility of Na(+) ions is promoted. The vibrational spectra of water in Na-rho-ZMOF exhibit distinct bands for librational motion, bending, and stretching. The librational motion has a frequency higher than bulk water due to confinement. With increasing loading and hence stronger coordinative attraction, the bending frequency shows a blue shift. Symmetric and asymmetric modes are observed in the stretching as a consequence of the strong water-ion interaction. This study provides a fundamental microscopic insight into the static and dynamic properties of water in charged ZMOFs and reveals the subtle interplay between water and nonframework ions.

  19. An ion mobility-mass spectrometry investigation of monocyte chemoattractant protein-1

    Science.gov (United States)

    Schenauer, Matthew R.; Leary, Julie A.

    2009-10-01

    In the present article we describe the gas-phase dissociation behavior of the dimeric form of monocyte chemoattractant protein-1 (MCP-1) using quadrupole-traveling wave ion mobility spectrometry-time of flight mass spectrometry (q-TWIMS-TOF MS) (Waters Synapt(TM)). Through investigation of the 9+ charge state of the dimer, we were able to monitor dissociation product ion (monomer) formation as a function of activation energy. Using ion mobility, we were able to observe precursor ion structural changes occurring throughout the activation process. Arrival time distributions (ATDs) for the 5+ monomeric MCP-1 product ions, derived from the gas-phase dissociation of the 9+ dimer, were then compared with ATDs obtained for the 5+ MCP-1 monomer isolated directly from solution. The results show that the dissociated monomer is as compact as the monomer arising from solution, regardless of the trap collision energy (CE) used in the dissociation. The solution-derived monomer, when collisionally activated, also resists significant unfolding within measure. Finally, we compared the collisional activation data for the MCP-1 dimer with an MCP-1 dimer non-covalently bound to a single molecule of the semi-synthetic glycosaminoglycan (GAG) analog Arixtra(TM); the latter a therapeutic anti-thrombin III-activating pentasaccharide. We observed that while dimeric MCP-1 dissociated at relatively low trap CEs, the Arixtra-bound dimer required much higher energies, which also induced covalent bond cleavage in the bound Arixtra molecule. Both the free and Arixtra-bound dimers became less compact and exhibited longer arrival times with increasing trap CEs, albeit the Arixtra-bound complex at slightly higher energies. That both dimers shifted to longer arrival times with increasing activation energy, while the dissociated MCP-1 monomers remained compact, suggests that the longer arrival times of the Arixtra-free and Arixtra-bound dimers may represent a partial breach of non

  20. Gas chromatography/ion mobility spectrometry as a hyphenated technique for improved explosives detection and analysis

    Science.gov (United States)

    Mercado, AL; Marsden, Paul

    1995-01-01

    Ion Mobility Spectrometry (IMS) is currently being successfully applied to the problem of on-line trace detection of plastic and other explosives in airports and other facilities. The methods of sample retrieval primarily consist of batch sampling for particulate residue on a filter card for introduction into the IMS. The sample is desorbed into the IMS using air as the carrier and negative ions of the explosives are detected, some as an adduct with a reagent ion such as Cl(-). Based on studies and tests conducted by different airport authorities, this method seems to work well for low vapor pressure explosives such as RDX and PETN, as well as TNT that are highly adsorptive and can be found in nanogram quantities on contaminated surfaces. Recently, the changing terrorist threat and the adoption of new marking agents for plastic explosives has meant that the sample introduction and analysis capabilities of the IMS must be enhanced in order to keep up with other detector developments. The IMS has sufficient analytical resolution for a few threat compounds but the IMS Plasmogram becomes increasingly more difficult to interpret when the sample mixture gets more complex.

  1. Ion Mobility Spectrometry - High Resolution LTQ-Orbitrap Mass Spectrometry for Analysis of Homemade Explosives

    Science.gov (United States)

    Hagan, Nathan; Goldberg, Ilana; Graichen, Adam; St. Jean, Amanda; Wu, Ching; Lawrence, David; Demirev, Plamen

    2017-08-01

    The detailed chemical characterization of homemade explosives (HMEs) and other chemicals that can mimic or mask the presence of explosives is important for understanding and improving the performance of commercial instrumentation used for explosive detection. To that end, an atmospheric-pressure drift tube ion mobility spectrometry (IMS) instrument has been successfully coupled to a commercial tandem mass spectrometry (MS) system. The tandem MS system is comprised of a linear ion trap and a high resolution Orbitrap analyzer. This IMS-MS combination allows extensive characterization of threat chemical compounds, including HMEs, and complex real-world background chemicals that can interfere with detection. Here, the composition of ion species originating from a specific HME, erythritol tetranitrate, has been elucidated using accurate mass measurements, isotopic ratios, and tandem MS. Gated IMS-MS and high-resolution MS have been used to identify minor impurities that can be indicative of the HME source and/or synthesis route. Comparison between data obtained on the IMS/MS system and on commercial stand-alone IMS instruments used as explosive trace detectors (ETDs) has also been performed. Such analysis allows better signature assignments of threat compounds, modified detection algorithms, and improved overall ETD performance.

  2. Benchmark Comparison for a Multi-Processing Ion Mobility Calculator in the Free Molecular Regime

    Science.gov (United States)

    Shrivastav, Vaibhav; Nahin, Minal; Hogan, Christopher J.; Larriba-Andaluz, Carlos

    2017-08-01

    A benchmark comparison between two ion mobility and collision cross-section (CCS) calculators, MOBCAL and IMoS, is presented here as a standard to test the efficiency and performance of both programs. Utilizing 47 organic ions, results are in excellent agreement between IMoS and MOBCAL in He and N2, when both programs use identical input parameters. Due to a more efficiently written algorithm and to its parallelization, IMoS is able to calculate the same CCS (within 1%) with a speed around two orders of magnitude faster than its MOBCAL counterpart when seven cores are used. Due to the high computational cost of MOBCAL in N2, reaching tens of thousands of seconds even for small ions, the comparison between IMoS and MOBCAL is stopped at 70 atoms. Large biomolecules (>10000 atoms) remain computationally expensive when IMoS is used in N2 (even when employing 16 cores). Approximations such as diffuse trajectory methods (DHSS, TDHSS) with and without partial charges and projected area approximation corrections can be used to reduce the total computational time by several folds without hurting the accuracy of the solution. These latter methods can in principle be used with coarse-grained model structures and should yield acceptable CCS results.

  3. Full-waveform inversion: Filling the gaps

    KAUST Repository

    Beydoun, Wafik B.

    2015-09-01

    After receiving an outstanding response to its inaugural workshop in 2013, SEG once again achieved great success with its 2015 SEG Middle East Workshop, “Full-waveform inversion: Filling the gaps,” which took place 30 March–1 April 2015 in Abu Dhabi, UAE. The workshop was organized by SEG, and its partner sponsors were Saudi Aramco (gold sponsor), ExxonMobil, and CGG. Read More: http://library.seg.org/doi/10.1190/tle34091106.1

  4. Compressive full waveform lidar

    Science.gov (United States)

    Yang, Weiyi; Ke, Jun

    2017-05-01

    To avoid high bandwidth detector, fast speed A/D converter, and large size memory disk, a compressive full waveform LIDAR system, which uses a temporally modulated laser instead of a pulsed laser, is studied in this paper. Full waveform data from NEON (National Ecological Observatory Network) are used. Random binary patterns are used to modulate the source. To achieve 0.15 m ranging resolution, a 100 MSPS A/D converter is assumed to make measurements. SPIRAL algorithm with canonical basis is employed when Poisson noise is considered in the low illuminated condition.

  5. Comparison of Ambient and Atmospheric Pressure Ion Sources for Cystic Fibrosis Exhaled Breath Condensate Ion Mobility-Mass Spectrometry Metabolomics

    Science.gov (United States)

    Zang, Xiaoling; Pérez, José J.; Jones, Christina M.; Monge, María Eugenia; McCarty, Nael A.; Stecenko, Arlene A.; Fernández, Facundo M.

    2017-08-01

    Cystic fibrosis (CF) is an autosomal recessive disorder caused by mutations in the gene that encodes the cystic fibrosis transmembrane conductance regulator (CFTR) protein. The vast majority of the mortality is due to progressive lung disease. Targeted and untargeted CF breath metabolomics investigations via exhaled breath condensate (EBC) analyses have the potential to expose metabolic alterations associated with CF pathology and aid in assessing the effectiveness of CF therapies. Here, transmission-mode direct analysis in real time traveling wave ion mobility spectrometry time-of-flight mass spectrometry (TM-DART-TWIMS-TOF MS) was tested as a high-throughput alternative to conventional direct infusion (DI) electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) methods, and a critical comparison of the three ionization methods was conducted. EBC was chosen as the noninvasive surrogate for airway sampling over expectorated sputum as EBC can be collected in all CF subjects regardless of age and lung disease severity. When using pooled EBC collected from a healthy control, ESI detected the most metabolites, APCI a log order less, and TM-DART the least. TM-DART-TWIMS-TOF MS was used to profile metabolites in EBC samples from five healthy controls and four CF patients, finding that a panel of three discriminant EBC metabolites, some of which had been previously detected by other methods, differentiated these two classes with excellent cross-validated accuracy.

  6. Ambient temperature nanoelectrospray ion mobility detector for high performance liquid chromatography in determining amines.

    Science.gov (United States)

    Chen, Chuang; Hou, Keyong; Wang, Weiguo; Li, Jinghua; Li, Haiyang

    2014-09-01

    A nanoelectrospray ionization ion mobility spectrometer (nanoESI-IMS) working at ambient pressure and ambient temperature was developed as a detector of high performance liquid chromatography (HPLC) to achieve sensitive detection of amines with no derivatization and meanwhile provide another dimension of separation. The easier desolvation property of the charged droplets formed in nanoESI source enabled complete desolvation of the product ions of sixteen amines and drugs using the nanoESI-IMS at ambient temperature. Working at ambient temperature was good for suppressing the dissociation of thermal volatile ions, such as only the proton adducted molecular ions were observed for morphine in the nanoESI-IMS. Besides, the resolving power of the nanoESI-IMS also showed an increasing tendency as lowering the working temperature, an increment of 19 percent and 10 percent was observed for diethylamine and triethylamine as the temperature dropped from 92°C to 32°C. The resolving power of the nanoESI-IMS at 32°C for the 16 tested compounds was amid 33-44. With the nanoESI-IMS coupled to HPLC, a six-compound mixture including isomers was successfully separated and detected without any derivatization. And linear response ranges of 1 to 20, 0.5 to 20, and 0.8 to 20μgml(-1) and limits of detection of 0.25, 0.15, and 0.17μgml(-1) for triethylamine, diethylamine, and butylamine, respectively, were obtained with the hyphenated system. These results showed the excellent performance of the two-dimensional separation and detection method in direct qualitative and quantitative analyses of amines.

  7. Serpentine Ultralong Path with Extended Routing (SUPER) High Resolution Traveling Wave Ion Mobility-MS using Structures for Lossless Ion Manipulations.

    Science.gov (United States)

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

    2017-04-18

    Ion mobility (IM) separations have a broad range of analytical applications, but insufficient resolution often limits their utility. Here, we report on ion mobility separations in a structures for lossless ion manipulations (SLIM) serpentine ultralong path with extended routing (SUPER) traveling wave (TW) ion mobility (IM) module in conjunction with mass spectrometry (MS). Ions were confined in the SLIM by rf fields in conjunction with a DC guard bias, enabling essentially lossless TW transmission over greatly extended paths. The extended routing utilized multiple passes (e.g., ∼1094 m over 81 passes through the 13.5 m serpentine path) and was facilitated by the introduction of a lossless ion switch that allowed ions to be directed to either the MS detector or for another pass through the serpentine separation region, allowing theoretically unlimited IM path lengths. The multipass SUPER IM-MS provided resolution approximately proportional to the square root of the number of passes (or total path length). More than 30-fold higher IM resolution (∼340 vs ∼10) for Agilent tuning mix m/z 622 and 922 ions was achieved for 40 passes compared to commercially available drift tube IM and other TWIM-based platforms. An initial evaluation of the isomeric sugars lacto-N-hexaose and lacto-N-neohexaose showed the isomeric structures to be baseline resolved, and a new conformational feature for lacto-N-neohexaose was revealed after 9 passes. The new SLIM SUPER high resolution TWIM platform has broad utility in conjunction with MS and is expected to enable a broad range of previously challenging or intractable separations.

  8. Mobilities

    DEFF Research Database (Denmark)

    simple movements of people, goods, and information from A to B. The ‘mobilities turn’ has made it its hallmark to explore the ‘more than’ effects of a world increasingly on the move. This new title in the Routledge Series ‘Critical Concepts in Built Environment’ creates a state-of-the-art reference work......The world is on the move. This is a widespread understanding by many inhabitants of contemporary society across the Globe. But what does it actually mean? During over one decade the ‘mobilities turn’ within the social sciences have provided a new set of insights into the repercussions of mobilities...... to social networks, personal identities, and our relationship to the built environment. The omnipresence of mobilities within everyday life, high politics, technology, and tourism (to mention but a few) all point to a key insight harnessed by the ‘mobilities turn’. Namely that mobilities is much more than...

  9. Enhanced Mixture Separations of Metal Adducted Tetrasaccharides Using Frequency Encoded Ion Mobility Separations and Tandem Mass Spectrometry

    Science.gov (United States)

    Morrison, Kelsey A.; Bendiak, Brad K.; Clowers, Brian H.

    2016-10-01

    Using five isomeric tetrasaccharides in combination with seven multivalent metals, the impact on mobility separations and resulting CID spectra were examined using a hybrid ion mobility atmospheric pressure drift tube system coupled with a linear ion trap. By enhancing the duty cycle of the drift tube system using a linearly chirped frequency, the collision-induced dissociation spectra were encoded in the mobility domain according to the drift times of each glycan isomer precursor. Differential fragmentation patterns correlated with precursor drift times ensured direct assignment of fragments with precursor structure whether as individual standards or in a mixture of isomers. In addition to certain metal ions providing higher degrees of separation than others, in select cases more than one arrival time distribution was observed for a single pure carbohydrate isomer. These observations suggest the existence of alternative coordination sites within a single monomeric species, but more interesting was the observation of different fragmentation ion yields for carbohydrate dimers formed through metal adduction. Positive-ion data were also compared with negative-ion species, where dimer formation did not occur and single peaks were observed for each isomeric tetrasaccharide-alditol. This enhanced analytical power has implications not only for carbohydrate molecules but also for a wide variety of complex mixtures of molecules where dissociation spectra may potentially be derived from combinations of monomeric, homodimeric, and heterodimeric species having identical nominal m/z values.

  10. A flowing atmospheric pressure afterglow as an ion source coupled to a differential mobility analyzer for volatile organic compound detection.

    Science.gov (United States)

    Bouza, Marcos; Orejas, Jaime; López-Vidal, Silvia; Pisonero, Jorge; Bordel, Nerea; Pereiro, Rosario; Sanz-Medel, Alfredo

    2016-05-23

    Atmospheric pressure glow discharges have been widely used in the last decade as ion sources in ambient mass spectrometry analyses. Here, an in-house flowing atmospheric pressure afterglow (FAPA) has been developed as an alternative ion source for differential mobility analysis (DMA). The discharge source parameters (inter-electrode distance, current and helium flow rate) determining the atmospheric plasma characteristics have been optimized in terms of DMA spectral simplicity with the highest achievable sensitivity while keeping an adequate plasma stability and so the FAPA working conditions finally selected were: 35 mA, 1 L min(-1) of He and an inter-electrode distance of 8 mm. Room temperature in the DMA proved to be adequate for the coupling and chemical analysis with the FAPA source. Positive and negative ions for different volatile organic compounds were tested and analysed by FAPA-DMA using a Faraday cup as a detector and proper operation in both modes was possible (without changes in FAPA operational parameters). The FAPA ionization source showed simpler ion mobility spectra with narrower peaks and a better, or similar, sensitivity than conventional UV-photoionization for DMA analysis in positive mode. Particularly, the negative mode proved to be a promising field of further research for the FAPA ion source coupled to ion mobility, clearly competitive with other more conventional plasmas such as corona discharge.

  11. Quantitative analysis of volatile organic compounds using ion mobility spectra and cascade correlation neural networks

    Science.gov (United States)

    Harrington, Peter DEB.; Zheng, Peng

    1995-01-01

    Ion Mobility Spectrometry (IMS) is a powerful technique for trace organic analysis in the gas phase. Quantitative measurements are difficult, because IMS has a limited linear range. Factors that may affect the instrument response are pressure, temperature, and humidity. Nonlinear calibration methods, such as neural networks, may be ideally suited for IMS. Neural networks have the capability of modeling complex systems. Many neural networks suffer from long training times and overfitting. Cascade correlation neural networks train at very fast rates. They also build their own topology, that is a number of layers and number of units in each layer. By controlling the decay parameter in training neural networks, reproducible and general models may be obtained.

  12. Hardware/Software Codesign in a Compact Ion Mobility Spectrometer Sensor System for Subsurface Contaminant Detection

    Directory of Open Access Journals (Sweden)

    Gribb MollyM

    2008-01-01

    Full Text Available Abstract A field-programmable-gate-array-(FPGA- based data acquisition and control system was designed in a hardware/software codesign environment using an embedded Xilinx Microblaze soft-core processor for use with a subsurface ion mobility spectrometer (IMS system, designed for detection of gaseous volatile organic compounds (VOCs. An FPGA is used to accelerate the digital signal processing algorithms and provide accurate timing and control. An embedded soft-core processor is used to ease development by implementing nontime critical portions of the design in software. The design was successfully implemented using a low-cost, off-the-shelf Xilinx Spartan-III FPGA and supporting digital and analog electronics.

  13. Integrated statistical learning of metabolic ion mobility spectrometry profiles for pulmonary disease identification

    DEFF Research Database (Denmark)

    Hauschild, A.C.; Baumbach, Jan; Baumbach, J.

    2012-01-01

    Exhaled air carries information on human health status. Ion mobility spectrometers combined with a multi-capillary column (MCC/IMS) is a well-known technology for detecting volatile organic compounds (VOCs) within human breath. This technique is relatively inexpensive, robust and easy to use...... sophisticated statistical learning techniques for VOC-based feature selection and supervised classification into patient groups. We analyzed breath data from 84 volunteers, each of them either suffering from chronic obstructive pulmonary disease (COPD), or both COPD and bronchial carcinoma (COPD + BC), as well...... as from 35 healthy volunteers, comprising a control group (CG). We standardized and integrated several statistical learning methods to provide a broad overview of their potential for distinguishing the patient groups. We found that there is strong potential for separating MCC/IMS chromatograms of healthy...

  14. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    Energy Technology Data Exchange (ETDEWEB)

    Wojcik, Roza; Webb, Ian; Deng, Liulin; Garimella, Sandilya; Prost, Spencer; Ibrahim, Yehia; Baker, Erin; Smith, Richard

    2017-01-01

    Understanding the biological mechanisms related to lipids and glycolipids is challenging due to the vast number of possible isomers. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid structures. However, difficulties in distinguishing many structural isomers (e.g. distinct acyl chain positions, double bond locations, as well as glycan isomers) inhibit the understanding of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations based upon the use of traveling waves in a serpentine long path length multi-pass Structures for Lossless Manipulations (SLIM) to enhance isomer resolution. The multi-pass arrangement allowed separations ranging from ~16 m (1 pass) to ~470 m (32 passes) to be investigated for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer specific biological and disease processes.

  15. Uncovering biologically significant lipid isomers with liquid chromatography, ion mobility spectrometry and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kyle, Jennifer E.; Zhang, Xing; Weitz, Karl K.; Monroe, Matthew E.; Ibrahim, Yehia M.; Moore, Ronald J.; Cha, Jeeyeon; Sun, Xiaofei; Lovelace, Erica S.; Wagoner, Jessica; Polyak, Steve; Metz, Thomas O.; Dey, Sudhansu K.; Smith, Richard D.; Burnum-Johnson, Kristin E.; Baker, Erin Shammel

    2016-01-01

    Understanding how biological molecules are generated, metabolized and eliminated in living systems is important for interpreting processes such as immune response and disease pathology. While genomic and proteomic studies have provided vast amounts of information over the last several decades, interest in lipidomics has also grown due to improved analytical technologies revealing altered lipid metabolism in type 2 diabetes, cancer, and lipid storage disease. Liquid chromatography and mass spectrometry (LC-MS) measurements are currently the dominant approach for characterizing the lipidome by providing detailed information on the spatial and temporal composition of lipids. However, interpreting lipids’ biological roles is challenging due to the existence of numerous structural and stereoisomers (i.e. distinct acyl chain and double-bond positions), which are unresolvable using present LC-MS approaches. Here we show that combining structurally-based ion mobility spectrometry (IMS) with LC-MS measurements distinguishes lipid isomers and allows insight into biological and disease processes.

  16. Optimal Design of FPGA Switch Matrix with Ion Mobility Based Nonvolatile ReRAM

    Directory of Open Access Journals (Sweden)

    Peng Hai-yun

    2015-01-01

    Full Text Available There are high demands for research of new device with greater accessing speed and stability to replace the current SRAM storage cell. The resistive random access memory (ReRAM is a metal oxide which is based on nonvolatile memory device possessing the characteristics of high read/write speed, high storage density, low power, low cost, very small cell, being nonvolatile, and unlimited writing endurance. The device has extreme short erasing time and the stored charge cannot be destroyed after power-off. Therefore, the ReRAM device is a significant storage device for many applications in the next generation. In this paper, we first explored the mechanism of the ReRAM device based on ion mobility model and then applied this device to optimize the design of FPGA switching matrix. The results show that it is beneficial to enhance the FPGA performance to replace traditional SRAM cells with ReRAM cells for the switching matrix.

  17. Atmospheric pressure air direct current glow discharge ionization source for ion mobility spectrometry.

    Science.gov (United States)

    Dong, Can; Wang, Weiguo; Li, Haiyang

    2008-05-15

    A new atmospheric pressure air direct current glow discharge (DCGD) ionization source has been developed for ion mobility spectrometry (IMS) to overcome the regularity problems associated with the conventional (63)Ni source and the instability of the negative corona discharge. Its general electrical characteristics were experimentally investigated. By equipping it to IMS, a higher sensitivity was obtained compared to that of a (63)Ni source and corona discharge, and a linear dynamic range from 20 ppb to 20 ppm was obtained for m-xylene. Primary investigations showed that alkanes, such as pentane, which are nondetectable or insensitively detectable with (63)Ni-IMS, can be efficiently detected by DCGD-IMS and the detection limit of 10 ppb can be reached. The preliminary results have shown that the new DCGD ionization source has great potential applications in IMS, such as online monitoring of environment pollutants and halogenated compounds.

  18. Recent Applications of Ion Mobility Spectrometry in Diagnosis of Vaginal Infections

    Directory of Open Access Journals (Sweden)

    Zeev Karpas

    2012-01-01

    Full Text Available Vaginal infections (vaginosis globally affect more than 15% of the female population of reproductive age. However, diagnosis of vaginosis and differentiating between the three common types: bacterial vaginosis (BV, vulvovaginal candidiasis (VVC, and trichomoniasis are challenging. Elevated levels of the biogenic amines, trimethylamine (TMA, putrescine, and cadaverine have been found in vaginal discharge fluid of women with vaginosis. Ion mobility spectrometry (IMS is particularly suitable for measurement of amines even in complex biological matrices due to their high proton affinity and has been shown to be suitable for the diagnosis of vaginal infections. Recent developments that have increased the accuracy of the technique for diagnosis of BV and simplified sample introduction are described here.

  19. Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry.

    Science.gov (United States)

    Lalli, Priscila M; Iglesias, Bernardo A; Deda, Daiana K; Toma, Henrique E; de Sa, Gilberto F; Daroda, Romeu J; Araki, Koiti; Eberlin, Marcos N

    2012-02-15

    The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2).

  20. Advancing the High Throughput Identification of Liver Fibrosis Protein Signatures Using Multiplexed Ion Mobility Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Baker, Erin Shammel; Burnum-Johnson, Kristin E.; Jacobs, Jon M.; Diamond, Deborah L.; Brown, Roslyn N.; Ibrahim, Yehia M.; Orton, Daniel J.; Piehowski, Paul D.; Purdy, David E.; Moore, Ronald J.; Danielson, William F.; Monroe, Matthew E.; Crowell, Kevin L.; Slysz, Gordon W.; Gritsenko, Marina A.; Sandoval, John D.; Lamarche, Brian L.; Matzke, Melissa M.; Webb-Robertson, Bobbie-Jo M.; Simons, Brenna C.; McMahon, Brian J.; Bhattacharya, Renuka; Perkins, James D.; Carithers, Robert L.; Strom, Susan; Self, Steven; Katze, Michael G.; Anderson, Gordon A.; Smith, Richard D.

    2014-04-01

    Rapid diagnosis of disease states using less invasive, safer, and more clinically acceptable approaches than presently employed is an imperative goal for the field of medicine. While mass spectrometry (MS)-based proteomics approaches have attempted to meet these objectives, challenges such as the enormous dynamic range of protein concentrations in clinically relevant biofluid samples coupled with the need to address human biodiversity have slowed their employment. Herein, we report on the use of a new platform that addresses these challenges by coupling technical advances in rapid gas phase multiplexed ion mobility spectrometry (IMS) separations [1, 2] with liquid chromatography (LC) and MS to dramatically increase measurement sensitivity and throughput, further enabling future MS-based clinical applications. An initial application of the LC-IMS-MS platform for the analysis of blood serum samples from stratified post-liver transplant patients with recurrent fibrosis progression illustrates its potential utility for disease characterization and use in personalized medicine [3, 4].

  1. Molecular Structural Characterization and Quantitative Prediction of Reduced Ion Mobility Constants for Diversified Organic Compounds

    Institute of Scientific and Technical Information of China (English)

    HE Liu; LIANG Gui-Zhao; LI Zhi-Liang

    2008-01-01

    Based on two-dimensional topological structures, a novel molecular electronega- tivity interaction vector with hybridization (MEHIV) was developed to describe atomic hybri- dization state in different molecular environments. Five quantitative models by MEHIV cha- racterization and multiple linear regression modeling were successfully established to predict reduced ion mobility constants (K0) of alkanes, aromatic hydrocarbons, fatty alcohols, fatty aldehydes and ketones and carboxylic esters. The correlation coefficients Rcv by leave-one-out cross-validation are 0.792, 0.787, 0.949, 0.972 and 0.981, respectively, and the standard deviations SDcv are 0.067, 0.086, 0.064, 0.043 and 0.042, respectively. These results suggested that MEHIV is an excellent topological index descriptor with many advantages such as straightforward physicochemical meaning, high characterization competence, convenient expan- sibility and easy manipulation.

  2. Ion mobility spectrometry fingerprints: A rapid detection technology for adulteration of sesame oil.

    Science.gov (United States)

    Zhang, Liangxiao; Shuai, Qian; Li, Peiwu; Zhang, Qi; Ma, Fei; Zhang, Wen; Ding, Xiaoxia

    2016-02-01

    A simple and rapid detection technology was proposed based on ion mobility spectrometry (IMS) fingerprints to determine potential adulteration of sesame oil. Oil samples were diluted by n-hexane and analyzed by IMS for 20s. Then, chemometric methods were employed to establish discriminant models for sesame oils and four other edible oils, pure and adulterated sesame oils, and pure and counterfeit sesame oils, respectively. Finally, Random Forests (RF) classification model could correctly classify all five types of edible oils. The detection results indicated that the discriminant models built by recursive support vector machine (R-SVM) method could identify adulterated sesame oil samples (⩾ 10%) with an accuracy value of 94.2%. Therefore, IMS was shown to be an effective method to detect the adulterated sesame oils. Meanwhile, IMS fingerprints work well to detect the counterfeit sesame oils produced by adding sesame oil essence into cheaper edible oils. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. A Priori Intrinsic PTM Size Parameters for Predicting the Ion Mobilities of Modified Peptides

    Science.gov (United States)

    Kaszycki, Julia L.; Shvartsburg, Alexandre A.

    2017-02-01

    The rising profile of ion mobility spectrometry (IMS) in proteomics has driven the efforts to predict peptide cross-sections. In the simplest approach, these are derived by adding the contributions of all amino acid residues and post-translational modifications (PTMs) defined by their intrinsic size parameters (ISPs). We show that the ISPs for PTMs can be calculated from properties of constituent atoms, and introduce the "impact scores" that govern the shift of cross-sections from the central mass-dependent trend for unmodified peptides. The ISPs and scores tabulated for 100 more common PTMs enable predicting the domains for modified peptides in the IMS/MS space that would guide subproteome investigations.

  4. Characterization of TATP gas phase product ion chemistry via isotope labeling experiments using ion mobility spectrometry interfaced with a triple quadrupole mass spectrometer.

    Science.gov (United States)

    Tomlinson-Phillips, Jill; Wooten, Alfred; Kozole, Joseph; Deline, James; Beresford, Pamela; Stairs, Jason

    2014-09-01

    Identification of the fragment ion species associated with the ion reaction mechanism of triacetone triperoxide (TATP), a homemade peroxide-based explosive, is presented. Ion mobility spectrometry (IMS) has proven to be a key analytical technique in the detection of trace explosive material. Unfortunately, IMS alone does not provide chemical identification of the ions detected; therefore, it is unknown what ion species are actually formed and separated by the IMS. In IMS, ions are primarily characterized by their drift time, which is dependent on the ion׳s mass and molecular cross-section; thus, IMS as a standalone technique does not provide structural signatures, which is in sharp contrast to the chemical and molecular information that is generally obtained from other customary analytical techniques, such as NMR, Raman and IR spectroscopy and mass spectrometry. To help study the ion chemistry that gives rise to the peaks observed in IMS, the hardware of two different commercial IMS instruments has been directly coupled to triple quadrupole (QQQ) mass spectrometers, in order to ascertain each ion׳s corresponding mass/charge (m/z) ratios with different dopants at two temperatures. Isotope labeling was then used to help identify and confirm the molecular identity of the explosive fragment and adduct ions of TATP. The m/z values and isotope labeling experiments were used to help propose probable molecular formulas for the ion fragments. In this report, the fragment and adduct ions m/z 58 and 240 of TATP have been confirmed to be [C3H6NH·H](+) and [TATP·NH4](+), respectively; while the fragment ions m/z 73 and 89 of TATP are identified as having the molecular formulas [C4H9NH2](+) and [C4H9O2](+), respectively. It is anticipated that the work in this area will not only help to facilitate improvements in mobility-based detection (IMS and MS), but also aid in the development and optimization of MS-based detection algorithms for TATP.

  5. Recent progress on nanostructured 4 V cathode materials for Li-ion batteries for mobile electronics

    OpenAIRE

    Xiaodong Xu; Sanghan Lee; Sookyung Jeong; Youngsik Kim; Jaephil Cho

    2013-01-01

    Mobile electronics have developed so rapidly that battery technology has hardly been able to keep pace. The increasing desire for lighter and thinner Li-ion batteries with higher capacities is a continuing and constant goal for in research. Achieving higher energy densities, which is mainly dependent on cathode materials, has become a critical issue in the development of new Li-ion batteries. In this review, we will outline the progress on nanostructured 4 V cathode materials of Li-ion batter...

  6. An integrative clinical database and diagnostics platform for biomarker identification and analysis in ion mobility spectra of human exhaled air

    DEFF Research Database (Denmark)

    Schneider, Till; Hauschild, Anne-Christin; Baumbach, Jörg Ingo;

    2013-01-01

    Over the last decade the evaluation of odors and vapors in human breath has gained more and more attention, particularly in the diagnostics of pulmonary diseases. Ion mobility spectrometry coupled with multi-capillary columns (MCC/IMS), is a well known technology for detecting volatile organic...

  7. Computational methods for metabolomic data analysis of ion mobility spectrometry data-reviewing the state of the art

    DEFF Research Database (Denmark)

    Hauschild, Anne-Christin; Schneider, Till; Pauling, Josch;

    2012-01-01

    Ion mobility spectrometry combined with multi-capillary columns (MCC/IMS) is a well known technology for detecting volatile organic compounds (VOCs). We may utilize MCC/IMS for scanning human exhaled air, bacterial colonies or cell lines, for example. Thereby we gain information about the human...

  8. Development of an Ion Mobility Spectrometry-Orbitrap Mass Spectrometer Platform

    Energy Technology Data Exchange (ETDEWEB)

    Ibrahim, Yehia M.; Garimella, Sandilya V. B.; Prost, Spencer A.; Wojcik, Roza; Norheim, Randolph V.; Baker, Erin S.; Rusyn, Ivan; Smith, Richard D.

    2016-12-20

    Complex samples benefit from multidimensional measurements where higher resolution enables more complete characterization of biological and environmental systems. To address this challenge, we developed a drift tube-based ion mobility spectrometry-Orbitrap mass spectrometer (IMS-Orbitrap MS) platform. To circumvent the time scale disparity between the fast IMS separation and the much slower Orbitrap MS acquisition, we utilized a dual gate and pseudorandom sequences to multiplexed injection of ions and allowing operation in signal averaging (SA), single multiplexing (SM) and double multiplexing (DM) IMS modes to optimize the signal-to-noise ratio of the measurements. For the SM measurements, a previously developed algorithm was used to reconstruct the IMS data. A new algorithm was developed for the DM analyses involving a two-step process that first recovers the SM data and then decodes the SM data. The algorithm also performs multiple refining procedures in order to minimize demultiplexing artifacts. The new IMS-Orbitrap MS platform was demonstrated by the analysis of proteomic and petroleum samples, where the integration of IMS and high mass resolution proved essential for accurate assignment of molecular formulae.

  9. Simultaneous Proteomic Discovery and Targeted Monitoring using Liquid Chromatography, Ion Mobility Spectrometry, and Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Burnum-Johnson, Kristin E.; Nie, Song; Casey, Cameron P.; Monroe, Matthew E.; Orton, Daniel J.; Ibrahim, Yehia M.; Gritsenko, Marina A.; Clauss, Therese R. W.; Shukla, Anil K.; Moore, Ronald J.; Purvine, Samuel O.; Shi, Tujin; Qian, Weijun; Liu, Tao; Baker, Erin S.; Smith, Richard D.

    2016-09-25

    Current proteomics approaches are comprised of both broad discovery measurements as well as more quantitative targeted measurements. These two different measurement types are used to initially identify potentially important proteins (e.g., candidate biomarkers) and then enable improved quantification for a limited number of selected proteins. However, both approaches suffer from limitations, particularly the lower sensitivity, accuracy, and quantitation precision for discovery approaches compared to targeted approaches, and the limited proteome coverage provided by targeted approaches. Herein, we describe a new proteomics approach that allows both discovery and targeted monitoring (DTM) in a single analysis using liquid chromatography, ion mobility spectrometry and mass spectrometry (LC-IMS-MS). In DTM, heavy labeled peptides for target ions are spiked into tryptic digests and both the labeled and unlabeled peptides are broadly detected using LC-IMS-MS instrumentation, allowing the benefits of discovery and targeted approaches. To understand the possible improvement of the DTM approach, it was compared to LC-MS broad measurements using an accurate mass and time tag database and selected reaction monitoring (SRM) targeted measurements. The DTM results yielded greater peptide/protein coverage and a significant improvement in the detection of lower abundance species compared to LC-MS discovery measurements. DTM was also observed to have similar detection limits as SRM for the targeted measurements indicating its potential for combining the discovery and targeted approaches.

  10. New Lithium-ion Polymer Battery for the Extravehicular Mobility Unit Suit

    Science.gov (United States)

    Jeevarajan, J. A.; Darcy, E. C.

    2004-01-01

    The Extravehicular Mobility Unit (EMU) suit currently has a silver-zinc battery that is 20.5 V and 45 Ah capacity. The EMU's portable life support system (PLSS) will draw power from the battery during the entire period of an EVA. Due to the disadvantages of using the silver-zinc battery in terms of cost and performance, a new high energy density battery is being developed for future use, The new battery (Lithium-ion battery or LIB) will consist of Li-ion polymer cells that will provide power to the EMU suit. The battery design consists of five 8 Ah cells in parallel to form a single module of 40 Ah and five such modules will be placed in series to give a 20.5 V, 40 Ah battery. Charging will be accomplished on the Shuttle or Station using the new LIB charger or the existing ALPS (Air Lock Power Supply) charger. The LIB delivers a maximum of 3.8 A on the average, for seven continuous hours, at voltages ranging from 20.5 V to 16.0 V and it should be capable of supporting transient pulses during start up and once every hour to support PLSS fan and pump operation. Figure 1 shows the placement of the battery in the backpack area of the EMU suit. The battery and cells will undergo testing under different conditions to understand its performance and safety characteristics.

  11. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    Directory of Open Access Journals (Sweden)

    Roza Wojcik

    2017-01-01

    Full Text Available Understanding the biological roles and mechanisms of lipids and glycolipids is challenging due to the vast number of possible isomers that may exist. Mass spectrometry (MS measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid presence and changes. However, difficulties in distinguishing the many structural isomers, due to the distinct lipid acyl chain positions, double bond locations or specific glycan types, inhibit the delineation and assignment of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS separations by applying traveling waves in a serpentine multi-pass Structures for Lossless Ion Manipulations (SLIM platform to enhance the separation of selected lipid and glycolipid isomers. The multi-pass arrangement allowed the investigation of paths ranging from ~16 m (one pass to ~60 m (four passes for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer-specific biological activities and disease processes.

  12. Study of the magnets used for a mobile isocenter carbon ion gantry

    Science.gov (United States)

    Moreno, Jhonnatan Osorio; Pullia, Marco G.; Priano, Cristiana; Lante, Valeria; Necchi, Monica M.; Savazzi, Simone

    2013-01-01

    A conceptual design of a mobile isocenter carbon ion gantry was carried out in the framework of the Particle Training Network for European Radiotherapy (PARTNER) and Union of Light Ion Centres in Europe (ULICE) projects. To validate the magnets used in this gantry, Finite Element Method (FEM) simulations were performed with COMSOL multiphysics; the purpose was to evaluate the magnetic field quality and the influence of additional support structures for correctors, 90° bending dipole and quadrupoles, both in dynamic and static regimes. Due to the low ramp rates, the dynamic effects do not disturb the homogeneity and the magnetic field level. The differences between the stationary field and the corresponding dynamic field after the end of the ramps are in the order of 10–4; it implies that the magnets can be operated without significant field lag at the nominal ramp rate. However, even in static regime the magnetic length of corrector magnet decreases by 5% when the rotator mechanical structure is considered. The simulations suggest an optimization phase of the correctors in the rotator. PMID:23824120

  13. Study of the magnets used for a mobile isocenter carbon ion gantry.

    Science.gov (United States)

    Moreno, Jhonnatan Osorio; Pullia, Marco G; Priano, Cristiana; Lante, Valeria; Necchi, Monica M; Savazzi, Simone

    2013-07-01

    A conceptual design of a mobile isocenter carbon ion gantry was carried out in the framework of the Particle Training Network for European Radiotherapy (PARTNER) and Union of Light Ion Centres in Europe (ULICE) projects. To validate the magnets used in this gantry, Finite Element Method (FEM) simulations were performed with COMSOL multiphysics; the purpose was to evaluate the magnetic field quality and the influence of additional support structures for correctors, 90° bending dipole and quadrupoles, both in dynamic and static regimes. Due to the low ramp rates, the dynamic effects do not disturb the homogeneity and the magnetic field level. The differences between the stationary field and the corresponding dynamic field after the end of the ramps are in the order of 10(-4); it implies that the magnets can be operated without significant field lag at the nominal ramp rate. However, even in static regime the magnetic length of corrector magnet decreases by 5% when the rotator mechanical structure is considered. The simulations suggest an optimization phase of the correctors in the rotator.

  14. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 3. Estimating Surface Area Exposure by Deuterium Uptake

    Science.gov (United States)

    Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Donohoe, Gregory C.; Valentine, Stephen J.

    2016-03-01

    Gas-phase hydrogen deuterium exchange (HDX), collision cross section (CCS) measurement, and molecular dynamics simulation (MDS) techniques were utilized to develop and compare three methods for estimating the relative surface area exposure of separate peptide chains within bovine insulin ions. Electrosprayed [M - 3H]3- and [M - 5H]5- insulin ions produced a single conformer type with respective collision cross sections of 528 ± 5 Å2 and 808 ± 2 Å2. [M - 4H]4- ions were comprised of more compact (Ω = 676 ± 3 Å2) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å2) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M - 4H]4- and [M - 5H]5- ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis.

  15. Toward a Rational Design of Highly Folded Peptide Cation Conformations. 3D Gas-Phase Ion Structures and Ion Mobility Characterization.

    Science.gov (United States)

    Pepin, Robert; Laszlo, Kenneth J; Marek, Aleš; Peng, Bo; Bush, Matthew F; Lavanant, Helène; Afonso, Carlos; Tureček, František

    2016-10-01

    Heptapeptide ions containing combinations of polar Lys, Arg, and Asp residues with non-polar Leu, Pro, Ala, and Gly residues were designed to study polar effects on gas-phase ion conformations. Doubly and triply charged ions were studied by ion mobility mass spectrometry and electron structure theory using correlated ab initio and density functional theory methods and found to exhibit tightly folded 3D structures in the gas phase. Manipulation of the basic residue positions in LKGPADR, LRGPADK, KLGPADR, and RLGPADK resulted in only minor changes in the ion collision cross sections in helium. Replacement of the Pro residue with Leu resulted in only marginally larger collision cross sections for the doubly and triply charged ions. Disruption of zwitterionic interactions in doubly charged ions was performed by converting the C-terminal and Asp carboxyl groups to methyl esters. This resulted in very minor changes in the collision cross sections of doubly charged ions and even slightly diminished collision cross sections in most triply charged ions. The experimental collision cross sections were related to those calculated for structures of lowest free energy ion conformers that were obtained by extensive search of the conformational space and fully optimized by density functional theory calculations. The predominant factors that affected ion structures and collision cross sections were due to attractive hydrogen bonding interactions and internal solvation of the charged groups that overcompensated their Coulomb repulsion. Structure features typically assigned to the Pro residue and zwitterionic COO-charged group interactions were only secondary in affecting the structures and collision cross sections of these gas-phase peptide ions. Graphical Abstract ᅟ.

  16. Toward a Rational Design of Highly Folded Peptide Cation Conformations. 3D Gas-Phase Ion Structures and Ion Mobility Characterization

    Science.gov (United States)

    Pepin, Robert; Laszlo, Kenneth J.; Marek, Aleš; Peng, Bo; Bush, Matthew F.; Lavanant, Helène; Afonso, Carlos; Tureček, František

    2016-10-01

    Heptapeptide ions containing combinations of polar Lys, Arg, and Asp residues with non-polar Leu, Pro, Ala, and Gly residues were designed to study polar effects on gas-phase ion conformations. Doubly and triply charged ions were studied by ion mobility mass spectrometry and electron structure theory using correlated ab initio and density functional theory methods and found to exhibit tightly folded 3D structures in the gas phase. Manipulation of the basic residue positions in LKGPADR, LRGPADK, KLGPADR, and RLGPADK resulted in only minor changes in the ion collision cross sections in helium. Replacement of the Pro residue with Leu resulted in only marginally larger collision cross sections for the doubly and triply charged ions. Disruption of zwitterionic interactions in doubly charged ions was performed by converting the C-terminal and Asp carboxyl groups to methyl esters. This resulted in very minor changes in the collision cross sections of doubly charged ions and even slightly diminished collision cross sections in most triply charged ions. The experimental collision cross sections were related to those calculated for structures of lowest free energy ion conformers that were obtained by extensive search of the conformational space and fully optimized by density functional theory calculations. The predominant factors that affected ion structures and collision cross sections were due to attractive hydrogen bonding interactions and internal solvation of the charged groups that overcompensated their Coulomb repulsion. Structure features typically assigned to the Pro residue and zwitterionic COO-charged group interactions were only secondary in affecting the structures and collision cross sections of these gas-phase peptide ions.

  17. Some anomalous effects of sodium ions on the electrophoretic mobility and heteroaggregation of microgel particles.

    Science.gov (United States)

    Routh, Alexander F; Vincent, Brian

    2004-05-15

    Experiments on the kinetics of heteroaggregation between oppositely charged particles, using both dynamic light scattering and turbidity methods, are reported. The negatively charged particles were cross-linked poly( [Formula: see text] -isopropylacrylamide) [PNIPAM] microgel particles, prepared using a carboxylic-acid-based initiator; these particles are swollen at room temperature. The positive particles were poly(4-vinylpyridine) [P4VP] particles, prepared using an amidinium-based initiator; such particles do not respond to temperature changes but do swell below pH approximately 4, where the pyridine moieties become protonated. As expected, the rate of heteroaggregation was shown to be largely independent of added salt concentration (up to approximately 20 mM), for a variety of alkali metal chlorides (MCl, where M = Li, Na, K, or Rb). However, an unexpected, significant decrease in the aggregation rate was observed at certain specific sodium chloride concentrations (typically at approximately 1 and also approximately 4 mM). Similar effects were not seen with the other alkali metal chloride salts. This strange effect was eventually attributed to the fact that the net charge on the positively charged P4VP particles had been reduced by the adsorption of (anionic) silicate species leached from the glassware container. Sodium silicates are known to be significantly more soluble than those of the other alkali metal ions, particularly at high pH. Moreover, P4VP particles dispersed in water, ostensibly at neutral pH, do buffer the aqueous medium to pH values around 9 or higher. This mechanism was confirmed by determining the electrophoretic mobility of the P4VP particles as a function of pH in the presence of the various alkali metal chloride salts. The mobility remained positive in 1 mM salt solutions over the pH range 3 to 11 for all the salts, except for sodium chloride; in that case the mobility reversed sign at alkaline pH values. A similar effect was observed for

  18. Differential mobility spectrometry with nanospray ion source as a compact detector for small organics and inorganics.

    Science.gov (United States)

    Coy, Stephen L; Krylov, Evgeny V; Nazarov, Erkinjon G; Fornace, Albert J; Kidd, Richard D

    2013-09-01

    Electrospray ionization (ESI) is an important tool in chemical and biochemical survey and targeted analysis in many applications. For chemical detection and identification electrospray is usually used with mass spectrometry (MS). However, for screening and monitoring of chemicals of interest in light, low power field-deployable instrumentation, an alternative detection technology with chemical selectivity would be highly useful, especially since small, lightweight, chip-based gas and liquid chromatographic technologies are being developed. Our initial list of applications requiring portable instruments includes chemical surveys on Mars, medical diagnostics based on metabolites in biological samples, and water quality analysis. In this report, we evaluate ESI-Differential Mobility Spectrometry (DMS) as a compact, low-power alternative to MS detection. Use of DMS for chemically-selective detection of ESI suffers in comparison with mass spectrometry because portable MS peak capacity is greater than that of DMS by 10X or more, but the development of light, fast chip chromatography offers compensating resolution. Standalone DMS provides the chemical selectivity familiar from DMS-MS publications, and exploits the sensitivity of ion detection. We find that sub-microliter-per-minute flows and a correctly-designed interface prepare a desolvated ion stream that enables DMS to act as an effective ion filter. Results for a several small organic biomarkers and metabolites, including citric acid, azelaic acid, n-hexanoylglycine, thymidine, and caffeine, as well as compounds such as dinitrotoluene and others, have been characterized and demonstrate selective detection. Water-quality-related halogen-containing anions, fluoride through bromate, contained in liquid samples are also isolated by DMS. A reaction-chamber interface is highlighted as most practical for portable ESI-DMS instrumentation.

  19. Experimental evaluation and optimization of structures for lossless ion manipulations for ion mobility spectrometry with time-of-flight mass spectrometry.

    Science.gov (United States)

    Webb, Ian K; Garimella, Sandilya V B; Tolmachev, Aleksey V; Chen, Tsung-Chi; Zhang, Xinyu; Norheim, Randolph V; Prost, Spencer A; LaMarche, Brian; Anderson, Gordon A; Ibrahim, Yehia M; Smith, Richard D

    2014-09-16

    We report on the performance of structures for lossless ion manipulation (SLIM) as a means for transmitting ions and performing ion mobility separations (IMS). Ions were successfully transferred from an electrospray ionization (ESI) source to the TOF MS analyzer by means of a linear SLIM, demonstrating lossless ion transmission and an alternative arrangement including a 90° turn. First, the linear geometry was optimized for radial confinement by tuning RF on the central "rung" electrodes and potentials on the DC-only guard electrodes. Selecting an appropriate DC guard bias (2-6 V) and RF amplitude (≥160 V(p-p) at 750 kHz) resulted in the greatest ion intensities. Close to ideal IMS resolving power was maintained over a significant range of applied voltages. Second, the 90° turn was optimized for radial confinement by tuning RF on the rung electrodes and DC on the guard electrodes. However, both resolving power and ion transmission showed a dependence on these voltages, and the best conditions for both were >300 V(p-p) RF (685 kHz) and 7-11 V guard DC bias. Both geometries provide IMS resolving powers at the theoretical limit (R ~ 58), showing that degraded resolution from a "racetrack" effect from turning around a corner can be successfully avoided, and the capability also was maintained for essentially lossless ion transmission.

  20. Recent progress on nanostructured 4 V cathode materials for Li-ion batteries for mobile electronics

    Directory of Open Access Journals (Sweden)

    Xiaodong Xu

    2013-12-01

    Full Text Available Mobile electronics have developed so rapidly that battery technology has hardly been able to keep pace. The increasing desire for lighter and thinner Li-ion batteries with higher capacities is a continuing and constant goal for in research. Achieving higher energy densities, which is mainly dependent on cathode materials, has become a critical issue in the development of new Li-ion batteries. In this review, we will outline the progress on nanostructured 4 V cathode materials of Li-ion batteries for mobile electronics, covering LiCoO2, LiNixCoyMn1−x−yO2, LiMn2O4, LiNi0.5Mn1.5O4 and Li-rich layered oxide materials. We aim to provide some scientific insights into the development of superior cathode materials by discussing the advantages of nanostructure, surface-coating, and other key properties.

  1. Ion mobility spectrometric analysis of vaporous chemical warfare agents by the instrument with corona discharge ionization ammonia dopant ambient temperature operation.

    Science.gov (United States)

    Satoh, Takafumi; Kishi, Shintaro; Nagashima, Hisayuki; Tachikawa, Masumi; Kanamori-Kataoka, Mieko; Nakagawa, Takao; Kitagawa, Nobuyoshi; Tokita, Kenichi; Yamamoto, Soichiro; Seto, Yasuo

    2015-03-20

    The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman

  2. Serpentine Ultralong Path with Extended Routing (SUPER) High Resolution Traveling Wave Ion Mobility-MS using Structures for Lossless Ion Manipulations

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-05

    Ion mobility (IM) separations have a broad range of analytical applications, but insufficient resolution limits many applications. Here we report on traveling wave (TW) ion mobility (IM) separations in a Serpentine Ultra-long Path with Extended Routing (SUPER) Structures for Lossless Ion Manipulations (SLIM) module in conjunction with mass spectrometry (MS). The extended routing utilized multiple passes was facilitated by the introduction of a lossless ion switch at the end of the ion path that either directed ions to the MS detector or to another pass through the serpentine separation region, providing theoretically unlimited TWIM path lengths. Ions were confined in the SLIM by rf fields in conjunction with a DC guard bias, enabling essentially lossless TW transmission over greatly extended paths (e.g., ~1094 meters over 81 passes through the 13.5 m serpentine path). In this multi-pass SUPER TWIM provided resolution approximately proportional to the square root of the number of passes (or path length). More than 30-fold higher IM resolution for Agilent tuning mix m/z 622 and 922 ions (~340 vs. ~10) was achieved for 40 passes compared to commercially available drift tube IM and other TWIM-based platforms. An initial evaluation of the isomeric sugars Lacto-N-hexaose and Lacto-N-neohexaose showed the isomeric structures to be baseline resolved, and a new conformational feature for Lacto-N-neohexaose was revealed after 9 passes. The new SLIM SUPER high resolution TWIM platform has broad utility in conjunction with MS and is expected to enable a broad range of previously challenging or intractable separations.

  3. Unambiguous characterization of analytical markers in complex, seized opiate samples using an enhanced ion mobility trace detector-mass spectrometer.

    Science.gov (United States)

    Liuni, Peter; Romanov, Vladimir; Binette, Marie-Josée; Zaknoun, Hafid; Tam, Maggie; Pilon, Pierre; Hendrikse, Jan; Wilson, Derek J

    2014-11-04

    Ion mobility spectroscopy (IMS)-based trace-compound detectors (TCDs) are powerful and widely implemented tools for the detection of illicit substances. They combine high sensitivity, reproducibility, rapid analysis time, and resistance to dirt with an acceptable false alarm rate. The analytical specificity of TCD-IMS instruments for a given analyte depends strongly on a detailed knowledge of the ion chemistry involved, as well as the ability to translate this knowledge into field-robust analytical methods. In this work, we introduce an enhanced hybrid TCD-IMS/mass spectrometer (TCD-IMS/MS) that combines the strengths of ion-mobility-based target compound detection with unambiguous identification by tandem MS. Building on earlier efforts along these lines (Kozole et al., Anal. Chem. 2011, 83, 8596-8603), the current instrument is capable of positive and negative-mode analyses with tightly controlled gating between the IMS and MS modules and direct measurement of ion mobility profiles. We demonstrate the unique capabilities of this instrument using four samples of opium seized by the Canada Border Services Agency (CBSA), consisting of a mixture of opioid alkaloids and other naturally occurring compounds typically found in these samples. Although many analytical methods have been developed for analyzing naturally occurring opiates, this is the first detailed ion mobility study on seized opium samples. This work demonstrates all available analytical modes for the new IMS-MS system including "single-gate", "dual-gate", MS/MS, and precursor ion scan methods. Using a combination of these modes, we unambiguously identify all signals in the IMS spectra, including previously uncharacterized minor peaks arising from compounds that are common in raw opium.

  4. Quantum optical waveform conversion

    CERN Document Server

    Kielpinski, D; Wiseman, HM

    2010-01-01

    Currently proposed architectures for long-distance quantum communication rely on networks of quantum processors connected by optical communications channels [1,2]. The key resource for such networks is the entanglement of matter-based quantum systems with quantum optical fields for information transmission. The optical interaction bandwidth of these material systems is a tiny fraction of that available for optical communication, and the temporal shape of the quantum optical output pulse is often poorly suited for long-distance transmission. Here we demonstrate that nonlinear mixing of a quantum light pulse with a spectrally tailored classical field can compress the quantum pulse by more than a factor of 100 and flexibly reshape its temporal waveform, while preserving all quantum properties, including entanglement. Waveform conversion can be used with heralded arrays of quantum light emitters to enable quantum communication at the full data rate of optical telecommunications.

  5. Proton-driven amide bond-cleavage pathways of gas-phase peptide ions lacking mobile protons.

    Science.gov (United States)

    Bythell, Benjamin J; Suhai, Sándor; Somogyi, Arpád; Paizs, Béla

    2009-10-07

    The mobile proton model (Dongre, A. R., Jones, J. L., Somogyi, A. and Wysocki, V. H. J. Am. Chem. Soc. 1996, 118 , 8365-8374) of peptide fragmentation states that the ionizing protons play a critical role in the gas-phase fragmentation of protonated peptides upon collision-induced dissociation (CID). The model distinguishes two classes of peptide ions, those with or without easily mobilizable protons. For the former class mild excitation leads to proton transfer reactions which populate amide nitrogen protonation sites. This enables facile amide bond cleavage and thus the formation of b and y sequence ions. In contrast, the latter class of peptide ions contains strongly basic functionalities which sequester the ionizing protons, thereby often hindering formation of sequence ions. Here we describe the proton-driven amide bond cleavages necessary to produce b and y ions from peptide ions lacking easily mobilizable protons. We show that this important class of peptide ions fragments by different means from those with easily mobilizable protons. We present three new amide bond cleavage mechanisms which involve salt-bridge, anhydride, and imine enol intermediates, respectively. All three new mechanisms are less energetically demanding than the classical oxazolone b(n)-y(m) pathway. These mechanisms offer an explanation for the formation of b and y ions from peptide ions with sequestered ionizing protons which are routinely fragmented in large-scale proteomics experiments.

  6. Simultaneous determination of nitrite and nitrate in potato and water samples using negative electrospray ionization ion mobility spectrometry.

    Science.gov (United States)

    Jafari, M T; Torki, F; Saraji, M

    2012-01-01

    Nowadays, nitrite and nitrate ions are analyzed in biological samples using laborious and expensive methods; such as HPLC, CE, MS-MS. In this work, the simultaneous analysis of nitrite and nitrate ions was conducted by electrospray ionization-ion mobility spectrometry (ESI-IMS), without using any complicated or laborious derivitization step. Ion mobility spectrometry with low cost, inexpensive maintenance and very fast analysis makes an attractive technique for the simultaneous determination of these ions in foodstuff and drinking water samples. The analyte interference was systematically investigated for binary mixture analysis. The obtained results provided detection limits of 3.8 and 4.7 µg/L for nitrite and nitrate, respectively. A linear dynamic range of about 2 orders of magnitude, and relative standard deviations below 5% were obtained by the proposed method for the analysis of both ions. Also, the proposed method was used to analyze various real samples of potato and drinking water samples, and the obtained results confirmed the capability of negative ESI-IMS for the simultaneous detection of nitrite and nitrate.

  7. Experimental Evaluation and Optimization of Structures for Lossless Ion Manipulations for Ion Mobility Spectrometry with Time-of-Flight Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-05

    We report on the performance of Structures for Lossless Ion Manipulation (SLIM) devices as a means for transmitting ions and performing ion mobility separations (IMS). Ions were successfully transferred from an electrospray ionization (ESI) source to the TOF MS analyzer by means of a linear SLIM device and an alternative arrangement including a 90° turn. First, the linear geometry was optimized for radial confinement by tuning RF on the central ‘rung’ electrodes and potentials on the DC-only guard electrodes. Selecting an appropriate DC guard bias (2-6 V) and RF amplitude (≥160 Vp-p at 750 kHz) resulted in the greatest ion intensities. Close to ideal IMS resolving power was maintained over a range of applied voltages. Second, the 90° turn was optimized for radial confinement by tuning the RF on the rung electrodes and DC on the guard electrodes; however, both resolving power and ion transmission showed a dependence on these voltages and the best conditions for both were > 300 Vp-p RF (685 kHz) and 7-11 V guard DC bias. Both geometries provide IMS resolving powers at the theoretical limit (R~58), showing that the negative “racetrack” effect from turning around a corner can be successfully avoided, as well as the capability for essentially lossless ion transmission.

  8. A volatile organic analyzer for Space Station: Description and evaluation of a gas chromatography/ ion mobility

    Science.gov (United States)

    Limero, Thomas F.; James, John T.

    1994-01-01

    A Volatile Organic Analyzer (VOA) is being developed as an essential component of the Space Station's Environmental Health System (EHS) air quality monitoring strategy to provide warning to the crew and ground personnel if volatile organic compounds exceed established exposure limits. The short duration of most Shuttle flights and the relative simplicity of the contaminant removal mechanism have lessened the concern about crew exposure to air contaminants on the Shuttle. However, the longer missions associated with the Space Station, the complex air revitalization system and the proposed number of experiments have led to a desire for real-time monitoring of the contaminants in the Space Station atmosphere. Achieving the performance requirements established for the VOA within the Space Station resource (e.g., power, weight) allocations led to a novel approach that joined a gas chromatograph (GC) to an ion mobility spectrometer (IMS). The authors of this paper will discuss the rational for selecting the GC/IMS technology as opposed to the more established gas chromatography/mass spectrometry (GC/MS) for the foundation of the VOA. The data presented from preliminary evaluations will demonstrate the versatile capability of the GC/IMS to analyze the major contaminants expected in the Space Station atmosphere. The favorable GC/IMS characteristics illustrated in this paper included excellent sensitivity, dual-mode operation for selective detection, and mobility drift times to distinguish co-eluting GC peaks. Preliminary studies have shown that the GC/IMS technology can meet surpass the performance requirements of the Space Station VOA.

  9. Nanomaterial size distribution analysis via liquid nebulization coupled with ion mobility spectrometry (LN-IMS).

    Science.gov (United States)

    Jeon, Seongho; Oberreit, Derek R; Van Schooneveld, Gary; Hogan, Christopher J

    2016-02-21

    We apply liquid nebulization (LN) in series with ion mobility spectrometry (IMS, using a differential mobility analyzer coupled to a condensation particle counter) to measure the size distribution functions (the number concentration per unit log diameter) of gold nanospheres in the 5-30 nm range, 70 nm × 11.7 nm gold nanorods, and albumin proteins originally in aqueous suspensions. In prior studies, IMS measurements have only been carried out for colloidal nanoparticles in this size range using electrosprays for aerosolization, as traditional nebulizers produce supermicrometer droplets which leave residue particles from non-volatile species. Residue particles mask the size distribution of the particles of interest. Uniquely, the LN employed in this study uses both online dilution (with dilution factors of up to 10(4)) with ultra-high purity water and a ball-impactor to remove droplets larger than 500 nm in diameter. This combination enables hydrosol-to-aerosol conversion preserving the size and morphology of particles, and also enables higher non-volatile residue tolerance than electrospray based aerosolization. Through LN-IMS measurements we show that the size distribution functions of narrowly distributed but similarly sized particles can be distinguished from one another, which is not possible with Nanoparticle Tracking Analysis in the sub-30 nm size range. Through comparison to electron microscopy measurements, we find that the size distribution functions inferred via LN-IMS measurements correspond to the particle sizes coated by surfactants, i.e. as they persist in colloidal suspensions. Finally, we show that the gas phase particle concentrations inferred from IMS size distribution functions are functions of only of the liquid phase particle concentration, and are independent of particle size, shape, and chemical composition. Therefore LN-IMS enables characterization of the size, yield, and polydispersity of sub-30 nm particles.

  10. Ferric ions accumulate in the walls of metabolically inactivating Saccharomyces cerevisiae cells and are reductively mobilized during reactivation.

    Science.gov (United States)

    Wofford, Joshua D; Park, Jinkyu; McCormick, Sean P; Chakrabarti, Mrinmoy; Lindahl, Paul A

    2016-07-13

    Mössbauer and EPR spectra of fermenting yeast cells before and after cell wall (CW) digestion revealed that CWs accumulated iron as cells transitioned from exponential to post-exponential growth. Most CW iron was mononuclear nonheme high-spin (NHHS) Fe(III), some was diamagnetic and some was superparamagnetic. A significant portion of CW Fe was removable by EDTA. Simulations using an ordinary-differential-equations-based model suggested that cells accumulate Fe as they become metabolically inactive. When dormant Fe-loaded cells were metabolically reactivated in Fe-deficient bathophenanthroline disulfonate (BPS)-treated medium, they grew using Fe that had been mobilized from their CWs AND using trace amounts of Fe in the Fe-deficient medium. When grown in Fe-deficient medium, Fe-starved cells contained the lowest cellular Fe concentrations reported for a eukaryotic cell. During metabolic reactivation of Fe-loaded dormant cells, Fe(III) ions in the CWs of these cells were mobilized by reduction to Fe(II), followed by release from the CW and reimport into the cell. BPS short-circuited this process by chelating mobilized and released Fe(II) ions before reimport; the resulting Fe(II)(BPS)3 complex adsorbed on the cell surface. NHHS Fe(II) ions appeared transiently during mobilization, suggesting that these ions were intermediates in this process. In the presence of chelators and at high pH, metabolically inactive cells leached CW Fe; this phenomenon probably differs from metabolic mobilization. The iron regulon, as reported by Fet3p levels, was not expressed during post-exponential conditions; Fet3p was maximally expressed in exponentially growing cells. Decreased expression of the iron regulon and metabolic decline combine to promote CW Fe accumulation.

  11. Measurements of the ion fraction and mobility of alpha and beta decay products in liquid xenon using EXO-200

    CERN Document Server

    Albert, J B; Barbeau, P S; Beck, D; Belov, V; Breidenbach, M; Brunner, T; Burenkov, A; Cao, G F; Chambers, C; Cleveland, B; Coon, M; Craycraft, A; Daniels, T; Danilov, M; Daugherty, S J; Davis, C G; Davis, J; Delaquis, S; Der Mesrobian-Kabakian, A; DeVoe, R; Didberidze, T; Dolgolenko, A; Dolinski, M J; Dunford, M; Fairbank, W; Farine, J; Feldmeier, W; Fierlinger, P; Fudenberg, D; Gornea, R; Graham, K; Gratta, G; Hall, C; Hughes, M; Jewell, M J; Jiang, X S; Johnson, A; Johnson, T N; Johnston, S; Karelin, A; Kaufman, L J; Killick, R; Koffas, T; Kravitz, S; Kuchenkov, A; Kumar, K S; Leonard, D S; Licciardi, C; Lin, Y H; Ling, J; MacLellan, R; Marino, M G; Mong, B; Moore, D; Nelson, R; O'Sullivan, K; Odian, A; Ostrovskiy, I; Piepke, A; Pocar, A; Prescott, C Y; Robinson, A; Rowson, P C; Russell, J J; Schubert, A; Sinclair, D; Smith, E; Stekhanov, V; Tarka, M; Tolba, T; Tsang, R; Twelker, K; Vuilleumier, J -L; Waite, A; Walton, J; Walton, T; Weber, M; Wen, L J; Wichoski, U; Wright, J D; Wood, J; Yang, L; Yen, Y -R; Zeldovich, O Ya

    2015-01-01

    Alpha decays in the EXO-200 detector are used to measure the fraction of charged $^{218}\\mathrm{Po}$ and $^{214}\\mathrm{Bi}$ daughters created from alpha and beta decays, respectively. $^{222}\\mathrm{Rn}$ alpha decays in liquid xenon (LXe) are found to produce $^{218}\\mathrm{Po}^{+}$ ions $50.3 \\pm 3.0\\%$ of the time, while the remainder of the $^{218}\\mathrm{Po}$ atoms are neutral. The fraction of $^{214}\\mathrm{Bi}^{+}$ from $^{214}\\mathrm{Pb}$ beta decays in LXe is found to be $76.4 \\pm 5.7\\%$, inferred from the relative rates of $^{218}\\mathrm{Po}$ and $^{214}\\mathrm{Po}$ alpha decays in the LXe. The average velocity of $^{218}\\mathrm{Po}$ ions is observed to decrease for longer drift times. Initially the ions have a mobility of $0.390 \\pm 0.006~\\mathrm{cm}^2/(\\mathrm{kV}~\\mathrm{s})$, and at long drift times the mobility is $0.219 \\pm 0.004~\\mathrm{cm}^2/(\\mathrm{kV}~\\mathrm{s})$. Time constants associated with the change in mobility during drift of the $^{218}\\mathrm{Po}^{+}$ ions are found to be propor...

  12. Stable compositions and geometrical structures of titanium oxide cluster cations and anions studied by ion mobility mass spectrometry

    Science.gov (United States)

    Ohshimo, Keijiro; Norimasa, Naoya; Moriyama, Ryoichi; Misaizu, Fuminori

    2016-05-01

    Geometrical structures of titanium oxide cluster cations and anions have been investigated by ion mobility mass spectrometry and quantum chemical calculations based on density functional theory. Stable cluster compositions with respect to collision induced dissociation were also determined by changing ion injection energy to an ion drift cell for mobility measurements. The TinO2n-1+ cations and TinO2n- anions were predominantly observed at high injection energies, in addition to TinO2n+ for cations and TinO2n+1- for anions. Collision cross sections of TinO2n+ and TinO2n+1- for n = 1-7, determined by ion mobility mass spectrometry, were compared with those obtained theoretically as orientation-averaged cross sections for the optimized structures by quantum chemical calculations. All of the geometrical structures thus assigned have three-dimensional structures, which are in marked contrast with other oxides of late transition metals. One-oxygen atom dissociation processes from TinO2n+ and TinO2n+1- by collisions were also explained by analysis of spin density distributions.

  13. Assessment of the feasibility of the use of conductive polymers in the fabrication of ion mobility spectrometers.

    Science.gov (United States)

    Koimtzis, Theodoros; Goddard, Nick J; Wilson, Ian; Thomas, C L Paul

    2011-04-01

    The development of an ion mobility spectrometer with an injection molded plastic drift tube made from carbon-loaded nylon and the cyclo-olefinpolymer Zeonex is described. Thermogravimetric assessment combined with headspace analysis by ion mobility spectrometry and gas chromatography-mass spectrometry indicated that Zeonex encapsulated carbon-loaded nylon could be used to fabricate a snap-together injection molded stacked ring drift tube, 4.25 cm long that could be substituted for a conventional wire-wound heated ceramic drift tube of the same length into a high temperature ion mobility spectrometer. Temperature stability experiments indicated that such a combination of polymers produced stable water-based reactant ion peaks [(H(2)O)(n)H](+) up to a temperature of approximately 50 °C. Above this temperature, ammonia appeared to outgas, resulting in the production of [(H(2)O)(n)(NH(4))(m)H](+) type species before, at higher temperatures, the release of oligomeric entities suppressed resolved ion responses. Surface charging effects were also observed, and over a period of continuous operation of 4 h, these caused suppression of the signal intensity (1.11-0.954 V) and an apparent mobility shift in the observed responses (K(0) = 1.86-1.90 cm(2) V(-1) s(-1)). Substituting nylon, a polymer with a significantly lower surface resistivity, for the Zeonex demonstrated how surface charging phenomena could be managed though control of surface resistivity in future polymer formulations. The device was challenged successfully with test atmospheres of hexan-1-ol (K(0) = 1.66 cm(2) V(-1) s(-1) (monomer) and 1.32 cm(2) V(-1) s(-1)(dimer)) and dimethylmethyl phosphonate (K(0) = 1.70 cm(2) V(-1) s(-1) (monomer) and 1.44 cm(2) V(-1) s(-1) (dimer)). The potential advantages of developing polymeric systems using more advanced polymer formulations are discussed.

  14. Evaluation of ion mobility-mass spectrometry for determining the isomeric heterogeneity of oligosaccharide-alditols derived from bovine submaxillary mucin.

    Science.gov (United States)

    Li, Hongli; Bendiak, Brad; Kaplan, Kimberly; Davis, Eric; Siems, William F; Hill, Herbert H

    2013-10-15

    Rapid separation and independent analysis of isomeric species are needed for the structural characterization of carbohydrates in glycomics research. Ion mobility-mass spectrometry techniques were used to examine a series of isomeric neutral oligosaccharide-alditols derived from bovine submaxillary mucin. Several analytical techniques were employed: (1) off line separation of the oligosaccharide-alditol mixture by HPLC; (2) direct and rapid evaluation of isomeric heterogeneity of oligosaccharides by electrospray ionization-ion mobility-time of flight mass spectrometry; and (3) mobility-selected MS(2) and MS(3) to evaluate isomeric mobility peaks by dual gate ion mobility-tandem mass spectrometry. Multiple isomeric ion mobility peaks were observed for the majority of oligosaccharide-alditols, which was achieved on the millisecond time scale after LC separation. Fragmentation spectra obtained from the collision-induced dissociation of isomeric precursor ions could be essentially identical, or dramatically different for a given precursor m/z using the dual-gate ion mobility quadrupole ion trap mass spectrometer. This further confirmed the need for rapid physical resolution of isomeric precursor species prior to their tandem mass spectral analysis.

  15. Ion mobility spectrometry: a comprehensive and versatile tool for occupational pharmaceutical exposure assessment.

    Science.gov (United States)

    Armenta, S; Blanco, M

    2012-05-15

    The qualitative and quantitative capabilities of ion mobility spectrometry (IMS) as a comprehensive and powerful tool in workplace air monitoring have been demonstrated on the example of a Spanish pharmaceutical company. The developed IMS based procedure is capable of detecting and determining in air samples the active pharmaceutical ingredients (APIs) manipulated and/or produced in this pharmaceutical industry. Sensitivity, in the ng-pg range, selectivity, possibly to provide results in near real time, and reduction of analysis costs are the most important properties that ratify IMS as a serious alternative in occupational exposure assessment. The possibility of false positives by drift time interferences and false negatives by competitive ionization and also desorption process interferences has been deeply evaluated. Moreover, chemometric strategies based on self-modeling curve resolution (SMCR) have been applied to obtain qualitative and quantitative individual component information from overlapped peaks. The IMS procedure has been successfully applied to evaluate the concentration of APIs (nimesulide, dexketoprofen, deflazacort) handled by the pharmaceutical company employees in the making of tablets and granulates, and control measures have been suggested in accordance.

  16. Characterization and validation of ion mobility spectrometry in methamphetamine clandestine laboratory remediation.

    Science.gov (United States)

    Moran, Jordan; McCall, Holly; Yeager, Brittany; Bell, Suzanne

    2012-10-15

    This project evaluated the efficacy of ion mobility spectrometry (IMS) as a tool for determining remediation success at clandestine methamphetamine laboratory sites. Specifically, limits of detection (LOD), limits of quantitation (LOQ), and matrix effects were investigated as relevant to typical remediation sites and situations. The recoveries of pseudoephedrine and methamphetamine from a range of various surfaces likely to be found in a clandestine laboratory were examined. Portable IMS instruments with thermal desorption were found to be a reliable tool for evaluating the degree of remediation if sufficient procedural and instrumental controls are put into place. In general, detection limits were in the same range as state guidelines as well as laboratory methods using GC/MS and LC/MS. Direct vapor sampling can be used to detect high levels of methamphetamine and potential interferences, but cannot approach the detection limits needed for evaluation of remediation efforts. IMS cannot be used alone to determine the efficacy of remediation efforts; final confirmation using laboratory instrumentation is essential. For the purpose of this study, typical field settings of the IMS were used and the conditions were not optimized.

  17. Application of ion mobility spectrometry for the determination of tramadol in biological samples

    Directory of Open Access Journals (Sweden)

    Ali Sheibani

    2014-12-01

    Full Text Available In this study, a simple and rapid ion mobility spectrometry (IMS method has been described for the determination of tramadol. The operating instrumental parameters that could influence IMS were investigated and optimized (temperature; injection: 220 and IMS cell: 190°C, flow rate; carrier: 300 and drift: 600 mL/minute, voltage; corona: 2300 and drift: 7000 V, pulse width: 100 μs. Under optimum conditions, the calibration curves were linear within two orders of magnitude with R2 ≥ 0.998 for the determination of tramadol in human plasma, saliva, serum, and urine samples. The limits of detection and the limits of quantitation were between 0.1 and 0.3 and 0.3 and 1 ng/mL, respectively. The relative standard deviations were between 7.5 and 8.8%. The recovery results (90–103.9% indicate that the proposed method can be applied for tramadol analysis in different biological samples.

  18. Direct detection of trimethylamine in meat food products using ion mobility spectrometry.

    Science.gov (United States)

    Bota, Gheorghe M; Harrington, Peter B

    2006-01-15

    Biogenic amines are degradation products generated by bacteria in meat products. These amines can indicate bacterial contamination or have a carcinogenic effect to humans consuming spoiled meats; therefore, their rapid detection is essential. Trimethylamine (TMA) is a good target for the detection of biogenic amines because its volatility. TMA was directly detected in meat food products using ion mobility spectrometry (IMS). TMA concentrations were measured in chicken meat juice for a quantitative evaluation of the meat decaying process. The lowest detected TMA concentration in chicken juice was 0.6+/-0.2 ng and the lowest detected signal for TMA in a standard aqueous solution was 0.6 ng. IMS data were processed using partial least squares (PLS) and Fuzzy rule-building expert system (FuRES). Using these two chemometric methods, trimethylamine concentrations of different days of meat spoilage can be separated, indicating the decaying of meat products. Comparing the two methods, FuRES provided a better classification of different days of meat spoilage.

  19. Monitoring Conformational Landscape of Ovine Prion Protein Monomer Using Ion Mobility Coupled to Mass Spectrometry

    Science.gov (United States)

    Van der Rest, Guillaume; Rezaei, Human; Halgand, Frédéric

    2017-02-01

    Prion protein is involved in deadly neurodegenerative diseases. Its pathogenicity is linked to its structural conversion (α-helix to β-strand transition). However, recent studies suggest that prion protein can follow a plurality of conversion pathways, which hints towards different conformers that might coexist in solution. To gain insights on the plasticity of the ovine prion protein (PrP) monomer, wild type (A136, R154, Q171), mutants and deletions of ARQ were studied by traveling wave ion mobility experiments coupled to mass spectrometry. In order to perform the analysis of a large body of data sets, we designed and evaluated the performance of a processing pipeline based on Driftscope peak detection and a homemade script for automated peak assignment, annotation, and quantification on specific multiply charged protein data. Using this approach, we showed that in the gas phase, PrPs are represented by at least three conformer families differing in both charge state distribution and collisional cross-section, in agreement with the work of Hilton et al. (2010). We also showed that this plasticity is borne both by the N- and C-terminal domains. Effect of protein concentration, pH and temperature were also assessed, showing that (1) pH does not affect conformer distributions, (2) protein concentration modifies the conformational landscape of one mutant (I208M) only, and (3) heating leads to other unfolded species and to a modification of the conformer intensity ratios.

  20. Coming to Grips with Ambiguity: Ion Mobility-Mass Spectrometry for Protein Quaternary Structure Assignment

    Science.gov (United States)

    Eschweiler, Joseph D.; Frank, Aaron T.; Ruotolo, Brandon T.

    2017-10-01

    Multiprotein complexes are central to our understanding of cellular biology, as they play critical roles in nearly every biological process. Despite many impressive advances associated with structural characterization techniques, large and highly-dynamic protein complexes are too often refractory to analysis by conventional, high-resolution approaches. To fill this gap, ion mobility-mass spectrometry (IM-MS) methods have emerged as a promising approach for characterizing the structures of challenging assemblies due in large part to the ability of these methods to characterize the composition, connectivity, and topology of large, labile complexes. In this Critical Insight, we present a series of bioinformatics studies aimed at assessing the information content of IM-MS datasets for building models of multiprotein structure. Our computational data highlights the limits of current coarse-graining approaches, and compelled us to develop an improved workflow for multiprotein topology modeling, which we benchmark against a subset of the multiprotein complexes within the PDB. This improved workflow has allowed us to ascertain both the minimal experimental restraint sets required for generation of high-confidence multiprotein topologies, and quantify the ambiguity in models where insufficient IM-MS information is available. We conclude by projecting the future of IM-MS in the context of protein quaternary structure assignment, where we predict that a more complete knowledge of the ultimate information content and ambiguity within such models will undoubtedly lead to applications for a broader array of challenging biomolecular assemblies. [Figure not available: see fulltext.

  1. Determination of 3,4-methylenedioxypyrovalerone (MDPV) in oral and nasal fluids by ion mobility spectrometry.

    Science.gov (United States)

    Peiró, Maria de las Nieves; Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel

    2016-05-01

    A fast and sensitive methodology has been developed for the evaluation of the 3,4-methylenedioxypyrovalerone (MDPV) consumed. Based on ion mobility spectrometry (IMS), MDPV was directly determined in nasal fluids with a limit of detection (LOD) in the order of 22 ng mL(-1), which corresponds to an absolute amount of 33 ng of MDPV per swab. MDPV was also determined after liquid-liquid microextraction (LLME) in oral fluids to avoid matrix effects, obtaining a LOD value of 4.4 ng mL(-1) in oral fluid samples. The IMS spectrum for MDPV exhibited a peak with K0 = 1.210 ± 0.005 cm(2)V(-1) s(-1) at a drift time of 14.62 ms, the total analysis time being 4.5 min per oral fluid and 1.5 min per nasal fluid sample. Samples must be analyzed within 24 h following collection and dissolution in 2-propanol, based on the complementary stability studies.

  2. Ion mobility spectrometry as a fast analytical tool in benzalkonium chloride homologs determination.

    Science.gov (United States)

    Gallart-Mateu, D; Armenta, S; Esteve-Turrillas, F A; de la Guardia, M

    2017-03-01

    A novel procedure is proposed for the determination by ion mobility spectrometry (IMS) of C12, C14 and C16 benzalkonium chloride (BAC) homologs. The proposed method requires minimum sample treatment and the measurement was made in less than one minute. A high sensitivity was obtained for BAC determination by IMS with limit of detection values from 37 to 69µgL(-1). Accuracy of the proposed methodology was evaluated through the analysis of aqueous and alcoholic samples spiked with BAC at concentration levels from 0.002% to 20% (w/v), providing recovery values from 91% to 104%. BAC was determined in sanitary alcohols, nasal sprays, postharvest products, algaecides, and treated swimming pool water. Results obtained by the proposed IMS methodology were statistically comparable to those provided by a liquid chromatography-ultraviolet (LC-UV) reference methodology. The Green Certificate evaluation of the proposed IMS methodology provided 91 score points in the Eco-Scale as compared with 77 for LC-UV method.

  3. Native Mass Spectrometry, Ion mobility, and Collision-Induced Unfolding Categorize Malaria Antigen/Antibody Binding

    Science.gov (United States)

    Huang, Yining; Salinas, Nichole D.; Chen, Edwin; Tolia, Niraj H.; Gross, Michael L.

    2017-09-01

    Plasmodium vivax Duffy Binding Protein (PvDBP) is a promising vaccine candidate for P. vivax malaria. Recently, we reported the epitopes on PvDBP region II (PvDBP-II) for three inhibitory monoclonal antibodies (2D10, 2H2, and 2C6). In this communication, we describe the combination of native mass spectrometry and ion mobility (IM) with collision induced unfolding (CIU) to study the conformation and stabilities of three malarial antigen-antibody complexes. These complexes, when collisionally activated, undergo conformational changes that depend on the location of the epitope. CIU patterns for PvDBP-II in complex with antibody 2D10 and 2H2 are highly similar, indicating comparable binding topology and stability. A different CIU fingerprint is observed for PvDBP-II/2C6, indicating that 2C6 binds to PvDBP-II on an epitope different from 2D10 and 2H2. This work supports the use of CIU as a means of classifying antigen-antibody complexes by their epitope maps in a high throughput screening workflow. [Figure not available: see fulltext.

  4. Application of ion mobility spectrometry for the detection of human urine.

    Science.gov (United States)

    Rudnicka, Joanna; Mochalski, Paweł; Agapiou, Agapios; Statheropoulos, Milt; Amann, Anton; Buszewski, Bogusław

    2010-11-01

    The aim of the present study was to evaluate the suitability of ion mobility spectrometry (IMS) for the detection of human urine as an indication of human presence during urban search and rescue operations in collapsed buildings. To this end, IMS with a radioactive ionization source and a multicapillary column was used to detect volatile organic compounds (VOCs) emitted from human urine. A study involving a group of 30 healthy volunteers resulted in the selection of seven volatile species, namely acetone, propanal, 3-methyl-2-butanone, 2-methylpropanal, 4-heptanone, 2-heptanone and octanal, which were detected in all samples. Additionally, a preliminary study on the permeation of urine volatiles through the materials surrounding the voids of collapsed buildings was performed. In this study, quartz sand was used as a representative imitating material. Four compounds, namely 3-methyl-2-butanone, octanal, acetone and 2-heptanone, were found to permeate through the sand layers during all experiments. Moreover, their permeation times were the shortest. Although IMS can be considered as a potential technique suitable for the detection, localization and monitoring of VOCs evolved from human urine, further investigation is necessary prior to selecting field chemical methods for the early location of trapped victims.

  5. Detection of metabolites of trapped humans using ion mobility spectrometry coupled with gas chromatography.

    Science.gov (United States)

    Vautz, Wolfgang; Slodzynski, Rafael; Hariharan, Chandrasekhara; Seifert, Luzia; Nolte, Jürgen; Fobbe, Rita; Sielemann, Stefanie; Lao, Bolan C; Huo, Ran; Thomas, C L Paul; Hildebrand, Lars

    2013-02-19

    For the first time, ion mobility spectrometry coupled with rapid gas chromatography, using multicapillary columns, was applied for the development of a pattern of signs of life for the localization of entrapped victims after disaster events (e.g., earthquake, terroristic attack). During a simulation experiment with entrapped volunteers, 12 human metabolites could be detected in the air of the void with sufficient sensitivity to enable a valid decision on the presence of a living person. Using a basic normalized summation of the measured concentrations, all volunteers involved in the particular experiments could be recognized only few minutes after they entered the simulation void and after less than 3 min of analysis time. An additional independent validation experiment enabled the recognition of a person in a room of ∼25 m(3) after ∼30 min with sufficiently high sensitivity to detect even a person briefly leaving the room. Undoubtedly, additional work must be done on analysis time and weight of the equipment, as well as on validation during real disaster events. However, the enormous potential of the method as a significantly helpful tool for search-and-rescue operations, in addition to trained canines, could be demonstrated.

  6. Multi-Capillary Column-Ion Mobility Spectrometry of Volatile Metabolites Emitted by Saccharomyces Cerevisiae

    Directory of Open Access Journals (Sweden)

    Christoph Halbfeld

    2014-09-01

    Full Text Available Volatile organic compounds (VOCs produced during microbial fermentations determine the flavor of fermented food and are of interest for the production of fragrances or food additives. However, the microbial synthesis of these compounds from simple carbon sources has not been well investigated so far. Here, we analyzed the headspace over glucose minimal salt medium cultures of Saccharomyces cerevisiae using multi-capillary column-ion mobility spectrometry (MCC-IMS. The high sensitivity and fast data acquisition of the MCC-IMS enabled online analysis of the fermentation off-gas and 19 specific signals were determined. To four of these volatile compounds, we could assign the metabolites ethanol, 2-pentanone, isobutyric acid, and 2,3-hexanedione by MCC-IMS measurements of pure standards and cross validation with thermal desorption–gas chromatography-mass spectrometry measurements. Despite the huge biochemical knowledge of the biochemistry of the model organism S. cerevisiae, only the biosynthetic pathways for ethanol and isobutyric acid are fully understood, demonstrating the considerable lack of research of volatile metabolites. As monitoring of VOCs produced during microbial fermentations can give valuable insight into the metabolic state of the organism, fast and non-invasive MCC-IMS analyses provide valuable data for process control.

  7. Detection and identification of sugar alcohol sweeteners by ion mobility spectrometry.

    Science.gov (United States)

    Browne, Christopher A; Forbes, Thomas P; Sisco, Edward

    2016-07-28

    The rapid and sensitive detection of sugar alcohol sweeteners was demonstrated using ion mobility spectrometry (IMS). IMS provides a valuable alternative in sensitivity, cost, and analysis speed between the lengthy gold-standard liquid chromatography-mass spectrometry (LC-MS) technique and rapid point-of-measurement disposable colorimetric sensors, for the Food and Nutrition industry's quality control and other "foodomics" area needs. The IMS response, characteristic signatures, and limits of detection for erythritol, pentaerythritol, xylitol, inositol, sorbitol, mannitol, and maltitol were evaluated using precise inkjet printed samples. IMS system parameters including desorption temperature, scan time, and swipe substrate material were examined and optimized, demonstrating a strong dependence on the physicochemical properties of the respective sugar alcohol. The desorption characteristics of each compound were found to dominate the system response and overall sensitivity. Sugar alcohol components of commercial products - chewing gum and a sweetener packet - were detected and identified using IMS. IMS is demonstrated to be an advantageous field deployable instrument, easily operated by non-technical personnel, and enabling sensitive point-of-measurement quality assurance for sugar alcohols.

  8. A nanoscale soft-ionization membrane: A novel ionizer for ion mobility spectrometers for space applications

    Science.gov (United States)

    Hartley, Frank T.; Kanik, Isik

    2002-11-01

    The Jet Propulsion Laboratory (JPL) has developed a novel nanometer-thick "Soft Ionization Membrane" (SIM) which is capable of ionizing nearly 100% of the gases that pass through it. Both sides of the membrane are coated with a metallic conducting film. A modest potential of less than 10 Volts across the membrane produces an electric field in excess of 107 V/cm over a region that is smaller than the mean free path of gas molecules which ionizes the neutral molecules that passing through. Because the region of high electric field is smaller than the mean free path of gas molecules, there are virtually no high energy collisions and the system does not suffer from the fatal problem of avalanche breakdown. The soft ionization mechanism does not fracture the medium or cause any secondary ionization. Thus, a truly new ionization technique is enabled by a simple nanoscale micromachined device. The SIM is tiny, rugged and well suited for a wide variety of applications ranging from space micropropulsion systems to miniature analytical separation devices. In this paper we focus our attention on ion mobility spectrometers (IMSs) as a potential candidate to be incorporated with SIM.

  9. Early stages of insulin fibrillogenesis examined with ion mobility mass spectrometry and molecular modelling.

    Science.gov (United States)

    Cole, Harriet; Porrini, Massimiliano; Morris, Ryan; Smith, Tom; Kalapothakis, Jason; Weidt, Stefan; Mackay, C Logan; MacPhee, Cait E; Barran, Perdita E

    2015-10-21

    A prevalent type of protein misfolding causes the formation of β-sheet-rich structures known as amyloid fibrils. Research into the mechanisms of fibril formation has implications for both disease prevention and nanoscale templating technologies. This investigation into the aggregation of insulin utilises ion mobility mass spectrometry coupled with molecular modelling to identify and characterise oligomers formed during the 'lag' phase that precedes fibril growth. High resolution mass spectrometry and collision induced dissociation is used to unequivocally assign species as m/z coincident multimers or confomers, providing a robust analytical approach that supports the use of molecular dynamics to atomistically resolve the observed oligomers. We show that insulin oligomerises to form species In where 2 ≤ n ≤ 12 and within this set of oligomers we delineate over 60 distinct conformations, the most dominant of which are compact species. Modelling trained with experimental data suggests that the dominant compact dimers are enriched in β-sheet secondary structure and dominated by hydrophobic interactions, and provides a linear relationship between Rg and collision cross section. This approach provides detailed insight to the early stages of assembly of this much studied amyloidogenic protein, and can be used to inform models of nucleation and growth.

  10. Detection of nitro-based and peroxide-based explosives by fast polarity-switchable ion mobility spectrometer with ion focusing in vicinity of Faraday detector.

    Science.gov (United States)

    Zhou, Qinghua; Peng, Liying; Jiang, Dandan; Wang, Xin; Wang, Haiyan; Li, Haiyang

    2015-05-29

    Ion mobility spectrometer (IMS) has been widely deployed for on-site detection of explosives. The common nitro-based explosives are usually detected by negative IMS while the emerging peroxide-based explosives are better detected by positive IMS. In this study, a fast polarity-switchable IMS was constructed to detect these two explosive species in a single measurement. As the large traditional Faraday detector would cause a trailing reactant ion peak (RIP), a Faraday detector with ion focusing in vicinity was developed by reducing the detector radius to 3.3 mm and increasing the voltage difference between aperture grid and its front guard ring to 591 V, which could remove trailing peaks from RIP without loss of signal intensity. This fast polarity-switchable IMS with ion focusing in vicinity of Faraday detector was employed to detect a mixture of 10 ng 2,4,6-trinitrotoluene (TNT) and 50 ng hexamethylene triperoxide diamine (HMTD) by polarity-switching, and the result suggested that [TNT-H](-) and [HMTD+H](+) could be detected in a single measurement. Furthermore, the removal of trailing peaks from RIP by the Faraday detector with ion focusing in vicinity also promised the accurate identification of KClO4, KNO3 and S in common inorganic explosives, whose product ion peaks were fairly adjacent to RIP.

  11. Mobilization

    Science.gov (United States)

    1987-01-01

    istic and romantic emotionalism that typifies this genre. Longino, James C., et al. “A Study of World War Procurement and Industrial Mobilization...States. Harrisburg, PA: Military Service Publishing Co., 1941. CARL 355.22 J72b. Written in rough prose , this World War II era document explains the

  12. Feasibility of ultra-performance liquid chromatography-ion mobility-time-of-flight mass spectrometry in analyzing oxysterols.

    Science.gov (United States)

    Kylli, Petri; Hankemeier, Thomas; Kostiainen, Risto

    2017-03-03

    Oxysterols are oxygenated cholesterols that are important in many cell functions and they may also be indicative of certain diseases. The purpose of this work was to study the feasibility of ultra-performance liquid chromatography-ion mobility-time-of-flight mass spectrometry (UPLC-IM-TOFMS) using traveling wave cell in analyzing oxysterols and especially their isomers in biological samples. Oxysterols were analyzed as their p-toluenesulfonyl isocyanate derivatives, which improved the separation of isomeric oxysterols by ion mobility and ionization efficiency in the electrospray ionization step. The UPLC-IM-TOFMS method was shown to be fast and to provide good quantitative performance. The feasibility of the method was demonstrated in the analyses of oxysterols in fibroblast cell samples.

  13. Coupling Front-End Separations, Ion Mobility Spectrometry, and Mass Spectrometry For Enhanced Multidimensional Biological and Environmental Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Wojcik, Roza [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Zhang, Xing [Skaggs School of Pharmacy and Pharmaceutical Sciences, Anschutz Medical Campus, University of Colorado, Denver, Colorado 80045; Ibrahim, Yehia M. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Burnum-Johnson, Kristin E. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Orton, Daniel J. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Monroe, Matthew E. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Moore, Ronald J. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Smith, Richard D. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Baker, Erin S. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,

    2017-06-12

    Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. IMS alone is useful, but its coupling with mass spectrometry (MS) and front-end separations has been extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information in biological and environmental sample analyses. Multiple studies in disease screening and environmental evaluations have even shown these IMS-based multidimensional separations extract information not possible with each technique individually. This review highlights 3-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography (GC), supercritical fluid chromatography (SFC), liquid chromatography (LC), solid phase extractions (SPE), capillary electrophoresis (CE), field asymmetric ion mobility spectrometry (FAIMS), and microfluidic devices. The origination, current state, various applications, and future capabilities for these multidimensional approaches are described to provide insight into the utility and potential of each technique.

  14. FTP-Server for exchange, interpretation, and database-search of ion mobility spectra, literature, preprints and software

    Science.gov (United States)

    Baumbach, J. I.; Vonirmer, A.

    1995-01-01

    To assist current discussion in the field of ion mobility spectrometry, at the Institut fur Spectrochemie und angewandte Spektroskopie, Dortmund, start with 4th of December, 1994 work of an FTP-Server, available for all research groups at univerisities, institutes and research worker in industry. We support the exchange, interpretation, and database-search of ion mobility spectra through data format JCAMP-DS (Joint Committee on Atomic and Molecular Physical Data) as well as literature retrieval, pre-print, notice, and discussion board. We describe in general lines the entrance conditions, local addresses, and main code words. For further details, a monthly news report will be prepared for all common users. Internet email address for subscribing is included in document.

  15. The minimum detection limits of RDX and TNT deposited on various surfaces as determined by ion mobility spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rodacy, P.

    1993-08-01

    An Ion Mobility Spectrometer (IMS) was used to determine the detection limits of RDX and TNT on six different substrates. The preparation of the explosive deposits on the surfaces is examined as well as effects due to the size, uniformity, method of application, and time that a deposit has been on a surface. Sampling methods are discussed along with effects of the surface topology. The transfer of explosives from a hand to a surface, and methods to reduce the detection limits are presented.

  16. Electronics via waveform analysis

    CERN Document Server

    Craig, Edwin C

    1993-01-01

    The author believes that a good basic understanding of electronics can be achieved by detailed visual analyses of the actual voltage waveforms present in selected circuits. The voltage waveforms included in this text were photographed using a 35-rrun camera in an attempt to make the book more attractive. This book is intended for the use of students with a variety of backgrounds. For this reason considerable material has been placed in the Appendix for those students who find it useful. The Appendix includes many basic electricity and electronic concepts as well as mathematical derivations that are not vital to the understanding of the circuit being discussed in the text at that time. Also some derivations might be so long that, if included in the text, it could affect the concentration of the student on the circuit being studied. The author has tried to make the book comprehensive enough so that a student could use it as a self-study course, providing one has access to adequate laboratory equipment.

  17. Quantitative detection of benzene in toluene- and xylene-rich atmospheres using high-kinetic-energy ion mobility spectrometry (IMS).

    Science.gov (United States)

    Langejuergen, Jens; Allers, Maria; Oermann, Jens; Kirk, Ansgar; Zimmermann, Stefan

    2014-12-02

    One major drawback of ion mobility spectrometry (IMS) is the dependence of the response to a certain analyte on the concentration of water or the presence of other compounds in the sample gas. Especially for low proton affine analytes, e.g., benzene, which often exists in mixtures with other volatile organic compounds, such as toluene and xylene (BTX), a time-consuming preseparation is necessary. In this work, we investigate BTX mixtures using a compact IMS operated at decreased pressure (20 mbar) and high kinetic ion energies (HiKE-IMS). The reduced electric field in both the reaction tube and the drift tube can be independently increased up to 120 Td. Under these conditions, the water cluster distribution of reactant ions is shifted toward smaller clusters independent of the water content in the sample gas. Thus, benzene can be ionized via proton transfer from H3O(+) reactant ions. Also, a formation of benzene ions via charge transfer from NO(+) is possible. Furthermore, the time for interaction between ions and neutrals of different analytes is limited to such an extent that a simultaneous quantification of benzene, toluene, and xylene is possible from low ppbv up to several ppmv concentrations. The mobility resolution of the presented HiKE-IMS varies from R = 65 at high field (90 Td) to R = 73 at lower field (40 Td) in the drift tube, which is sufficient to separate the analyzed compounds. The detection limit for benzene is 29 ppbv (2 s of averaging) with 3700 ppmv water, 12.4 ppmv toluene, and 9 ppmv xylene present in the sample gas. Furthermore, a less-moisture-dependent benzene measurement with a detection limit of 32 ppbv with ca. 21 000 ppmv (90% relative humidity (RH) at 20 °C) water present in the sample gas is possible evaluating the signal from benzene ions formed via charge transfer.

  18. QUALITY ASSESSMENT OF SF6 INSULATION AT WARU 150 KV GIS COMPARTMENT USING PARTIAL DISCHARGE ION MOBILITY SPECTROMETER

    Directory of Open Access Journals (Sweden)

    Yulistya Negara

    2009-05-01

    Full Text Available Almost all of modern gas insulated switchgears (GIS use sulphur hexafluoride (SF6 as insulation material. Therefore, GIS quality much or less depends on quality of its SF6. Failure however can arise within operation of SF6 GIS due to quality decline of SF6. Quality decline of SF6 in GIS can be recognized by existence of decomposition product of SF6, which may appear due to partial discharge, arc during switching, etc. Therefore quality control of SF6 insulation in GIS is necessary in order to prevent failure occurred due to SF6 quality decline. In this study, quality assessment of SF6 at Waru 150 kV SF6 GIS is done using equipment namely partial discharge ion mobility spectrometer.  This equipment assesses quality of SF6 based on ions mobility. Concentration of decomposition product is then obtained from ion mobility of gas analyzed. For all compartment tested of Waru 150 kV SF6 GIS, it was found that the largest concentration of decomposition product is between 1000-2000 ppmv. Generally, SF6 condition at Waru 150 kV SF6 GIS is normal based on CIGRE standard.

  19. Fast vaporization solid phase microextraction and ion mobility spectrometry: A new approach for determination of creatinine in biological fluids.

    Science.gov (United States)

    Jafari, Mostafa; Ebrahimzadeh, Homeira; Banitaba, Mohamma Hossein

    2015-11-01

    In this work a rapid and simple method for creatinine determination in urine and plasma samples based on aqueous derivatization of creatinine and complete vaporization of sample (as low as 10 µL), followed by ion mobility spectrometry analysis has been proposed. The effect of four important parameters (extraction temperature, total volume of solution, desorption temperature and extraction time) on ion mobility signal has been studied. Under the optimized conditions, the quantitative response of ion mobility spectrometry for creatinine was linear in the range of 0-500 mg L(-1) with a detection limit of 0.6 mg L(-1) in urine and 0-250 mg L(-1) with a detection limit of 2.6 mg L(-1) in plasma sample. The limit of quantitation of creatinine was 2.1 mg L(-1) and 8.7 mg L(-1) in urine and plasma samples, respectively. The relative standard deviation of the method was found to be 13%. The method was successfully applied to the analysis of creatinine in biological samples, showing recoveries from 92% to 104% in urine and 101-110% in plasma samples.

  20. Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

    Energy Technology Data Exchange (ETDEWEB)

    Jha, Manis Kumar, E-mail: mkjha@nmlindia.org; Kumari, Anjan; Jha, Amrita Kumari; Kumar, Vinay; Hait, Jhumki; Pandey, Banshi Dhar

    2013-09-15

    Graphical abstract: Recovery of valuable metals from scrap batteries of mobile phone. - Highlights: • Recovery of Co and Li from spent LIBs was performed by hydrometallurgical route. • Under the optimum condition, 99.1% of lithium and 70.0% of cobalt were leached. • The mechanism of the dissolution of lithium and cobalt was studied. • Activation energy for lithium and cobalt were found to be 32.4 kJ/mol and 59.81 kJ/mol, respectively. • After metal recovery, residue was washed before disposal to the environment. - Abstract: In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H{sub 2}O{sub 2} (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H{sub 2}O{sub 2} in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 − (1 − X){sup 1/3} = k{sub c}t. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 − 3(1 − X){sup 2/3} + 2(1 − X) = k{sub c}t. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.

  1. Ion mobility spectrometry-mass spectrometry (IMS-MS) for on- and offline analysis of atmospheric gas and aerosol species

    Science.gov (United States)

    Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan; Junninen, Heikki; Massoli, Paola; Lambe, Andrew T.; Kimmel, Joel R.; Cubison, Michael J.; Graf, Stephan; Lin, Ying-Hsuan; Budisulistiorini, Sri H.; Zhang, Haofei; Surratt, Jason D.; Knochenmuss, Richard; Jayne, John T.; Worsnop, Douglas R.; Jimenez, Jose-Luis; Canagaratna, Manjula R.

    2016-07-01

    Measurement techniques that provide molecular-level information are needed to elucidate the multiphase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS-MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS-MS after ionization with a custom-built nitrate chemical ionization (CI) source. This CI-IMS-MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field campaign in the forested SE US. The ambient IMS-MS signals are consistent with laboratory IMS-MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-D IMS-MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS-MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisionally induced dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the

  2. Assessing Accuracy of Waveform Models against Numerical Relativity Waveforms

    Science.gov (United States)

    Pürrer, Michael; LVC Collaboration

    2016-03-01

    We compare currently available phenomenological and effective-one-body inspiral-merger-ringdown models for gravitational waves (GW) emitted from coalescing black hole binaries against a set of numerical relativity waveforms from the SXS collaboration. Simplifications are used in the construction of some waveform models, such as restriction to spins aligned with the orbital angular momentum, no inclusion of higher harmonics in the GW radiation, no modeling of eccentricity and the use of effective parameters to describe spin precession. In contrast, NR waveforms provide us with a high fidelity representation of the ``true'' waveform modulo small numerical errors. To focus on systematics we inject NR waveforms into zero noise for early advanced LIGO detector sensitivity at a moderately optimistic signal-to-noise ratio. We discuss where in the parameter space the above modeling assumptions lead to noticeable biases in recovered parameters.

  3. Optimizing defibrillation waveforms for ICDs.

    Science.gov (United States)

    Kroll, Mark W; Swerdlow, Charles D

    2007-04-01

    While no simple electrical descriptor provides a good measure of defibrillation efficacy, the waveform parameters that most directly influence defibrillation are voltage and duration. Voltage is a critical parameter for defibrillation because its spatial derivative defines the electrical field that interacts with the heart. Similarly, waveform duration is a critical parameter because the shock interacts with the heart for the duration of the waveform. Shock energy is the most often cited metric of shock strength and an ICD's capacity to defibrillate, but it is not a direct measure of shock effectiveness. Despite the physiological complexities of defibrillation, a simple approach in which the heart is modeled as passive resistor-capacitor (RC) network has proved useful for predicting efficient defibrillation waveforms. The model makes two assumptions: (1) The goal of both a monophasic shock and the first phase of a biphasic shock is to maximize the voltage change in the membrane at the end of the shock for a given stored energy. (2) The goal of the second phase of a biphasic shock is to discharge the membrane back to the zero potential, removing the charge deposited by the first phase. This model predicts that the optimal waveform rises in an exponential upward curve, but such an ascending waveform is difficult to generate efficiently. ICDs use electronically efficient capacitive-discharge waveforms, which require truncation for effective defibrillation. Even with optimal truncation, capacitive-discharge waveforms require more voltage and energy to achieve the same membrane voltage than do square waves and ascending waveforms. In ICDs, the value of the shock output capacitance is a key intermediary in establishing the relationship between stored energy-the key determinant of ICD size-and waveform voltage as a function of time, the key determinant of defibrillation efficacy. The RC model predicts that, for capacitive-discharge waveforms, stored energy is minimized

  4. Characterization of Polyolefin Pyrolysis Species Produced Under Ambient Conditions by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Farenc, Mathilde; Witt, Matthias; Craven, Kirsten; Barrère-Mangote, Caroline; Afonso, Carlos; Giusti, Pierre

    2017-03-01

    Polyolefins such as polyethylene (PE) and polypropylene (PP) are often characterized from their pyrolysis products by Py-MS. Nowadays the development of plasma-based direct probe atmospheric pressure sources allow the direct analysis of these polymers. These sources operate at atmospheric pressure, which implies a limited control of the ionization conditions. It was shown that side reactions could occur with species present in air, such as O2, which may lead to the formation of oxidized compounds. In this work, ion mobility-mass spectrometry (IM-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR) were used for the exhaustive characterization of the PP and PE pyrolysis ions produced using plasma-based atmospheric pressure ion sources. Both PP and PE yielded distributions of pyrolysis products presenting different amounts of unsaturation but also different numbers of oxygen atoms. In addition, the ions produced from PP presented a lower collision cross-section (CCS) than those produced from PE. In the same way, both PP and PE present repeated patterns separated by 14 m/z in the bidimensional drift time versus m/z plots. Within these plots, several trend lines can be evidenced, which are specific of each polymer investigated. Differences were observed between isotactic and atactic samples concerning the pyrolysis profile relative abundance and collision cross-section.

  5. Characterization of Polyolefin Pyrolysis Species Produced Under Ambient Conditions by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Farenc, Mathilde; Witt, Matthias; Craven, Kirsten; Barrère-Mangote, Caroline; Afonso, Carlos; Giusti, Pierre

    2017-01-01

    Polyolefins such as polyethylene (PE) and polypropylene (PP) are often characterized from their pyrolysis products by Py-MS. Nowadays the development of plasma-based direct probe atmospheric pressure sources allow the direct analysis of these polymers. These sources operate at atmospheric pressure, which implies a limited control of the ionization conditions. It was shown that side reactions could occur with species present in air, such as O2, which may lead to the formation of oxidized compounds. In this work, ion mobility-mass spectrometry (IM-MS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR) were used for the exhaustive characterization of the PP and PE pyrolysis ions produced using plasma-based atmospheric pressure ion sources. Both PP and PE yielded distributions of pyrolysis products presenting different amounts of unsaturation but also different numbers of oxygen atoms. In addition, the ions produced from PP presented a lower collision cross-section (CCS) than those produced from PE. In the same way, both PP and PE present repeated patterns separated by 14 m/z in the bidimensional drift time versus m/z plots. Within these plots, several trend lines can be evidenced, which are specific of each polymer investigated. Differences were observed between isotactic and atactic samples concerning the pyrolysis profile relative abundance and collision cross-section.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-20

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

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

    Science.gov (United States)

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

    2016-09-20

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

  8. Comprehensive theoretical analysis and experimental exploration of ultrafast microchip-based high-field asymmetric ion mobility spectrometry (FAIMS) technique.

    Science.gov (United States)

    Li, Lingfeng; Wang, Yonghuan; Chen, Chilai; Wang, Xiaozhi; Luo, Jikui

    2015-06-01

    High-field asymmetric ion mobility spectrometry (FAIMS) has become an efficient technique for separation and characterization of gas-phase ions at ambient pressure, which utilizes the mobility differences of ions at high and low fields. Micro FAIMS devices made by micro-electromechanical system technology have small gaps of the channels, high electric field and good installation precision, as thus they have received great attentions. However, the disadvantage of relatively low resolution limits their applications in some areas. In this study, theoretical analysis and experimental exploration were carried out to overcome the disadvantage. Multiple scans, characteristic decline curves of ion transmission and pattern recognitions were proposed to improve the performance of the microchip-based FAIMS. The results showed that although micro FAIMS instruments as a standalone chemical analyzer suffer from low resolution, by using one or more of the methods proposed, they can identify chemicals precisely and provide quantitative analysis with low detection limit in some applications. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Exhaled breath analysis for lung cancer detection using ion mobility spectrometry.

    Directory of Open Access Journals (Sweden)

    Hiroshi Handa

    Full Text Available Conventional methods for lung cancer detection including computed tomography (CT and bronchoscopy are expensive and invasive. Thus, there is still a need for an optimal lung cancer detection technique.The exhaled breath of 50 patients with lung cancer histologically proven by bronchoscopic biopsy samples (32 adenocarcinomas, 10 squamous cell carcinomas, 8 small cell carcinomas, were analyzed using ion mobility spectrometry (IMS and compared with 39 healthy volunteers. As a secondary assessment, we compared adenocarcinoma patients with and without epidermal growth factor receptor (EGFR mutation.A decision tree algorithm could separate patients with lung cancer including adenocarcinoma, squamous cell carcinoma and small cell carcinoma. One hundred-fifteen separated volatile organic compound (VOC peaks were analyzed. Peak-2 noted as n-Dodecane using the IMS database was able to separate values with a sensitivity of 70.0% and a specificity of 89.7%. Incorporating a decision tree algorithm starting with n-Dodecane, a sensitivity of 76% and specificity of 100% was achieved. Comparing VOC peaks between adenocarcinoma and healthy subjects, n-Dodecane was able to separate values with a sensitivity of 81.3% and a specificity of 89.7%. Fourteen patients positive for EGFR mutation displayed a significantly higher n-Dodecane than for the 14 patients negative for EGFR (p<0.01, with a sensitivity of 85.7% and a specificity of 78.6%.In this prospective study, VOC peak patterns using a decision tree algorithm were useful in the detection of lung cancer. Moreover, n-Dodecane analysis from adenocarcinoma patients might be useful to discriminate the EGFR mutation.

  10. Determining the topology of virus assembly intermediates using ion mobility spectrometry-mass spectrometry.

    Science.gov (United States)

    Knapman, Tom W; Morton, Victoria L; Stonehouse, Nicola J; Stockley, Peter G; Ashcroft, Alison E

    2010-10-30

    We have combined ion mobility spectrometry-mass spectrometry with tandem mass spectrometry to characterise large, non-covalently bound macromolecular complexes in terms of mass, shape (cross-sectional area) and stability (dissociation) in a single experiment. The results indicate that the quaternary architecture of a complex influences its residual shape following removal of a single subunit by collision-induced dissociation tandem mass spectrometry. Complexes whose subunits are bound to several neighbouring subunits to create a ring-like three-dimensional (3D) architecture undergo significant collapse upon dissociation. In contrast, subunits which have only a single neighbouring subunit within a complex retain much of their original shape upon complex dissociation. Specifically, we have determined the architecture of two transient, on-pathway intermediates observed during in vitro viral capsid assembly. Knowledge of the mass, stoichiometry and cross-sectional area of each viral assembly intermediate allowed us to model a range of potential structures based on the known X-ray structure of the coat protein building blocks. Comparing the cross-sectional areas of these potential architectures before and after dissociation provided tangible evidence for the assignment of the topologies of the complexes, which have been found to encompass both the 3-fold and the 5-fold symmetry axes of the final icosahedral viral shell. Such insights provide unique information about virus assembly pathways that could allow the design of anti-viral therapeutics directed at the assembly step. This methodology can be readily applied to the structural characterisation of many other non-covalently bound macromolecular complexes and their assembly pathways.

  11. An electrospray ionization-ion mobility spectrometer as detector for high- performance liquid chromatography.

    Science.gov (United States)

    Zühlke, Martin; Riebe, Daniel; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Zenichowski, Karl; Diener, Marc; Linscheid, Michael W

    2015-01-01

    The application of electrospray ionization (ESI) ion mobility (IM) spectrometry on the detection end of a high-performance liquid chromatograph has been a subject of study for some time. So far, this method has been limited to low flow rates or has required splitting of the liquid flow. This work presents a novel concept of an ESI source facilitating the stable operation of the spectrometer at flow rates between 10 μL mn(-1) and 1500 μL min(-1) without flow splitting, advancing the T-cylinder design developed by Kurnin and co-workers. Flow rates eight times faster than previously reported were achieved because of a more efficient dispersion of the liquid at increased electrospray voltages combined with nebulization by a sheath gas. Imaging revealed the spray operation to be in a rotationally symmetric multijet mode. The novel ESI-IM spectrometer tolerates high water contents (≤90%) and electrolyte concentrations up to 10mM, meeting another condition required of high-performance liquid chromatography (HPLC) detectors. Limits of detection of 50 nM for promazine in the positive mode and 1 μM for 1,3-dinitrobenzene in the negative mode were established. Three mixtures of reduced complexity (five surfactants, four neuroleptics, and two isomers) were separated in the millisecond regime in stand-alone operation of the spectrometer. Separations of two more complex mixtures (five neuroleptics and 13 pesticides) demonstrate the application of the spectrometer as an HPLC detector. The examples illustrate the advantages of the spectrometer over the established diode array detector, in terms of additional IM separation of substances not fully separated in the retention time domain as well as identification of substances based on their characteristic Ims.

  12. Real-time 2D separation by LC × differential ion mobility hyphenated to mass spectrometry.

    Science.gov (United States)

    Varesio, Emmanuel; Le Blanc, J C Yves; Hopfgartner, Gérard

    2012-03-01

    The liquid chromatography-mass spectrometry (LC-MS) analysis of complex samples such as biological fluid extracts is widespread when searching for new biomarkers as in metabolomics. The success of this hyphenation resides in the orthogonality of both separation techniques. However, there are frequent cases where compounds are co-eluting and the resolving power of mass spectrometry (MS) is not sufficient (e.g., isobaric compounds and interfering isotopic clusters). Different strategies are discussed to solve these cases and a mixture of eight compounds (i.e., bromazepam, chlorprothixene, clonapzepam, fendiline, flusilazol, oxfendazole, oxycodone, and pamaquine) with identical nominal mass (i.e., m/z 316) is taken to illustrate them. Among the different approaches, high-resolution mass spectrometry or liquid chromatography (i.e., UHPLC) can easily separate these compounds. Another technique, mostly used with low resolving power MS analyzers, is differential ion mobility spectrometry (DMS), where analytes are gas-phase separated according to their size-to-charge ratio. Detailed investigations of the addition of different polar modifiers (i.e., methanol, ethanol, and isopropanol) into the transport gas (nitrogen) to enhance the peak capacity of the technique were carried out. Finally, a complex urine sample fortified with 36 compounds of various chemical properties was analyzed by real-time 2D separation LC×DMS-MS(/MS). The addition of this orthogonal gas-phase separation technique in the LC-MS(/MS) hyphenation greatly improved data quality by resolving composite MS/MS spectra, which is mandatory in metabolomics when performing database generation and search.

  13. On-site Rapid Detection of Trace Non-volatile Inorganic Explosives by Stand-alone Ion Mobility Spectrometry via Acid-enhanced Evaporization

    OpenAIRE

    2014-01-01

    New techniques for the field detection of inorganic improvised explosive devices (IEDs) are urgently developed. Although ion mobility spectrometry (IMS) has been proved to be the most effective method for screening organic explosives, it still faces a major challenge to detect inorganic explosives owing to their low volatilities. Herein, we proposed a strategy for detecting trace inorganic explosives by thermal desorption ion mobility spectrometry (TD-IMS) with sample-to-sample analysis time ...

  14. Waveform analysis of sound

    CERN Document Server

    Tohyama, Mikio

    2015-01-01

    What is this sound? What does that sound indicate? These are two questions frequently heard in daily conversation. Sound results from the vibrations of elastic media and in daily life provides informative signals of events happening in the surrounding environment. In interpreting auditory sensations, the human ear seems particularly good at extracting the signal signatures from sound waves. Although exploring auditory processing schemes may be beyond our capabilities, source signature analysis is a very attractive area in which signal-processing schemes can be developed using mathematical expressions. This book is inspired by such processing schemes and is oriented to signature analysis of waveforms. Most of the examples in the book are taken from data of sound and vibrations; however, the methods and theories are mostly formulated using mathematical expressions rather than by acoustical interpretation. This book might therefore be attractive and informative for scientists, engineers, researchers, and graduat...

  15. Pseudo waveform inversion

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Chang Soo; Park, Keun Pil [Korea Inst. of Geology Mining and Materials, Taejon (Korea, Republic of); Suh, Jung Hee; Hyun, Byung Koo; Shin, Sung Ryul [Seoul National University, Seoul (Korea, Republic of)

    1995-12-01

    The seismic reflection exploration technique which is one of the geophysical methods for oil exploration became effectively to image the subsurface structure with rapid development of computer. However, the imagining of subsurface based on the conventional data processing is almost impossible to obtain the information on physical properties of the subsurface such as velocity and density. Since seismic data are implicitly function of velocities of subsurface, it is necessary to develop the inversion method that can delineate the velocity structure using seismic topography and waveform inversion. As a tool to perform seismic inversion, seismic forward modeling program using ray tracing should be developed. In this study, we have developed the algorithm that calculate the travel time of the complex geologic structure using shooting ray tracing by subdividing the geologic model into blocky structure having the constant velocity. With the travel time calculation, the partial derivatives of travel time can be calculated efficiently without difficulties. Since the current ray tracing technique has a limitation to calculate the travel times for extremely complex geologic model, our aim in the future is to develop the powerful ray tracer using the finite element technique. After applying the pseudo waveform inversion to the seismic data of Korea offshore, we can obtain the subsurface velocity model and use the result in bring up the quality of the seismic data processing. If conventional seismic data processing and seismic interpretation are linked with this inversion technique, the high quality of seismic data processing can be expected to image the structure of the subsurface. Future research area is to develop the powerful ray tracer of ray tracing which can calculate the travel times for the extremely complex geologic model. (author). 39 refs., 32 figs., 2 tabs.

  16. Signatures of Mechanically Interlocked Topology of Lasso Peptides by Ion Mobility-Mass Spectrometry: Lessons from a Collection of Representatives

    Science.gov (United States)

    Fouque, Kevin Jeanne Dit; Lavanant, Hélène; Zirah, Séverine; Hegemann, Julian D.; Zimmermann, Marcel; Marahiel, Mohamed A.; Rebuffat, Sylvie; Afonso, Carlos

    2016-11-01

    Lasso peptides are characterized by a mechanically interlocked structure, where the C-terminal tail of the peptide is threaded and trapped within an N-terminal macrolactam ring. Their compact and stable structures have a significant impact on their biological and physical properties and make them highly interesting for drug development. Ion mobility - mass spectrometry (IM-MS) has shown to be effective to discriminate the lasso topology from their corresponding branched-cyclic topoisomers in which the C-terminal tail is unthreaded. In fact, previous comparison of the IM-MS data of the two topologies has yielded three trends that allow differentiation of the lasso fold from the branched-cyclic structure: (1) the low abundance of highly charged ions, (2) the low change in collision cross sections (CCS) with increasing charge state and (3) a narrow ion mobility peak width. In this study, a three-dimensional plot was generated using three indicators based on these three trends: (1) mean charge divided by mass (ζ), (2) relative range of CCS covered by all protonated molecules (ΔΩ/Ω) and (3) mean ion mobility peak width (δΩ). The data were first collected on a set of twenty one lasso peptides and eight branched-cyclic peptides. The indicators were obtained also for eight variants of the well-known lasso peptide MccJ25 obtained by site-directed mutagenesis and further extended to five linear peptides, two macrocyclic peptides and one disulfide constrained peptide. In all cases, a clear clustering was observed between constrained and unconstrained structures, thus providing a new strategy to discriminate mechanically interlocked topologies.

  17. Signatures of Mechanically Interlocked Topology of Lasso Peptides by Ion Mobility-Mass Spectrometry: Lessons from a Collection of Representatives

    Science.gov (United States)

    Fouque, Kevin Jeanne Dit; Lavanant, Hélène; Zirah, Séverine; Hegemann, Julian D.; Zimmermann, Marcel; Marahiel, Mohamed A.; Rebuffat, Sylvie; Afonso, Carlos

    2017-02-01

    Lasso peptides are characterized by a mechanically interlocked structure, where the C-terminal tail of the peptide is threaded and trapped within an N-terminal macrolactam ring. Their compact and stable structures have a significant impact on their biological and physical properties and make them highly interesting for drug development. Ion mobility - mass spectrometry (IM-MS) has shown to be effective to discriminate the lasso topology from their corresponding branched-cyclic topoisomers in which the C-terminal tail is unthreaded. In fact, previous comparison of the IM-MS data of the two topologies has yielded three trends that allow differentiation of the lasso fold from the branched-cyclic structure: (1) the low abundance of highly charged ions, (2) the low change in collision cross sections (CCS) with increasing charge state and (3) a narrow ion mobility peak width. In this study, a three-dimensional plot was generated using three indicators based on these three trends: (1) mean charge divided by mass (ζ), (2) relative range of CCS covered by all protonated molecules (ΔΩ/Ω) and (3) mean ion mobility peak width (δΩ). The data were first collected on a set of twenty one lasso peptides and eight branched-cyclic peptides. The indicators were obtained also for eight variants of the well-known lasso peptide MccJ25 obtained by site-directed mutagenesis and further extended to five linear peptides, two macrocyclic peptides and one disulfide constrained peptide. In all cases, a clear clustering was observed between constrained and unconstrained structures, thus providing a new strategy to discriminate mechanically interlocked topologies.

  18. Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer System for In-Situ Detection of Organic Compounds

    Science.gov (United States)

    Kanik, I.; Johnson, P. V.; Beegle, L. W.; Cooks, R. G.; Laughlin, B. C.; Hill, H. H.

    2003-01-01

    The potential of an Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer (ESI/IMS/CIT-MS) as an analytical instrument for analyzing material extracted from rock and soil samples as part of a suite of instruments on the proposed 2009 Mars Science Lander (MSL) will be demonstrated. This instrument will be able to identify volatile compounds as well as resident organic molecules on the parts-per-billion (ppb) level. Also, it will be able to obtain an inventory of chemical species on the surface of Mars which will result in a better understanding of ongoing surface chemistry. Finally, questions relevant to biological processes will be answered with the complete inventory of surface and near surface organic molecules that the ESI/IMS/CIT is capable of performing.

  19. Waveform Catalog, Extreme Mass Ratio Binary (Capture)

    Data.gov (United States)

    National Aeronautics and Space Administration — Numerically-generated gravitational waveforms for circular inspiral into Kerr black holes. These waveforms were developed using Scott Hughes' black hole perturbation...

  20. A simple template-based transfer method to fabricate Bradbury-Nielsen gates with uniform tension for ion mobility spectrometry

    Science.gov (United States)

    Kai, Ni; Jingran, Guo; Guangli, Ou; Yu, Lei; Quan, Yu; Xiang, Qian; Xiaohao, Wang

    2014-08-01

    A Bradbury-Nielsen gate (BNG) consists of two interleaved and electrically isolated sets of wires. It is usually used to gate or modulate ion beams. Uniformly tense wires can remain parallel, equidistant, and coplanar over a wide working temperature range, which is critical to reliable BNG performance. Hence, this study analyzes the non-uniform tension of wires wound using traditional sequential winding methods in which the elastic modulus of the metal wire is much larger than that of the insulation substrate. To address this problem, a simple and reliable template-based transfer method is developed. First, a template with large elastic modulus is used to fabricate a wire mesh with uniform tension. The mesh is then transferred to the substrate. Theoretically, this method reduces the non-uniformity of the tension in wires to less than 2%; therefore, it is used to construct a BNG with stainless steel wire, a stainless steel template, and a printed circuit board substrate. The BNG was installed in our homebuilt ion mobility spectrometer. To confirm that the performance of the BNG meets the requirements of portable ion mobility spectrometry, signal intensity and resolution (approximately 30) were experimentally determined.

  1. A simple template-based transfer method to fabricate Bradbury–Nielsen gates with uniform tension for ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kai, Ni, E-mail: ni.kai@sz.tsinghua.edu.cn; Jingran, Guo; Guangli, Ou; Yu, Lei; Quan, Yu; Xiang, Qian; Xiaohao, Wang [Division of Advanced Manufacturing, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China)

    2014-08-15

    A Bradbury–Nielsen gate (BNG) consists of two interleaved and electrically isolated sets of wires. It is usually used to gate or modulate ion beams. Uniformly tense wires can remain parallel, equidistant, and coplanar over a wide working temperature range, which is critical to reliable BNG performance. Hence, this study analyzes the non-uniform tension of wires wound using traditional sequential winding methods in which the elastic modulus of the metal wire is much larger than that of the insulation substrate. To address this problem, a simple and reliable template-based transfer method is developed. First, a template with large elastic modulus is used to fabricate a wire mesh with uniform tension. The mesh is then transferred to the substrate. Theoretically, this method reduces the non-uniformity of the tension in wires to less than 2%; therefore, it is used to construct a BNG with stainless steel wire, a stainless steel template, and a printed circuit board substrate. The BNG was installed in our homebuilt ion mobility spectrometer. To confirm that the performance of the BNG meets the requirements of portable ion mobility spectrometry, signal intensity and resolution (approximately 30) were experimentally determined.

  2. Structures, Hydration, and Electrical Mobilities of Bisulfate Ion-Sulfuric Acid-Ammonia/Dimethylamine Clusters: A Computational Study.

    Science.gov (United States)

    Tsona, Narcisse T; Henschel, Henning; Bork, Nicolai; Loukonen, Ville; Vehkamäki, Hanna

    2015-09-17

    Despite the well-established role of small molecular clusters in the very first steps of atmospheric particle formation, their thermochemical data are still not completely available due to limitation of the experimental techniques to treat such small clusters. We have investigated the structures and the thermochemistry of stepwise hydration of clusters containing one bisulfate ion, sulfuric acid, base (ammonia or dimethylamine), and water molecules using quantum chemical methods. We found that water facilitates proton transfer from sulfuric acid or the bisulfate ion to the base or water molecules, and depending on the hydration level, the sulfate ion was formed in most of the base-containing clusters. The calculated hydration energies indicate that water binds more strongly to ammonia-containing clusters than to dimethylamine-containing and base-free clusters, which results in a wider hydrate distribution for ammonia-containing clusters. The electrical mobilities of all clusters were calculated using a particle dynamics model. The results indicate that the effect of humidity is negligible on the electrical mobilities of molecular clusters formed in the very first steps of atmospheric particle formation. The combination of the results of this study with those previously published on the hydration of neutral clusters by our group provides a comprehensive set of thermochemical data on neutral and negatively charged clusters containing sulfuric acid, ammonia, or dimethylamine.

  3. Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Haler, Jean R. N.; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

    2017-08-01

    Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. [Figure not available: see fulltext.

  4. Device for two-dimensional gas-phase separation and characterization of ion mixtures

    Science.gov (United States)

    Tang, Keqi; Shvartsburg, Alexandre A.; Smith, Richard D.

    2006-12-12

    The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

  5. Global structural changes of an ion channel during its gating are followed by ion mobility mass spectrometry

    NARCIS (Netherlands)

    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

  6. Apparent Mobilities of Na+,K+ and Ca2+ Ions in Variable Charge Soil Colloid Systems

    Institute of Scientific and Technical Information of China (English)

    LICHENG-BAO

    1992-01-01

    In this paper a simple method for determination of the apparent mobility of cation in a soil colloid system was described.With this method apparent mobilities of Na+,K+,and Ca2+ ions in the systems of the ferric luvisol,acrisol,and ferralsol were determined,and the reduction percentages of the mobilities were calculated.The results showed that the apparent mobilities of different cations at the same normalitey in a given soil system were in the order UNa>UK>UCa;those of the same cations among different soil systems were in the order ferralsol> acrisol> ferric luvisol,but the reduction percentages were in a reverse order,which among different cations at the same normality was Ca2+>K+>Na+ for ferric luvisol and acrisol systems,but was K+>Ca2+>Na+ for farralsol system.These results were interpreted in terms of different amounts of negative charge the clay fraction of different soils carries,and different mechanisms by which the soils adsorb the cations.

  7. Multiples waveform inversion

    KAUST Repository

    Zhang, D. L.

    2013-01-01

    To increase the illumination of the subsurface and to eliminate the dependency of FWI on the source wavelet, we propose multiples waveform inversion (MWI) that transforms each hydrophone into a virtual point source with a time history equal to that of the recorded data. These virtual sources are used to numerically generate downgoing wavefields that are correlated with the backprojected surface-related multiples to give the migration image. Since the recorded data are treated as the virtual sources, knowledge of the source wavelet is not required, and the subsurface illumination is greatly enhanced because the entire free surface acts as an extended source compared to the radiation pattern of a traditional point source. Numerical tests on the Marmousi2 model show that the convergence rate and the spatial resolution of MWI is, respectively, faster and more accurate then FWI. The potential pitfall with this method is that the multiples undergo more than one roundtrip to the surface, which increases attenuation and reduces spatial resolution. This can lead to less resolved tomograms compared to conventional FWI. The possible solution is to combine both FWI and MWI in inverting for the subsurface velocity distribution.

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

    Science.gov (United States)

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

    1999-01-01

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

  9. Detection of lead ions with AlGaAs/InGaAs pseudomorphic high electron mobility transistor

    Science.gov (United States)

    Jiqiang, Niu; Yang, Zhang; Min, Guan; Chengyan, Wang; Lijie, Cui; Qiumin, Yang; Yiyang, Li; Yiping, Zeng

    2016-11-01

    Lead poisoning is a serious environmental concern, which is a health threat. Existing technologies always have some drawbacks, which restrict their application ranges, such as real time monitoring. To solve this problem, glutathione was functionalized on the Au-coated gate area of the pseudomorphic high electron mobility transistor (pHEMT) to detect trace amounts of Pb2+. The positive charge of lead ions will cause a positive potential on the Au gate of the pHEMT sensor, which will increase the current between the source and the drain. The response range for Pb2+ detection has been determined in the concentrations from 0.1 pmol/L to 10 pmol/L. To our knowledge, this is currently the best result for detecting lead ions. Project supported by the National Natural Science Foundation of China (Nos. 61204012, 61274049, 61376058), the Beijing Natural Science Foundation (Nos. 4142053, 4132070), and the Beijing Nova Program (Nos. 2010B056, xxhz201503).

  10. The structures of small gold cluster anions as determined by a combination of ion mobility measurements and density functional calculations

    Science.gov (United States)

    Furche, Filipp; Ahlrichs, Reinhart; Weis, Patrick; Jacob, Christoph; Gilb, Stefan; Bierweiler, Thomas; Kappes, Manfred M.

    2002-10-01

    A combined experimental and theoretical study of small gold cluster anions is performed. The experimental effort consists of ion mobility measurements that lead to the assignment of the collision cross sections for the different cluster sizes at room temperature. The theoretical study is based on ab initio molecular dynamics calculations with the goal to find energetically favorable candidate structures. By comparison of the theoretical results with the measured collision cross sections as well as vertical detachment energies (VDEs) from the literature, we assign structures for the small Aun- ions (nVDEs alone is generally not possible, the collision cross sections provide a direct and rather sensitive measure of the cluster structure. In contrast to what was expected from other metal clusters and previous theoretical studies, the structural transition occurs at an unusually large cluster size of twelve atoms.

  11. STRS Compliant FPGA Waveform Development

    Science.gov (United States)

    Nappier, Jennifer; Downey, Joseph

    2008-01-01

    The Space Telecommunications Radio System (STRS) Architecture Standard describes a standard for NASA space software defined radios (SDRs). It provides a common framework that can be used to develop and operate a space SDR in a reconfigurable and reprogrammable manner. One goal of the STRS Architecture is to promote waveform reuse among multiple software defined radios. Many space domain waveforms are designed to run in the special signal processing (SSP) hardware. However, the STRS Architecture is currently incomplete in defining a standard for designing waveforms in the SSP hardware. Therefore, the STRS Architecture needs to be extended to encompass waveform development in the SSP hardware. A transmit waveform for space applications was developed to determine ways to extend the STRS Architecture to a field programmable gate array (FPGA). These extensions include a standard hardware abstraction layer for FPGAs and a standard interface between waveform functions running inside a FPGA. Current standards were researched and new standard interfaces were proposed. The implementation of the proposed standard interfaces on a laboratory breadboard SDR will be presented.

  12. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Oberreit, Derek [Department of Mechanical Engineering, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Fluid Measurement Technologies, Inc., Saint Paul, Minnesota 55110 (United States); Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J., E-mail: hogan108@umn.edu [Department of Mechanical Engineering, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    2015-09-14

    The sorption of vapor molecules onto pre-existing nanometer sized clusters is of importance in understanding particle formation and growth in gas phase environments and devising gas phase separation schemes. Here, we apply a differential mobility analyzer-mass spectrometer based approach to observe directly the sorption of vapor molecules onto iodide cluster ions of the form (MI){sub x}M{sup +} (x = 1-13, M = Na, K, Rb, or Cs) in air at 300 K and with water saturation ratios in the 0.01-0.64 range. The extent of vapor sorption is quantified in measurements by the shift in collision cross section (CCS) for each ion. We find that CCS measurements are sensitive enough to detect the transient binding of several vapor molecules to clusters, which shift CCSs by only several percent. At the same time, for the highest saturation ratios examined, we observed CCS shifts of up to 45%. For x < 4, cesium, rubidium, and potassium iodide cluster ions are found to uptake water to a similar extent, while sodium iodide clusters uptake less water. For x ≥ 4, sodium iodide cluster ions uptake proportionally more water vapor than rubidium and potassium iodide cluster ions, while cesium iodide ions exhibit less uptake. Measured CCS shifts are compared to predictions based upon a Kelvin-Thomson-Raoult (KTR) model as well as a Langmuir adsorption model. We find that the Langmuir adsorption model can be fit well to measurements. Meanwhile, KTR predictions deviate from measurements, which suggests that the earliest stages of vapor uptake by nanometer scale species are not well described by the KTR model.

  13. Direct analysis of pharmaceutical drug formulations using ion mobility spectrometry/quadrupole-time-of-flight mass spectrometry combined with desorption electrospray ionization.

    Science.gov (United States)

    Weston, Daniel J; Bateman, Robert; Wilson, Ian D; Wood, Tim R; Creaser, Colin S

    2005-12-01

    A novel approach to the rapid analysis of pharmaceutical drug formulations using hyphenated ion mobility spectrometry (IMS) and time-of-flight mass spectrometry (ToF-MS) that requires no sample pretreatment or chromatographic separation is described. A modified quadrupole time-of-flight mass spectrometer containing an ion mobility drift cell was used for gas-phase electrophoretic separation of ions prior to ToF-MS detection. The generation of sample ions directly from tablets and cream formulations was effected by desorption electrospray ionization (DESI) using a modified electrospray ion source. The analysis of a range of over-the-counter and prescription tablet formulations is described, including histamine H2 receptor antagonist (ranitidine), analgesic (paracetamol), opiate (codeine), and aromatase inhibitor anticancer (anastrozole) drugs. The successful determination of active drugs from soft formulations, such as an antiseptic cream (chlorhexidine) and a nicotine-containing skin patch, is also presented. Limits of detection for the active drugs using the DESI/IMS/ToF-MS method fell within the high-picomole to nanomole range. In all cases, the use of ion mobility drift tube separation showed increased selectivity for active drug responses (present as low as 0.14% w/w) over excipient responses such as poly(ethylene glycol). Tandem mass spectrometric analysis of precursor ions separated by IMS allowed positive confirmation of active drugs with little loss of ion mobility efficiency. The ability to analyze hard or soft pharmaceutical formulations directly by DESI combined with ion mobility spectrometry/mass spectrometry in approximately 2 min demonstrates the potential applicability of this novel method to pharmaceutical screening of low-molecular-weight drug formulations with high selectivity over the formulation vehicle.

  14. Energy-Resolved Ion Mobility-Mass Spectrometry—A Concept to Improve the Separation of Isomeric Carbohydrates

    Science.gov (United States)

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3 %. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  15. Energy-resolved ion mobility-mass spectrometry--a concept to improve the separation of isomeric carbohydrates.

    Science.gov (United States)

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3%. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  16. A comparative study between different alternatives to prepare gaseous standards for calibrating UV-Ion Mobility Spectrometers.

    Science.gov (United States)

    Criado-García, Laura; Garrido-Delgado, Rocío; Arce, Lourdes; Valcárcel, Miguel

    2013-07-15

    An UV-Ion Mobility Spectrometer is a simple, rapid, inexpensive instrument widely used in environmental analysis among other fields. The advantageous features of its underlying technology can be of great help towards developing reliable, economical methods for determining gaseous compounds from gaseous, liquid and solid samples. Developing an effective method using UV-Ion Mobility Spectrometry (UV-IMS) to determine volatile analytes entails using appropriate gaseous standards for calibrating the spectrometer. In this work, two home-made sample introduction systems (SISs) and a commercial gas generator were used to obtain such gaseous standards. The first home-made SIS used was a static head-space to measure compounds present in liquid samples and the other home-made system was an exponential dilution set-up to measure compounds present in gaseous samples. Gaseous compounds generated by each method were determined on-line by UV-IMS. Target analytes chosen for this comparative study were ethanol, acetone, benzene, toluene, ethylbenzene and xylene isomers. The different alternatives were acceptable in terms of sensitivity, precision and selectivity.

  17. Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Jafari, Mohammad T; Riahi, Farhad

    2014-05-23

    The capability of corona discharge ionization ion mobility spectrometry (CD-IMS) for direct analysis of the samples extracted by dispersive liquid-liquid microextraction (DLLME) was investigated and evaluated, for the first time. To that end, an appropriate new injection port was designed and constructed, resulting in possibility of direct injection of the known sample volume, without tedious sample preparation steps (e.g. derivatization, solvent evaporation, and re-solving in another solvent…). Malathion as a test compound was extracted from different matrices by a rapid and convenient DLLME method. The positive ion mobility spectra of the extracted malathion were obtained after direct injection of carbon tetrachloride or methanol solutions. The analyte responses were compared and the statistical results revealed the feasibility of direct analysis of the extracted samples in carbon tetrachloride, resulting in a convenient methodology. The coupled method of DLLME-CD-IMS was exhaustively validated in terms of sensitivity, dynamic range, recovery, and enrichment factor. Finally, various real samples of apple, river and underground water were analyzed, all verifying the feasibility and success of the proposed method for the easy extraction of the analyte using DLLME separation before the direct analysis by CD-IMS.

  18. Quantitative calibration of vapor levels of TNT, RDX, and PETN using a diffusion generator with gravimetry and ion mobility spectrometry.

    Science.gov (United States)

    Eiceman, G A; Preston, D; Tiano, G; Rodriguez, J; Parmeter, J E

    1997-12-12

    A prototype generator for creating a continuous stream of explosive vapor was referenced quantitatively both to a standard weight from the National Institute of Standards and Technology (NIST) and to the response of an ion mobility spectrometer. Vapors from solid explosive, in a precision bore glass tube at constant temperature, diffuse into an inert gas flow. Mass output rates were determined by (1) sample temperature, and (2) sample tube dimensions (length and cross-sectional area). A reference to NIST was achieved gravimetrically though a microbalance calibrated with a reference weight; mass output rates were obtained for 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX) and pentaerythritol tetranitrate (PETN) at three or more oven temperatures between 79 degrees C and 150 degrees C. The mass output rate was stable over hundreds of hours of continuous operation and the output was adjustable from a few picograms per second to several nanograms per second through variation of the oven temperature. An independent calibration of the vapor generator for TNT at 79 degrees C using an ion mobility spectrometer matched exactly the gravimetric-based findings. In most instances, measured mass output rates compared favorably with theoretically calculated mass output rates, with discrepancies in a few cases resulting primarily from uncertainties in terms (vapor pressures and diffusion coefficients) used to perform the calculations. Agreement is generally not good for PETN, where molecular decomposition contributed to higher than expected measured mass outputs.

  19. A kinetic study on decomposition of proton-bound dimer using data obtained by ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jazan, Elham, E-mail: jazan@iaush.ac.ir; Ghazali Khoob, Abdolhosein S.

    2014-08-17

    Graphical abstract: - Highlights: • The capability of corona discharge-IMS for easy study of kinetic properties was confirmed. • An equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived. • The effects of temperatures and sample concentration were investigated for monomer–dimer tail. - Abstract: In this study, an equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived using the data obtained by ion mobility spectrometry (IMS) technique. The ion mobility spectra of cyclohexanone (as the test compound) were obtained at various temperatures and different electric fields. The applied electric field for each temperature was varied between 375 and 500 V cm{sup −1} and the rate constant values of 188.24, 180.54, 280.64, 288.34 and 379.60 s{sup −1} were obtained at different temperatures of 463, 468, 473, 478 and 483 K, respectively. Subsequently, the activation energy and pre-exponential factor were calculated to be 69.5 kJ mol{sup −1} and 1.2 × 10{sup 10} s{sup −1}, respectively. In addition, the standard enthalpy changes were calculated for the dimer decomposition reaction of cyclohexanone at the above-mentioned temperatures.

  20. Analysis of ecstasy in oral fluid by ion mobility spectrometry and infrared spectroscopy after liquid-liquid extraction.

    Science.gov (United States)

    Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel; Brassier, Judit; Alcalà, Manel; Blanco, Marcelo

    2015-03-06

    We developed and evaluated two different strategies for determining abuse drugs based on (i) the analysis of saliva by ion mobility spectrometry (IMS) after thermal desorption and (ii) the joint use of IMS and infrared (IR) spectroscopy after liquid-liquid microextraction (LLME) to enable the sensitivity-enhanced detection and double confirmation of ecstasy (MDMA) abuse. Both strategies proved effective for the intended purpose. Analysing saliva by IMS after thermal desorption, which provides a limit of detection (LOD) of 160μgL(-1), requires adding 0.2M acetic acid to the sample and using the truncated negative second derivative of the ion mobility spectrum. The joint use of IMS and IR spectroscopy after LLME provides an LOD of 11μgL(-1) with the former technique and 800μgL(-1) with the latter, in addition to a limit of confirmation (LOC) of 1.5mgL(-1). Using IMS after thermal desorption simplifies the operational procedure, and using it jointly with IR spectroscopy after LLME allows double confirmation of MDMA abuse with two techniques based on different principles (viz., IMS drift times and IR spectra). Also, it affords on-site analyses, albeit at a lower throughput.

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

    Science.gov (United States)

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

    2002-01-01

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

  2. Proton Mobility in b2 Ion Formation and Fragmentation Reactions of Histidine-Containing Peptides

    Science.gov (United States)

    Nelson, Carissa R.; Abutokaikah, Maha T.; Harrison, Alex G.; Bythell, Benjamin J.

    2016-03-01

    A detailed energy-resolved study of the fragmentation reactions of protonated histidine-containing peptides and their b2 ions has been undertaken. Density functional theory calculations were utilized to predict how the fragmentation reactions occur so that we might discern why the mass spectra demonstrated particular energy dependencies. We compare our results to the current literature and to synthetic b2 ion standards. We show that the position of the His residue does affect the identity of the subsequent b2 ion (diketopiperazine versus oxazolone versus lactam) and that energy-resolved CID can distinguish these isomeric products based on their fragmentation energetics. The histidine side chain facilitates every major transformation except trans-cis isomerization of the first amide bond, a necessary prerequisite to diketopiperazine b2 ion formation. Despite this lack of catalyzation, trans-cis isomerization is predicted to be facile. Concomitantly, the subsequent amide bond cleavage reaction is rate-limiting.

  3. Structural analysis of ruthenium-arene complexes using ion mobility mass spectrometry, collision-induced dissociation, and DFT.

    Science.gov (United States)

    Czerwinska, Izabella; Far, Johann; Kune, Christopher; Larriba-Andaluz, Carlos; Delaude, Lionel; De Pauw, Edwin

    2016-04-21

    Ion mobility mass spectrometry (IM-MS) and collision-induced dissociation (CID) techniques were used to investigate the influence of the phosphine ligand on the physicochemical properties of [RuCl2(p-cymene)(PCy3)] (), [RuCl2(p-cymene)(PPh3)] (), and [RuCl2(p-cymene)(PTA)] () in the gas phase (PTA is 1,3,5-triaza-7-phosphaadamantane). Electrospray ionization of complexes and led to the corresponding [RuCl(p-cymene)(PR3)](+) ions via the dissociation of a chlorido ligand, whereas RAPTA-C () afforded two molecular ions by in-source oxidation ([Ru(III)Cl2(p-cymene)(PTA)](+)) or protonation ([RuCl2(p-cymene)(PTA+H)](+)). Control experiments showed that the balance between these two ionization paths was strongly influenced by the nature of the solvent used for infusion. Collision cross sections (CCSs) of the four molecular ions accurately reflected the variations of steric bulk inferred from the Tolman steric parameters (θ) of the phosphine ligands. Moreover, DFT calculations combined with a model based on the kinetic theory of gases (the trajectory method of the IMoS software) afforded reliable CCS predictions. The almost two times higher dipole moment of [RuCl2(p-cymene)(PTA+H)](+) (μ = 13.75 D) compared to [Ru(III)Cl2(p-cymene)(PTA)](+) (μ = 7.18 D) was held responsible for increased ion-induced dipole interactions with a polarizable drift gas such as N2. Further experiments with He and CO2 confirmed that increasing the polarizability of the buffer gas improved the separation between the two molecular ions derived from complex . The fragmentation patterns of complexes were determined by CID. The sequence of collision voltages at which 50% of a precursor ion dissociates (V50) recorded for the molecular ions derived from compounds was in good agreement with simple electronic considerations based on the donor strength of the phosphine ligand. Thus, the CCS and V50 parameters used to determine the shape and stability of ionic species in the gas phase are complementary

  4. Determination of ion mobility collision cross sections for unresolved isomeric mixtures using tandem mass spectrometry and chemometric deconvolution.

    Science.gov (United States)

    Harper, Brett; Neumann, Elizabeth K; Stow, Sarah M; May, Jody C; McLean, John A; Solouki, Touradj

    2016-10-01

    Ion mobility (IM) is an important analytical technique for determining ion collision cross section (CCS) values in the gas-phase and gaining insight into molecular structures and conformations. However, limited instrument resolving powers for IM may restrict adequate characterization of conformationally similar ions, such as structural isomers, and reduce the accuracy of IM-based CCS calculations. Recently, we introduced an automated technique for extracting "pure" IM and collision-induced dissociation (CID) mass spectra of IM overlapping species using chemometric deconvolution of post-IM/CID mass spectrometry (MS) data [J. Am. Soc. Mass Spectrom., 2014, 25, 1810-1819]. Here we extend those capabilities to demonstrate how extracted IM profiles can be used to calculate accurate CCS values of peptide isomer ions which are not fully resolved by IM. We show that CCS values obtained from deconvoluted IM spectra match with CCS values measured from the individually analyzed corresponding peptides on uniform field IM instrumentation. We introduce an approach that utilizes experimentally determined IM arrival time (AT) "shift factors" to compensate for ion acceleration variations during post-IM/CID and significantly improve the accuracy of the calculated CCS values. Also, we discuss details of this IM deconvolution approach and compare empirical CCS values from traveling wave (TW)IM-MS and drift tube (DT)IM-MS with theoretically calculated CCS values using the projected superposition approximation (PSA). For example, experimentally measured deconvoluted TWIM-MS mean CCS values for doubly-protonated RYGGFM, RMFGYG, MFRYGG, and FRMYGG peptide isomers were 288.8 Å(2), 295.1 Å(2), 296.8 Å(2), and 300.1 Å(2); all four of these CCS values were within 1.5% of independently measured DTIM-MS values.

  5. External Second Gate, Fourier Transform Ion Mobility Spectrometry: Parametric Optimization for Detection of Weapons of Mass Destruction

    Directory of Open Access Journals (Sweden)

    Edward E. Tarver

    2004-03-01

    Full Text Available Abstract: Ion mobility spectrometry (IMS is recognized as one of the most sensitive and robust techniques for the detection of narcotics, explosives and chemical warfare agents. IMS is widely used in forensic, military and security applications. Increasing threat of terrorist attacks, the proliferation of narcotics, Chemical Weapons Convention (CWC treaty verification as well as humanitarian de-mining efforts have mandated that equal importance be placed on the time required to obtain results as well as the quality of the analytical data. [1] In this regard IMS is virtually unrivaled when both speed of response and sensitivity have to be considered. [2] The problem with conventional (signal averaging IMS systems is the fixed duty cycle of the entrance gate that restricts to less than 1%, the number of available ions contributing to the measured signal. Furthermore, the signal averaging process incorporates scan-to-scan variations that degrade the spectral resolution contributing to misidentifications and false positives. With external second gate, Fourier Transform ion mobility spectrometry (FT-IMS the entrance gate frequency is variable and can be altered in conjunction with other data acquisition parameters (scan time and sampling rate to increase the spectral resolution to reduce false alarms and improve the sensitivity for early warning and contamination avoidance. In addition, with FT-IMS the entrance gate operates with a 50% duty cycle and so affords a seven-fold increase in sensitivity. Recent data on high explosives are presented to demonstrate the parametric optimization in sensitivity and resolution of our system.

  6. High mobility graphene ion-sensitive field-effect transistors by noncovalent functionalization

    Science.gov (United States)

    Fu, W.; Nef, C.; Tarasov, A.; Wipf, M.; Stoop, R.; Knopfmacher, O.; Weiss, M.; Calame, M.; Schönenberger, C.

    2013-11-01

    Noncovalent functionalization is a well-known nondestructive process for property engineering of carbon nanostructures, including carbon nanotubes and graphene. However, it is not clear to what extend the extraordinary electrical properties of these carbon materials can be preserved during the process. Here, we demonstrated that noncovalent functionalization can indeed delivery graphene field-effect transistors (FET) with fully preserved mobility. In addition, these high-mobility graphene transistors can serve as a promising platform for biochemical sensing applications.Noncovalent functionalization is a well-known nondestructive process for property engineering of carbon nanostructures, including carbon nanotubes and graphene. However, it is not clear to what extend the extraordinary electrical properties of these carbon materials can be preserved during the process. Here, we demonstrated that noncovalent functionalization can indeed delivery graphene field-effect transistors (FET) with fully preserved mobility. In addition, these high-mobility graphene transistors can serve as a promising platform for biochemical sensing applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03940d

  7. Proteome profiling for assessing diversity: analysis of individual heads of Drosophila melanogaster using LC-ion mobility-MS.

    Science.gov (United States)

    Taraszka, John A; Gao, Xinfeng; Valentine, Stephen J; Sowell, Renã A; Koeniger, Stormy L; Miller, David F; Kaufman, Thomas C; Clemmer, David E

    2005-01-01

    The proteomes of three heads of individual Drosophila melanogaster organisms have been analyzed and compared by a combination of liquid chromatography, ion mobility spectrometry, and mass spectrometry approaches. In total, 197 proteins are identified among all three individuals (an average of 120 +/- 20 proteins per individual), of which at least 101 proteins are present in all three individuals. Within all three datasets, more than 25 000 molecular ions (an average of 9000 +/- 2000 per individual) corresponding to protonated precursor ions of individual peptides have been observed. A comparison of peaks among the datasets reveals that peaks corresponding to protonated peptides that are found in all heads are more intense than those features that appear between pairs of or within only one of the individuals. Moreover, there is little variability in the relative intensities of the peaks common among all individuals. It appears that it is the lower abundance components of the proteome that play the most significant role in determining unique features of individuals.

  8. Note: Design and construction of a simple and reliable printed circuit board-substrate Bradbury-Nielsen gate for ion mobility spectrometry

    Science.gov (United States)

    Du, Yongzhai; Cang, Huaiwen; Wang, Weiguo; Han, Fenglei; Chen, Chuang; Li, Lin; Hou, Keyong; Li, Haiyang

    2011-08-01

    A less laborious, structure-simple, and performance-reliable printed circuit board (PCB) based Bradbury-Nielsen gate for high-resolution ion mobility spectrometry was introduced and investigated. The gate substrate was manufactured using a PCB etching process with small holes (Φ 0.1 mm) drilled along the gold-plated copper lines. Two interdigitated sets of rigid stainless steel spring wire (Φ 0.1 mm) that stands high temperature and guarantees performance stability were threaded through the holes. Our homebuilt ion mobility spectrometer mounted with the gate gave results of about 40 for resolution while keeping a signal intensity of over 0.5 nano-amperes.

  9. Note: Design and construction of a simple and reliable printed circuit board-substrate Bradbury-Nielsen gate for ion mobility spectrometry.

    Science.gov (United States)

    Du, Yongzhai; Cang, Huaiwen; Wang, Weiguo; Han, Fenglei; Chen, Chuang; Li, Lin; Hou, Keyong; Li, Haiyang

    2011-08-01

    A less laborious, structure-simple, and performance-reliable printed circuit board (PCB) based Bradbury-Nielsen gate for high-resolution ion mobility spectrometry was introduced and investigated. The gate substrate was manufactured using a PCB etching process with small holes (Φ 0.1 mm) drilled along the gold-plated copper lines. Two interdigitated sets of rigid stainless steel spring wire (Φ 0.1 mm) that stands high temperature and guarantees performance stability were threaded through the holes. Our homebuilt ion mobility spectrometer mounted with the gate gave results of about 40 for resolution while keeping a signal intensity of over 0.5 nano-amperes.

  10. Waveform-dependent absorbing metasurfaces

    CERN Document Server

    Wakatsuchi, Hiroki; Rushton, Jeremiah J; Sievenpiper, Daniel F

    2014-01-01

    We present the first use of a waveform-dependent absorbing metasurface for high-power pulsed surface currents. The new type of nonlinear metasurface, composed of circuit elements including diodes, is capable of storing high power pulse energy to dissipate it between pulses, while allowing propagation of small signals. Interestingly, the absorbing performance varies for high power pulses but not for high power continuous waves (CWs), since the capacitors used are fully charged up. Thus, the waveform dependence enables us to distinguish various signal types (i.e. CW or pulse) even at the same frequency, which potentially creates new kinds of microwave technologies and applications.

  11. Enhancement of biological mass spectrometry by using separations based on changes in ion mobility (FAIMS and DMS).

    Science.gov (United States)

    Purves, Randy W

    2013-01-01

    Analysis of complex biological samples for low-level analytes by liquid chromatography-tandem mass spectrometry (LC-MS/MS) often requires additional selectivity. Differential mobility techniques (FAIMS and DMS) have been shown to enhance LC-MS/MS analyses by separating ions in the gas-phase on a millisecond timescale by use of a mechanism that is complementary to both liquid chromatography and mass spectrometry. In this overview, a simplified description of the operation of these devices is given and an example presented that illustrates the utility of FAIMS (DMS) for solving a challenging analytical assay. Important recent advances in the field, including work with gas modifiers, are presented, along with an outlook for the technology.

  12. Target identification of volatile metabolites to allow the differentiation of lactic acid bacteria by gas chromatography-ion mobility spectrometry.

    Science.gov (United States)

    Gallegos, Janneth; Arce, Cristina; Jordano, Rafael; Arce, Lourdes; Medina, Luis M

    2017-04-01

    The purpose of this work was to study the potential of gas chromatography-ion mobility spectrometry (GC-IMS) to differentiate lactic acid bacteria (LAB) through target identification and fingerprints of volatile metabolites. The LAB selected were used as reference strains for their influence in the flavour of cheese. The four strains of LAB can be distinguished by the fingerprints generated by the volatile organic compounds (VOCs) emitted. 2-butanone, 2-pentanone, 2-heptanone and 3-methyl-1-butanol were identified as relevant VOCs for Lactobacillus casei and Lactobacillus paracasei subsp. paracasei. 2-Butanone and 3-methyl-1-butanol were identified in Lactococcus lactis subsp. lactis and Lactococcus cremoris subsp. cremoris. The IMS signals monitoring during a 24-30h period showed the growth of the LAB in vitro. The results demonstrated that GC-IMS is a useful technology for bacteria recognition and also for screening the aromatic potential of new isolates of LAB.

  13. Detection of tetrahydrocannabinol residues on hands by ion-mobility spectrometry (IMS). Correlation of IMS data with saliva analysis.

    Science.gov (United States)

    Sonnberg, Saskia; Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel

    2015-08-01

    Ion-mobility spectroscopy (IMS) was evaluated as a high-throughput, cheap, and efficient analytical tool for detecting residues of tetrahydrocannabinol (THC) on hands. Regarding the usefulness of hand residues as potential samples for determining THC handling and abuse, we studied the correlation between data obtained from cannabis consumers who were classified as positive after saliva analysis and from those who were classified as positive on the basis of the information from hand-residue analysis. Sampling consisted of wiping the hands with borosilicate glass microfiber filters and introducing these directly into the IMS after thermal desorption. The possibility of false positive responses, resulting from the presence of other compounds with a similar drift time to THC, was evaluated and minimised by applying the truncated negative second-derivative algorithm. The possibility of false negative responses, mainly caused by competitive ionisation resulting from nicotine, was also studied. Graphical abstract THC residues: from hands to analytical signals.

  14. [Rapid detection of residual cyclohexanone in disposable medical devices by ultraviolet photoionization ion mobility spectrometry (UV-IMS)].

    Science.gov (United States)

    Li, Hu; Han, Hai-yan; Niu, Wen-qi; Wang, Hong-mei; Huang, Chao-qun; Jiang, Hai-he; Chu, Yan-nan

    2012-01-01

    In the manufacture of disposable PVC medical devices, cyclohexanone is frequently used as an adhesive reagent, which can be released into the tube airspace or stored solution and thus may cause some adverse effects on patients in therapy. In this paper, an ultraviolet photoionization ion mobility spectrometry (UV-IMS) technique has been developed to detect cyclohexanone through monitoring the gas composition within a package of infusion sets. The concentrations of cyclohexanone were prepared by means of exponential dilution method, and the experiments show that the UV-IMS has a limit of detection at 15 ppb and its measurable linear dynamics range is over three orders of magnitude. The concentrations of cyclohexanone in three brands of infusion sets packages were determined to be 16.78, 17.59 and 46.69 ppm respectively. The UV-IMS is proposed as a tool for the quality control of medical devices to monitor illegal uses of chemical solvents like cyclohexanone.

  15. Evaluation of a new miniaturized ion mobility spectrometer and its coupling to fast gas chromatography multicapillary columns.

    Science.gov (United States)

    Aguilera-Herrador, E; Cárdenas, S; Ruzsanyi, V; Sielemann, S; Valcárcel, M

    2008-12-19

    A new miniaturized ion mobility spectrometer (microIMS) has been constructed and evaluated. The results obtained for a selected group of volatile organic compounds have been compared with those provided by an IMS of bigger dimensions with satisfactory conclusions. Moreover, its performance in terms of analytes resolution is better than those values given for other miniaturized instruments described in the literature. The possibility of an adjustable shutter opening time and the low intensity of the radiation source are also remarkable characteristics of the miniaturized detector. The small size of the microIMS enables its portability and its wide-range of applications as a sensor device. Six different substances supposed as respiratory markers of different diseases have been selected to prove the feasibility of the spectrometer constructed.

  16. Atmospheric Solid Analysis Probe-Ion Mobility Mass Spectrometry: An Original Approach to Characterize Grafting on Cyclic Olefin Copolymer Surfaces.

    Science.gov (United States)

    Vieillard, Julien; Hubert-Roux, Marie; Brisset, Florian; Soulignac, Cecile; Fioresi, Flavia; Mofaddel, Nadine; Morin-Grognet, Sandrine; Afonso, Carlos; Le Derf, Franck

    2015-12-01

    A cyclic olefin copolymer (COC) was grafted with aryl layers from aryldiazonium salts, and then we combined infrared spectrometry, atomic force microscopy (AFM), and ion mobility mass spectrometry with atmospheric solid analysis probe ionization (ASAP-IM-MS) to characterize the aryl layers. ASAP is a recent atmospheric ionization method dedicated to the direct analysis of solid samples. We demonstrated that ASAP-IM-MS is complementary to other techniques for characterizing bromine and sulfur derivatives of COC on surfaces. ASAP-IM-MS was useful for optimizing experimental grafting conditions and to elucidate hypotheses around aryl layer formation during the grafting process. Thus, ASAP-IM-MS is a good candidate tool to characterize covalent grafting on COC surfaces.

  17. Electrospray ionization ion mobility mass spectrometry provides novel insights into the pattern and activity of fetal hippocampus gangliosides.

    Science.gov (United States)

    Sarbu, Mirela; Vukelić, Željka; Clemmer, David E; Zamfir, Alina D

    2017-08-01

    Gangliosides (GGs), a particular class of glycosphingolipids ubiquitously found in tissues and body fluids, exhibit the highest expression in the central nervous system, especially in brain. GGs are involved in crucial processes, such as neurogenesis, synaptogenesis, synaptic transmission, cell adhesion, growth and proliferation. For these reasons, efforts are constantly invested into development and refinement of specific methods for GG analysis. We have recently shown that ion mobility separation (IMS) mass spectrometry (MS) has the capability to provide consistent compositional and structural information on GGs at high sensitivity, resolution and mass accuracy. In the present paper, we have implemented IMS MS for the first time in the study of a highly complex native GG mixture extracted and purified from human fetal hippocampus. As compared to previous studies, where no separation techniques prior to MS were applied, IMS MS technique has not just generated valuable novel information on the GG pattern characteristic for hippocampus in early developmental stage, but also provided data related to the GG molecular involvement in the synaptic functions by the discovery of 25 novel structures modified by CH3COO(-). The detection and identification in fetal hippocampus of a much larger number of GG species than ever reported before was possible due to the ion mobility separation according to the charge state, the carbohydrate chain length and the degree of sialylation. By applying IMS in conjunction with collision induced dissociation (CID) tandem MS (MS/MS), novel GG species modified by CH3COO(-) attachment, discovered here for the first time, were sequenced and structurally investigated in details. The present findings, based on IMS MS, provide a more reliable insight into the expression and role of gangliosides in human hippocampus, with a particular emphasis on their cholinergic activity at this level. Copyright © 2017 Elsevier B.V. and Société Française de

  18. Characterization of polysorbate 85, a nonionic surfactant, by liquid chromatography vs. ion mobility separation coupled with tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Solak Erdem, Nilüfer; Alawani, Nadrah; Wesdemiotis, Chrys, E-mail: wesdemiotis@uakron.edu

    2014-01-15

    Graphical abstract: -- Highlights: •Liquid chromatography (LC) separates amphiphilic blends according to hydrophobicity. •Ion mobility (IM) spectrometry separates these blends based on molecular size/shape. •LC–MS provides the separation resolution needed for quantifying fatty acid content. •IM–MS enables rapid, solvent-free separation and the detection of trace components. •With either method, tandem MS allows to count the hydrophobic substituents. -- Abstract: Liquid chromatography (LC) and ion mobility (IM) separation have been coupled with mass spectrometry (MS) and tandem mass spectrometry (MS{sup 2}) to characterize a commercially important nonionic surfactant, polysorbate 85. The constituents of this amphiphilic blend contained a sorbitan or isosorbide core that was chain extended with poly(ethylene oxide) (PEO) and partially esterified at the PEO termini with oleic acid or, to a lesser extent, other fatty acids. Using interactive LC in reverse-phase mode, the oligomers of the surfactant were separated according to their hydrophobicity/hydrophilicity balance. On the other hand, IM spectrometry dispersed the surfactant oligomers by their charge and collision cross section (i.e. size/shape). With either separation method, an increased number of fatty ester groups and/or lack of the polar sorbitan (or isosorbide) core led to higher retention/drift times, enabling the separation of isobaric species or species with superimposed isotope patterns, so that their ester content could be conclusively identified by MS{sup 2}. LC–MS and IM–MS permitted the detection of several byproducts besides the major PEO-sorbitan oleate oligomers. LC–MS provides the separation resolution needed for quantitative determination of the degree of esterification. IM–MS, which minimizes analysis time and solvent use, is ideally suitable for a fast, qualitative survey of samples differing in their minor constituents or impurities.

  19. Online Hydrogen-Deuterium Exchange Traveling Wave Ion Mobility Mass Spectrometry (HDX-IM-MS): a Systematic Evaluation

    Science.gov (United States)

    Cryar, Adam; Groves, Kate; Quaglia, Milena

    2017-06-01

    Hydrogen-deuterium exchange mass spectrometry (HDX-MS) is an important tool for measuring and monitoring protein structure. A bottom-up approach to HDX-MS provides peptide level deuterium uptake values and a more refined localization of deuterium incorporation compared with global HDX-MS measurements. The degree of localization provided by HDX-MS is proportional to the number of peptides that can be identified and monitored across an exchange experiment. Ion mobility spectrometry (IMS) has been shown to improve MS-based peptide analysis of biological samples through increased separation capacity. The integration of IMS within HDX-MS workflows has been commercialized but presently its adoption has not been widespread. The potential benefits of IMS, therefore, have not yet been fully explored. We herein describe a comprehensive evaluation of traveling wave ion mobility integrated within an online-HDX-MS system and present the first reported example of UDMSE acquisition for HDX analysis. Instrument settings required for optimal peptide identifications are described and the effects of detector saturation due to peak compression are discussed. A model system is utilized to confirm the comparability of HDX-IM-MS and HDX-MS uptake values prior to an evaluation of the benefits of IMS at increasing sample complexity. Interestingly, MS and IM-MS acquisitions were found to identify distinct populations of peptides that were unique to the respective methods, a property that can be utilized to increase the spatial resolution of HDX-MS experiments by >60%. [Figure not available: see fulltext.

  20. Alignment of retention time obtained from multicapillary column gas chromatography used for VOC analysis with ion mobility spectrometry.

    Science.gov (United States)

    Perl, Thorsten; Bödeker, Bertram; Jünger, Melanie; Nolte, Jürgen; Vautz, Wolfgang

    2010-07-01

    Multicapillary column (MCC) ion mobility spectrometers (IMS) are increasingly in demand for medical diagnosis, biological applications and process control. In a MCC-IMS, volatile compounds are differentiated by specific retention time and ion mobility when rapid preseparation techniques are applied, e.g. for the analysis of complex and humid samples. Therefore, high accuracy in the determination of both parameters is required for reliable identification of the signals. The retention time in the MCC is the subject of the present investigation because, for such columns, small deviations in temperature and flow velocity may cause significant changes in retention time. Therefore, a universal correction procedure would be a helpful tool to increase the accuracy of the data obtained from a gas-chromatographic preseparation. Although the effect of the carrier gas flow velocity and temperature on retention time is not linear, it could be demonstrated that a linear alignment can compensate for the changes in retention time due to common minor deviations of both the carrier gas flow velocity and the column temperature around the MCC-IMS standard operation conditions. Therefore, an effective linear alignment procedure for the correction of those deviations has been developed from the analyses of defined gas mixtures under various experimental conditions. This procedure was then applied to data sets generated from real breath analyses obtained in clinical studies using different instruments at different measuring sites for validation. The variation in the retention time of known signals, especially for compounds with higher retention times, was significantly improved. The alignment of the retention time--an indispensable procedure to achieve a more precise identification of analytes--using the proposed method reduces the random error caused by small accidental deviations in column temperature and flow velocity significantly.

  1. Ion mobility mass spectrometry as a potential tool to assign disulfide bonds arrangements in peptides with multiple disulfide bridges.

    Science.gov (United States)

    Echterbille, Julien; Quinton, Loïc; Gilles, Nicolas; De Pauw, Edwin

    2013-05-07

    Disulfide bridges play a major role in defining the structural properties of peptides and proteins. However, the determination of the cysteine pairing is still challenging. Peptide sequences are usually achieved using tandem mass spectrometry (MS/MS) spectra of the totally reduced unfolded species, but the cysteine pairing information is lost. On the other hand, MS/MS experiments performed on native folded species show complex spectra composed of nonclassical ions. MS/MS alone does not allow either the cysteine pairing or the full sequence of an unknown peptide to be determined. The major goal of this work is to set up a strategy for the full structural characterization of peptides including disulfide bridges annotation in the sequence. This strategy was developed by combining ion mobility spectrometry (IMS) and collision-induced dissociation (CID). It is assumed that the opening of one S-S bridge in a peptide leads to a structural evolution which results in a modification of IMS drift time. In the presence of multiple S-S bridges, the shift in arrival time will depend on which disulfide(s) has (have) been reduced and on the shape adopted by the generated species. Due to specific fragmentations observed for each species, CID experiments performed after the mobility separation could provide not only information on peptide sequence but also on the localization of the disulfide bridges. To achieve this goal, synthetic peptides containing two disulfides were studied. The openings of the bridges were carried out following different experimental conditions such as reduction, reduction/alkylation, or oxidation. Due to disulfide scrambling highlighted with the reduction approaches, oxidation of S-S bonds into cysteic acids appeared to be the best strategy. Cysteine connectivity was then unambiguously determined for the two peptides, without any disulfide scrambling interference.

  2. Mobile Ion Induced Slow Carrier Dynamics in Organic-Inorganic Perovskite CH₃NH₃PbBr₃.

    Science.gov (United States)

    Chen, Sheng; Wen, Xiaoming; Sheng, Rui; Huang, Shujuan; Deng, Xiaofan; Green, Martin A; Ho-Baillie, Anita

    2016-03-02

    Here, we investigate photoluminescence (PL) and time-resolved photoluminescence (TRPL) in CH3NH3PbBr3 perovskite under continuous illumination, using optical and electro-optical techniques. Under continuous excitation at constant intensity, PL intensity and PL decay (carrier recombination) exhibit excitation intensity dependent reductions in the time scale of seconds to minutes. The enhanced nonradiative recombination is ascribed to light activated negative ions and their accumulation which exhibit a slow dynamics in a time scale of seconds to minutes. The observed result suggests that the organic-inorganic hybrid perovskite is a mixed electronic-ionic semiconductor. The key findings in this work suggest that ions are photoactivated or electro-activated and their accumulation at localized sites can result in a change of carrier dynamics. The findings are therefore useful for the understanding of instability of perovskite solar cells and shed light on the necessary strategies for performance improvement.

  3. Determination of biogenic amines in canned fish samples using head-space solid phase microextraction based on nanostructured polypyrrole fiber coupled to modified ionization region ion mobility spectrometry.

    Science.gov (United States)

    Parchami, Razieh; Kamalabadi, Mahdie; Alizadeh, Naader

    2017-01-20

    The head-space solid phase microextraction (HS-SPME) was applied to extraction and determination of histamine (HIS), putrescine (PUT), cadaverine (CAD), tyramine (TYR) in canned fish samples by ion mobility spectrometry (IMS) without any derivatization process. HIS and CAD have the same mobilities in nitrogen as buffer gas and their corresponding peaks are severely overlapped in ion mobility spectrum. Peak separation was acquired in the presence of 18-crown-6 vapor as complexation reagent into carrier gas and modified ionization region of IMS (MIR-IMS) at optimum flow rate. The interaction between 18-crown-6 and the mentioned amines forms nanocluster product ions with different cross section areas and ion mobilities. The effects of main extraction parameters on the efficiency of HS-SPME-MIR-IMS were investigated and optimized. Relative standard deviations (RSD%) of the biogenic amines determination at 50μgL(-1) concentration level were obtained in range 5.7%-6.3%. Limits of detection for analytes were in the range of 0.6-1ngg(-1). HS-SPME-MIR-IMS results indicate that the proposed method can be successfully used in biogenic amines analysis in water and food samples. Method validation was conducted by comparing our results with those obtained through GC-MS method.

  4. Corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry for monitoring of volatile organic compounds.

    Science.gov (United States)

    Sabo, Martin; Matejčík, Štefan

    2012-06-19

    We demonstrate the application of corona discharge ion mobility spectrometry with orthogonal acceleration time of flight mass spectrometry (CD IMS-oaTOF) for volatile organic compounds (VOCs) monitoring. Two-dimensional (2D) IMS-oaTOF spectra of VOCs were recorded in nearly real time. The corona discharge atmospheric pressure chemical ionization (APCI) source was operated in positive mode in nitrogen and air. The CD ion source generates in air H(3)O(+)(H(2)O)(n) and NO(+). The NO(+) offers additional possibility for selective ionization and for an increase of the sensitivity of monoaromatic compounds. In addition to H(3)O(+)(H(2)O)(n) and NO(+), we have carried out ionization of VOCs using acetone as dopant gas ((CH(3))(2)COH(+)). Sixteen model VOCs (tetrahydrofuran, butanol, n-propanol, iso-propano, acetone, methanol, ethanol, toluene, benzene, amomnia, dioxan, triethylamine, acetonitrile, formaldehyde, m-xylene, 2,2,2-trifluoroethylamine) were tested using these ionization techniques.

  5. Express analysis of explosives, chemical warfare agents and drugs with multicapillary column gas chromatography and ion mobility increment spectrometry.

    Science.gov (United States)

    Buryakov, Igor A

    2004-02-05

    Description of a gas chromatograph designed for express analysis of explosives (2,4-dinitrotoluene, 2,4,6-trinitrotoluene, pentaerythritol tetranitrate), chemical warfare agents (mustard gas, lewisite, sarin) and drugs (heroin, cocaine hydrochloride, crack) is given. The devices comprises a multicapillary chromatographic column and an ion mobility increment spectrometer (MCC-IMIS). The main analytical characteristics of an IMIS (estimated detection limit (DL), linear dynamic range (LDR), speed of response) and a chromatographic column (separation power, degree of separation, a number of possible peaks at a chromatogram section, divided by analysis time) are determined. The maximum value of DL equal to 5 pg/ml was registered for cis-alpha-LW, and the lowest one of 0.001 pg/ml was for cocaine. The maximum value of LDR equal to 1000 was registered for sarin and the lowest one of 150 was for the ions of lewisite. Speed of response of one compound detection with the IMIS was 0.7 s.

  6. Applications of ion mobility spectrometry (IMS) to the analysis of gamma-hydroxybutyrate and gamma-hydroxyvalerate in toxicological matrices.

    Science.gov (United States)

    Mercer, Jennifer; Shakleya, Diaa; Bell, Suzanne

    2006-10-01

    The predator drug gamma-hydroxybutyrate (GHB) and its lactone form gamma-butyrolactone (GBL) continue to present significant analytical challenges to forensic toxicologists and chemists. The five-carbon analogue (gamma hydroxyvalerate GHV) and the corresponding lactone GVL) are emerging as substitutes for GHB, adding further complications. Ion mobility spectrometry (IMS) was investigated as a method of screening urine and breath for the presence of these drugs and their degradation products. Sample was introduced into the instrument via a programmable split/splitless injection port with thermal desorption. The injection method in effect replaces problematic solvent extraction methods with a physical extraction, an efficient method in the present case considering the hydrophilic nature of GHB. No chromatography was employed and results were obtained within a few seconds. The negative ion mode showed the greatest sensitivity with detection limits in the low parts-per-million range for GHB and GHV. Because GHB is often delivered in alcoholic beverages, ethanol and acetaldehyde, along with potential interfering compounds methanol, isopropanol, and acetone, were also analyzed. None were found to interfere. The thermally induced ring opening prevented differentiation of GHB and GBL using direct injection/thermal desorption protocol, but IMS does show promise as a rapid, simple, and affordable screening technique for GHB and related compounds.

  7. An MSK Waveform for Radar Applications

    Science.gov (United States)

    Quirk, Kevin J.; Srinivasan, Meera

    2009-01-01

    We introduce a minimum shift keying (MSK) waveform developed for use in radar applications. This waveform is characterized in terms of its spectrum, autocorrelation, and ambiguity function, and is compared with the conventionally used bi-phase coded (BPC) radar signal. It is shown that the MSK waveform has several advantages when compared with the BPC waveform, and is a better candidate for deep-space radar imaging systems such as NASA's Goldstone Solar System Radar.

  8. Radar Waveform Design in Active Communications Channel

    OpenAIRE

    Ric A. Romero; Shepherd, Kevin D.

    2013-01-01

    In this paper, we investigate spectrally adaptive radar transmit waveform design and its effects on an active communication system. We specifically look at waveform design for point targets. The transmit waveform is optimized by accounting for the modulation spectrum of the communication system while trying to efficiently use the remaining spectrum. With the use of spectrally-matched radar waveform, we show that the SER detection performance of the communication system ...

  9. Distance Geometry Protocol to Generate Conformations of Natural Products to Structurally Interpret Ion Mobility-Mass Spectrometry Collision Cross Sections

    Science.gov (United States)

    2015-01-01

    Ion mobility-mass spectrometry (IM-MS) allows the separation of ionized molecules based on their charge-to-surface area (IM) and mass-to-charge ratio (MS), respectively. The IM drift time data that is obtained is used to calculate the ion-neutral collision cross section (CCS) of the ionized molecule with the neutral drift gas, which is directly related to the ion conformation and hence molecular size and shape. Studying the conformational landscape of these ionized molecules computationally provides interpretation to delineate the potential structures that these CCS values could represent, or conversely, structural motifs not consistent with the IM data. A challenge in the IM-MS community is the ability to rapidly compute conformations to interpret natural product data, a class of molecules exhibiting a broad range of biological activity. The diversity of biological activity is, in part, related to the unique structural characteristics often observed for natural products. Contemporary approaches to structurally interpret IM-MS data for peptides and proteins typically utilize molecular dynamics (MD) simulations to sample conformational space. However, MD calculations are computationally expensive, they require a force field that accurately describes the molecule of interest, and there is no simple metric that indicates when sufficient conformational sampling has been achieved. Distance geometry is a computationally inexpensive approach that creates conformations based on sampling different pairwise distances between the atoms within the molecule and therefore does not require a force field. Progressively larger distance bounds can be used in distance geometry calculations, providing in principle a strategy to assess when all plausible conformations have been sampled. Our results suggest that distance geometry is a computationally efficient and potentially superior strategy for conformational analysis of natural products to interpret gas-phase CCS data. PMID:25360896

  10. Generating nonlinear FM chirp waveforms for radar.

    Energy Technology Data Exchange (ETDEWEB)

    Doerry, Armin Walter

    2006-09-01

    Nonlinear FM waveforms offer a radar matched filter output with inherently low range sidelobes. This yields a 1-2 dB advantage in Signal-to-Noise Ratio over the output of a Linear FM waveform with equivalent sidelobe filtering. This report presents design and implementation techniques for Nonlinear FM waveforms.

  11. Determining the risk of cardiovascular disease using ion mobility of lipoproteins

    Energy Technology Data Exchange (ETDEWEB)

    Benner, W. Henry; Krauss, Ronald M.; Blanche, Patricia J.

    2010-05-11

    A medical diagnostic method and instrumentation system for analyzing noncovalently bonded agglomerated biological particles is described. The method and system comprises: a method of preparation for the biological particles; an electrospray generator; an alpha particle radiation source; a differential mobility analyzer; a particle counter; and data acquisition and analysis means. The medical device is useful for the assessment of human diseases, such as cardiac disease risk and hyperlipidemia, by rapid quantitative analysis of lipoprotein fraction densities. Initially, purification procedures are described to reduce an initial blood sample to an analytical input to the instrument. The measured sizes from the analytical sample are correlated with densities, resulting in a spectrum of lipoprotein densities. The lipoprotein density distribution can then be used to characterize cardiac and other lipid-related health risks.

  12. Method of assessing a lipid-related health risk based on ion mobility analysis of lipoproteins

    Science.gov (United States)

    Benner, W. Henry; Krauss, Ronald M.; Blanche, Patricia J.

    2010-12-14

    A medical diagnostic method and instrumentation system for analyzing noncovalently bonded agglomerated biological particles is described. The method and system comprises: a method of preparation for the biological particles; an electrospray generator; an alpha particle radiation source; a differential mobility analyzer; a particle counter; and data acquisition and analysis means. The medical device is useful for the assessment of human diseases, such as cardiac disease risk and hyperlipidemia, by rapid quantitative analysis of lipoprotein fraction densities. Initially, purification procedures are described to reduce an initial blood sample to an analytical input to the instrument. The measured sizes from the analytical sample are correlated with densities, resulting in a spectrum of lipoprotein densities. The lipoprotein density distribution can then be used to characterize cardiac and other lipid-related health risks.

  13. Use of ion mobility mass spectrometry and a collision cross-section algorithm to study an organometallic ruthenium anticancer complex and its adducts with a DNA oligonucleotide.

    Science.gov (United States)

    Williams, Jonathan P; Lough, Julie Ann; Campuzano, Iain; Richardson, Keith; Sadler, Peter J

    2009-11-01

    We report the development of an enhanced algorithm for the calculation of collision cross-sections in combination with Travelling-Wave ion mobility mass spectrometry technology and its optimisation and evaluation through the analysis of an organoruthenium anticancer complex [(eta6-biphenyl)Ru(II)(en)Cl]+. Excellent agreement was obtained between the experimentally determined and theoretically determined collision cross-sections of the complex and its major product ion formed via collision-induced dissociation. Collision cross-sections were also experimentally determined for adducts of this ruthenium complex with the single-stranded oligonucleotide hexamer d(CACGTG). Ion mobility tandem mass spectrometry measurements have allowed the binding sites for ruthenium on the oligonucleotide to be determined.

  14. The role of proton mobility in determining the energy-resolved vibrational activation/dissociation channels of N-glycopeptide ions.

    Science.gov (United States)

    Kolli, Venkata; Roth, Heidi A; De La Cruz, Gabriela; Fernando, Ganga S; Dodds, Eric D

    2015-10-01

    Site-specific glycoproteomic analysis largely hinges on the use of tandem mass spectrometry (MS/MS) to identify glycopeptides. Experiments of this type are usually aimed at drawing connections between individual oligosaccharide structures and their specific sites of attachment to the polypeptide chain. These determinations inherently require ion dissociation methods capable of interrogating both the monosaccharide and amino acid connectivity of the glycopeptide. Collision-induced dissociation (CID) shows potential to satisfy this requirement, as the vibrational activation/dissociation of protonated N-glycopeptides has been observed to access cleavage of either glycosidic bonds of the glycan or amide bonds of the peptide in an energy-resolved manner. Nevertheless, the relative energy requirement for these fragmentation pathways varies considerably among analytes. This research addresses the influence of proton mobility on the vibrational energy necessary to achieve either glycan or peptide cleavage in a collection of protonated N-glycopeptide ions. While greater proton mobility of the precursor ion was found to correlate with lower energy requirements for precursor ion depletion and appearance of glycosidic fragments, the vibrational energy deposition necessary for appearance of peptide backbone fragments showed no relation to the precursor ion proton mobility. These results are consistent with observations suggesting that peptide fragments arise from an intermediate fragment which is generally of lower proton mobility than the precursor ion. Such findings have potential to facilitate the rational selection of CID conditions which are best suited to provide either glycan or peptide cleavage products in MS/MS based N-glycoproteomic analysis.

  15. 基于迁移管法气压对氮气正电晕放电离子迁移率的影响%Influence of Air Pressure on Corona Discharge Ion Mobility of Nitrogen Based on Drift Tube Method

    Institute of Scientific and Technical Information of China (English)

    刘云鹏; 吴振扬; 朱雷; 裴少通

    2016-01-01

    The ion mobility in low gas pressure is a key parameter for corona discharge of power transmission line in high altitude area. Meanwhile, nitrogen as the main reaction gas in positive corona discharge, its existing value of the ion mobility takes no consideration of gas pressure. Actually, the measurements of ion mobility in different gas pressures have great significance to establish the ion current and corona loss calculation models. A needle-ring corona discharge experiment platform is designed and set up, which can simulate different gas pressures. What's more, the execution of the ion gate is improved from off-on-off to off-on, thus the waveforms with higher amplitudes of the ion could be gained. Thanks to the designed platform, the measured ion mobility of pure nitrogen under normal atmospheric condition is 1.113cm2V−1S−1. Besides, the positive nitrogen ion mobility at gas pressure of 101.19~44.52kPa is measured. The experimental results indicate that the ion mobility decreases nonlinearly with the increasing of gas pressure and has a certain trend of saturation. Finally, an index correction method is put forward.%低气压下离子迁移率是高海拔地区输电线路导线电晕放电的关键参数之一,同时氮气作为正电晕放电参与反应的主要气体,目前均作为常量对待,其测量结果对于建立考虑海拔因素的离子流、电晕损失等计算模型具有重要意义,因此对不同气压下氮气正离子迁移率的测量显得尤为重要。在已有研究的基础上,自主设计了可模拟不同氮气气压条件下离子迁移率测量平台,并将离子门的动作方式由关闭—导通—关闭改进为关闭—导通,从而得到幅值尽可能大的离子流波形。利用此平台测量得到大气条件下纯氮气环境离子的迁移率为1.113cm2V−1S−1,并通过试验研究了气压在101.19~44.52kPa范围内氮气环境离子迁移率变化情况,研究发现氮气正离子迁

  16. EPOS-S: Integrated access to seismological waveforms

    Science.gov (United States)

    Sleeman, Reinoud; Strollo, Angelo; Michelini, Alberto; Clinton, John; Gueguen, Philippe; Luzi, Lucia; Pinar, Ali; Diaz, Jordi; Ceken, Ulubey; Evangelidis, Christos; Haslinger, Florian

    2016-04-01

    The main challenges of the EPOS TCS Seismology are to improve and to extend existing services to access earthquake waveforms (ORFEUS), parameters (EMSC) and hazard data and products (EFEHR), and producing a single framework that is technically integrated within the EPOS architecture. Technical developments in the services for seismological waveforms and associated data, including the compilation of station metadata and installing common data archival and sharing policies are within ORFEUS and its Working Groups. The focus is on 1) the development of the next generation software architecture for the European Integrated (seismological) Data Archive EIDA based on standardized webservices, the implementation of a data quality service and the realisation of a mediator service; 2) the development of EIDA-compliant services for strong motion data and acceleration data and the extension of the station metadata model; 3) the integration of data from mobile networks and OBS waveforms into EIDA by implementing mechanisms for coordination of transnational access and multinational experiments at available pools of OBS and mobile seismic stations; 4) achieve close integration with other EPOS TCS and the ICS with regard to interoperability and common use of tools & services, common and coordinated data models and metadata formats, and common computational platforms and IT solution implementations. This presentation will present the status of and current developments towards the above objectives.

  17. Workflows for Full Waveform Inversions

    Science.gov (United States)

    Boehm, Christian; Krischer, Lion; Afanasiev, Michael; van Driel, Martin; May, Dave A.; Rietmann, Max; Fichtner, Andreas

    2017-04-01

    Despite many theoretical advances and the increasing availability of high-performance computing clusters, full seismic waveform inversions still face considerable challenges regarding data and workflow management. While the community has access to solvers which can harness modern heterogeneous computing architectures, the computational bottleneck has fallen to these often manpower-bounded issues that need to be overcome to facilitate further progress. Modern inversions involve huge amounts of data and require a tight integration between numerical PDE solvers, data acquisition and processing systems, nonlinear optimization libraries, and job orchestration frameworks. To this end we created a set of libraries and applications revolving around Salvus (http://salvus.io), a novel software package designed to solve large-scale full waveform inverse problems. This presentation focuses on solving passive source seismic full waveform inversions from local to global scales with Salvus. We discuss (i) design choices for the aforementioned components required for full waveform modeling and inversion, (ii) their implementation in the Salvus framework, and (iii) how it is all tied together by a usable workflow system. We combine state-of-the-art algorithms ranging from high-order finite-element solutions of the wave equation to quasi-Newton optimization algorithms using trust-region methods that can handle inexact derivatives. All is steered by an automated interactive graph-based workflow framework capable of orchestrating all necessary pieces. This naturally facilitates the creation of new Earth models and hopefully sparks new scientific insights. Additionally, and even more importantly, it enhances reproducibility and reliability of the final results.

  18. Why Waveform Correlation Sometimes Fails

    Science.gov (United States)

    Carmichael, J.

    2015-12-01

    Waveform correlation detectors used in explosion monitoring scan noisy geophysical data to test two competing hypotheses: either (1) an amplitude-scaled version of a template waveform is present, or, (2) no signal is present at all. In reality, geophysical wavefields that are monitored for explosion signatures include waveforms produced by non-target sources that are partially correlated with the waveform template. Such signals can falsely trigger correlation detectors, particularly at low thresholds required to monitor for smaller target explosions. This challenge is particularly formidable when monitoring known test sites for seismic disturbances, since uncatalogued natural seismicity is (generally) more prevalent at lower magnitudes, and could be mistaken for small explosions. To address these challenges, we identify real examples in which correlation detectors targeting explosions falsely trigger on both site-proximal earthquakes (Figure 1, below) and microseismic "noise". Motivated by these examples, we quantify performance loss when applying these detectors, and re-evaluate the correlation-detector's hypothesis test. We thereby derive new detectors from more general hypotheses that admit unknown background seismicity, and apply these to real data. From our treatment, we derive "rules of thumb'' for proper template and threshold selection in heavily cluttered signal environments. Last, we answer the question "what is the probability of falsely detecting an earthquake collocated at a test site?", using correlation detectors that include explosion-triggered templates. Figure Top: An eight-channel data stream (black) recorded from an earthquake near a mine. Red markers indicate a detection. Middle: The correlation statistic computed by scanning the template against the data stream at top. The red line indicates the threshold for event declaration, determined by a false-alarm on noise probability constraint, as computed from the signal-absent distribution using

  19. Phenomenological gravitational waveforms from spinning coalescing binaries

    CERN Document Server

    Sturani, R; Cadonati, L; Guidi, G M; Healy, J; Shoemaker, D; Vicere', A

    2010-01-01

    An accurate knowledge of the coalescing binary gravitational waveform is crucial for match filtering techniques, which are currently used in the observational searches performed by the LIGO-Virgo collaboration. Following an earlier paper by the same authors we expose the construction of analytical phenomenological waveforms describing the signal sourced by generically spinning binary systems. The gap between the initial inspiral part of the waveform, described by spin-Taylor approximants, and its final ring-down part, described by damped exponentials, is bridged by a phenomenological phase calibrated by comparison with the dominant spherical harmonic mode of a set of waveforms including both numerical and phenomenological waveforms of a different type. All waveforms considered describe equal mass systems with dimension-less spin magnitudes equal to 0.6. The noise-weighted overlap integral between numerical and phenomenological waveforms ranges between 0.93 and 0.98 for a wide span of mass values.

  20. Investigation of isomeric flavanol structures in black tea thearubigins using ultraperformance liquid chromatography coupled to hybrid quadrupole/ion mobility/time of flight mass spectrometry.

    Science.gov (United States)

    Yassin, Ghada H; Grun, Christian; Koek, Jean H; Assaf, Khaleel I; Kuhnert, Nikolai

    2014-11-01

    Ultra performance liquid chromatography (UPLC) when coupled to ion mobility (IMS)/orthogonal acceleration time of flight mass spectrometry is a suitable technique for analyzing complex mixtures such as the black tea thearubigins. With the aid of this advanced instrumental analysis, we were able to separate and identify different isomeric components in the complex mixture which could previously not be differentiated by a conventional high performance liquid chromatography/tandem mass spectrometry. In this study, the difference between isomeric structures theasinensins, proanthocyanidins B-type and rutin (quercetin-3O-rutinoside) were studied, and these are present abundantly in many botanical sources. The differentiation between these structures was accomplished according to their acquired mobility drift times differing from the traditional investigations in mass spectrometry, where calculation of theoretical collisional cross sections allowed assignment of the individual isomeric structures. The present work demonstrates UPLC-IMS-MS as an efficient technology for isolating and separating isobaric and isomeric structures existing in complex mixtures discriminating between them according to their characteristic fragment ions and mobility drift times. Therefore, a rational assignment of isomeric structures in many phenolic secondary metabolites based on the ion mobility data might be useful in mass spectrometry-based structure analysis in the future.

  1. Evaluation and application of static headspace-multicapillary column-gas chromatography-ion mobility spectrometry for complex sample analysis.

    Science.gov (United States)

    Denawaka, Chamila J; Fowlis, Ian A; Dean, John R

    2014-04-18

    An evaluation of static headspace-multicapillary column-gas chromatography-ion mobility spectrometry (SHS-MCC-GC-IMS) has been undertaken to assess its applicability for the determination of 32 volatile compounds (VCs). The key experimental variables of sample incubation time and temperature have been evaluated alongside the MCC-GC variables of column polarity, syringe temperature, injection temperature, injection volume, column temperature and carrier gas flow rate coupled with the IMS variables of temperature and drift gas flow rate. This evaluation resulted in six sets of experimental variables being required to separate the 32 VCs. The optimum experimental variables for SHS-MCC-GC-IMS, the retention time and drift time operating parameters were determined; to normalise the operating parameters, the relative drift time and normalised reduced ion mobility for each VC were determined. In addition, a full theoretical explanation is provided on the formation of the monomer, dimer and trimer of a VC. The optimum operating condition for each VC calibration data was obtained alongside limit of detection (LOD) and limit of quantitation (LOQ) values. Typical detection limits ranged from 0.1ng bis(methylthio)methane, ethylbutanoate and (E)-2-nonenal to 472ng isovaleric acid with correlation coefficient (R(2)) data ranging from 0.9793 (for the dimer of octanal) through to 0.9990 (for isobutyric acid). Finally, the developed protocols were applied to the analysis of malodour in sock samples. Initial work involved spiking an inert matrix and sock samples with appropriate concentrations of eight VCs. The average recovery from the inert matrix was 101±18% (n=8), while recoveries from the sock samples were lower, that is, 54±30% (n=8) for sock type 1 and 78±24% (n=6) for sock type 2. Finally, SHS-MCC-GC-IMS was applied to sock malodour in a field trial based on 11 volunteers (mixed gender) over a 3-week period. By applying the SHS-MCC-GC-IMS database, four VCs were

  2. Ion mobility-mass spectrometry of charge-reduced protein complexes reveals general trends in the collisional ejection of compact subunits.

    Science.gov (United States)

    Bornschein, Russell E; Ruotolo, Brandon T

    2015-10-21

    Multiprotein complexes have been shown to play critical roles across a wide range of cellular functions, but most probes of protein quaternary structure are limited in their ability to analyze complex mixtures and polydisperse structures using small amounts of total protein. Ion mobility-mass spectrometry offers a solution to many of these challenges, but relies upon gas-phase measurements of intact multiprotein complexes, subcomplexes, and subunits that correlate well with solution structures. The greatest bottleneck in such workflows is the generation of representative subcomplexes and subunits. Collisional activation of complexes can act to produce product ions reflective of protein complex composition, but such product ions are typically challenging to interpret in terms of their relationship to solution structure due to their typically string-like conformations following activation and subsequent dissociation. Here, we used ion-ion chemistry to perform a broad survey of the gas-phase dissociation of charge-reduced protein complex ions, revealing general trends associated with the collisional ejection of compact, rather than unfolded, protein subunits. Furthermore, we also discover peptide and co-factor dissociation channels that dominate the product ion populations generated for such charge reduced complexes. We assess both sets of observations and discuss general principles that can be extended to the analysis of protein complex ions having unknown structures.

  3. Ion mobility spectrometry as a simple and rapid method to measure the plasma propofol concentrations for intravenous anaesthesia monitoring

    Science.gov (United States)

    Wang, Xin; Zhou, Qinghua; Jiang, Dandan; Gong, Yulei; Li, Enyou; Li, Haiyang

    2016-11-01

    The plasma propofol concentration is important information for anaesthetists to monitor and adjust the anaesthesia depth for patients during a surgery operation. In this paper, a stand-alone ion mobility spectrometer (IMS) was constructed for the rapid measurement of the plasma propofol concentrations. Without any sample pre-treatment, the plasma samples were dropped on a piece of glass microfiber paper and then introduced into the IMS cell by the thermal desorption directly. Each individual measurement could be accomplished within 1 min. For the plasma propofol concentrations from 1 to 12 μg mL-1, the IMS response was linear with a correlation coefficient R2 of 0.998, while the limit of detection was evaluated to be 0.1 μg mL-1. These measurement results did meet the clinical application requirements. Furthermore, other clinically-often-used drugs, including remifentanil, flurbiprofen and atracurium, were found no significant interference with the qualitative and quantitative analysis of the plasma propofol. The plasma propofol concentrations measured by IMS were correlated well with those measured by the high performance liquid chromatography (HPLC). The results confirmed an excellent agreement between these two methods. Finally, this method was applied to monitor the plasma propofol concentrations for a patient undergoing surgery, demonstrating its capability of anaesthesia monitoring in real clinical environments.

  4. Determination of benzene, toluene and xylene concentration in humid air using differential ion mobility spectrometry and partial least squares regression.

    Science.gov (United States)

    Maziejuk, M; Szczurek, A; Maciejewska, M; Pietrucha, T; Szyposzyńska, M

    2016-05-15

    Benzene, toluene and xylene (BTX compounds) are chemicals of greatest concern due to their impact on humans and the environment. In many cases, quantitative information about each of these compounds is required. Continuous, fast-response analysis, performed on site would be desired for this purpose. Several methods have been developed to detect and quantify these compounds in this way. Methods vary considerably in sensitivity, accuracy, ease of use and cost-effectiveness. The aim of this work is to show that differential ion mobility spectrometry (DMS) may be applied for determining concentration of BTX compounds in humid air. We demonstrate, this goal is achievable by applying multivariate analysis of the measurement data using partial least squares (PLS) regression. The approach was tested at low concentrations of these compounds in the range of 5-20 ppm and for air humidity in a range 0-12 g/kg. These conditions correspond to the foreseeable application of the developed approach in occupational health and safety measurements. The average concentration assessment error was about 1 ppm for each: benzene, toluene and xylene. We also successfully determined water vapor content in air. The error achieved was 0.2 g/kg. The obtained results are very promising regarding further development of DMS technique as well as its application.

  5. Evaluation of ion mobility spectroscopy for determining charge-solvated versus salt-bridge structures of protonated trimers.

    Science.gov (United States)

    Wong, Richard L; Williams, Evan R; Counterman, Anne E; Clemmer, David E

    2005-07-01

    The cross sections of five different protonated trimers consisting of two base molecules and trifluoroacetic acid were measured by using ion mobility spectrometry. The gas-phase basicities of these five base molecules span an 8-kcal/mol range. These cross sections are compared with those determined from candidate low-energy salt-bridge and charge-solvated structures identified by using molecular mechanics calculations using three different force fields: AMBER*, MMFF, and CHARMm. With AMBER*, the charge-solvated structures are all globular and the salt-bridge structures are all linear, whereas with CHARMm, these two forms of the protonated trimers can adopt either shape. Globular structures have smaller cross sections than linear structures. Conclusions about the structure of these protonated trimers are highly dependent on the force field used to generate low-energy candidate structures. With AMBER*, all of the trimers are consistent with salt-bridge structures, whereas with MMFF the measured cross sections are more consistent with charge-solvated structures, although the assignments are ambiguous for two of the protonated trimers. Conclusions based on structures generated by using CHARMm suggest a change in structure from charge-solvated to salt-bridge structures with increasing gas-phase basicity of the constituent bases, a result that is most consistent with structural conclusions based on blackbody infrared radiative dissociation experiments for these protonated trimers and theoretical calculations on the uncharged base-acid pairs.

  6. Mobilization of Copper ions by Flavonoids in Human Peripheral Lymphocytes Leads to Oxidative DNA Breakage: A Structure Activity Study

    Directory of Open Access Journals (Sweden)

    Hussain Arif

    2015-11-01

    Full Text Available Epidemiological studies have linked dietary consumption of plant polyphenols with lower incidence of various cancers. In particular, flavonoids (present in onion, tomato and other plant sources induce apoptosis and cytotoxicity in cancer cells. These can therefore be used as lead compounds for the synthesis of novel anticancer drugs with greater bioavailability. In the present study, we examined the chemical basis of cytotoxicity of flavonoids by studying the structure–activity relationship of myricetin (MN, fisetin (FN, quercetin (QN, kaempferol (KL and galangin (GN. Using single cell alkaline gel electrophoresis (comet assay, we established the relative efficiency of cellular DNA breakage as MN > FN > QN > KL > GN. Also, we determined that the cellular DNA breakage was the result of mobilization of chromatin-bound copper ions and the generation of reactive oxygen species. The relative DNA binding affinity order was further confirmed using molecular docking and thermodynamic studies through the interaction of flavonoids with calf thymus DNA. Our results suggest that novel anti-cancer molecules should have ortho-dihydroxy groups in B-ring and hydroxyl groups at positions 3 and 5 in the A-ring system. Additional hydroxyl groups at other positions further enhance the cellular cytotoxicity of the flavonoids.

  7. Computational Methods for Metabolomic Data Analysis of Ion Mobility Spectrometry Data—Reviewing the State of the Art

    Directory of Open Access Journals (Sweden)

    Anne-Christin Hauschild

    2012-10-01

    Full Text Available Ion mobility spectrometry combined with multi-capillary columns (MCC/IMS is a well known technology for detecting volatile organic compounds (VOCs. We may utilize MCC/IMS for scanning human exhaled air, bacterial colonies or cell lines, for example. Thereby we gain information about the human health status or infection threats. We may further study the metabolic response of living cells to external perturbations. The instrument is comparably cheap, robust and easy to use in every day practice. However, the potential of the MCC/IMS methodology depends on the successful application of computational approaches for analyzing the huge amount of emerging data sets. Here, we will review the state of the art and highlight existing challenges. First, we address methods for raw data handling, data storage and visualization. Afterwards we will introduce de-noising, peak picking and other pre-processing approaches. We will discuss statistical methods for analyzing correlations between peaks and diseases or medical treatment. Finally, we study up-to-date machine learning techniques for identifying robust biomarker molecules that allow classifying patients into healthy and diseased groups. We conclude that MCC/IMS coupled with sophisticated computational methods has the potential to successfully address a broad range of biomedical questions. While we can solve most of the data pre-processing steps satisfactorily, some computational challenges with statistical learning and model validation remain.

  8. Computational methods for metabolomic data analysis of ion mobility spectrometry data-reviewing the state of the art.

    Science.gov (United States)

    Hauschild, Anne-Christin; Schneider, Till; Pauling, Josch; Rupp, Kathrin; Jang, Mi; Baumbach, Jörg Ingo; Baumbach, Jan

    2012-10-16

    Ion mobility spectrometry combined with multi-capillary columns (MCC/IMS) is a well known technology for detecting volatile organic compounds (VOCs). We may utilize MCC/IMS for scanning human exhaled air, bacterial colonies or cell lines, for example. Thereby we gain information about the human health status or infection threats. We may further study the metabolic response of living cells to external perturbations. The instrument is comparably cheap, robust and easy to use in every day practice. However, the potential of the MCC/IMS methodology depends on the successful application of computational approaches for analyzing the huge amount of emerging data sets. Here, we will review the state of the art and highlight existing challenges. First, we address methods for raw data handling, data storage and visualization. Afterwards we will introduce de-noising, peak picking and other pre-processing approaches. We will discuss statistical methods for analyzing correlations between peaks and diseases or medical treatment. Finally, we study up-to-date machine learning techniques for identifying robust biomarker molecules that allow classifying patients into healthy and diseased groups. We conclude that MCC/IMS coupled with sophisticated computational methods has the potential to successfully address a broad range of biomedical questions. While we can solve most of the data pre-processing steps satisfactorily, some computational challenges with statistical learning and model validation remain.

  9. Laser desorption-ion mobility spectrometry as a useful tool for imaging of thin layer chromatography surface.

    Science.gov (United States)

    Ilbeigi, Vahideh; Sabo, Martin; Valadbeigi, Younes; Matejcik, Stefan; Tabrizchi, Mahmoud

    2016-08-12

    We present a novel method for coupling thin layer chromatography (TLC) with ion mobility spectrometry (IMS) using laser desorption technique (LD). After separation of the compounds by TLC, the TLC surface was sampled by the LD-IMS without any further manipulation or preparation. The position of the laser was fixed and the TLC plate was moved in desired directions by the motorized micro-positioning stage. The method was successfully applied to analyze the TLC plates containing explosives (tri nitro toluene, 1,3,5-trinitro- 1,3,5-triazacyclohexane, pentaerythritol tetranitrate, 2,4-dinitro toluene and 3,4-dinitro toluene), amino acids (alanine, proline and isoleucine), nicotine and diphenylamine mixtures and detection limits for these compounds were determined. Combination of TLC with LD-IMS technique offers additional separation dimension, allowing separation of overlapping TLC analytes. The time for TLC sampling by LD-IMS was less than 80s. The scan rate for LD is adjustable so that fast and effective analysis of the mixtures is possible with the proposed method. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Detection of malignant pleural mesothelioma in exhaled breath by multicapillary column/ion mobility spectrometry (MCC/IMS).

    Science.gov (United States)

    Lamote, Kevin; Vynck, Matthijs; Van Cleemput, Joris; Thas, Olivier; Nackaerts, Kristiaan; van Meerbeeck, Jan P

    2016-09-26

    Malignant pleural mesothelioma (MPM) is predominantly caused by previous asbestos exposure. Diagnosis often happens in advanced stages restricting any therapeutic perspectives. Early stage detection via breath analysis was explored using multicapillary column/ion mobility spectrometry (MCC/IMS) to detect volatile organic compounds (VOCs) in the exhaled breath of MPM patients in comparison to former occupational asbestos-exposed and non-exposed controls. Breath and background samples of 23 MPM patients, 22 asymptomatic former asbestos (AEx) workers and 21 healthy non-asbestos exposed persons were taken for analysis. After background correction, we performed a logistic least absolute shrinkage and selection operator (lasso) regression to select the most important VOCs, followed by receiver operating characteristic (ROC) analysis. MPM patients were discriminated from both controls with 87% sensitivity, 70% specificity and respective positive and negative predictive values of 61% and 91%. The overall accuracy was 76% and the area under the ROC-curve was 0.81. AEx individuals could be discriminated from MPM patients with 87% sensitivity, 86% specificity and respective positive and negative predictive values of 87% and 86%. The overall accuracy was 87% with an area under the ROC-curve of 0.86. Breath analysis by MCC/IMS allows MPM patients to be discriminated from controls and holds promise for further investigation as a screening tool for former asbestos-exposed persons at risk of developing MPM.

  11. Data size reduction strategy for the classification of breath and air samples using multicapillary column-ion mobility spectrometry.

    Science.gov (United States)

    Szymańska, Ewa; Brodrick, Emma; Williams, Mark; Davies, Antony N; van Manen, Henk-Jan; Buydens, Lutgarde M C

    2015-01-20

    Ion mobility spectrometry combined with multicapillary column separation (MCC-IMS) is a well-known technology for detecting volatile organic compounds (VOCs) in gaseous samples. Due to their large data size, processing of MCC-IMS spectra is still the main bottleneck of data analysis, and there is an increasing need for data analysis strategies in which the size of MCC-IMS data is reduced to enable further analysis. In our study, the first untargeted chemometric strategy is developed and employed in the analysis of MCC-IMS spectra from 264 breath and ambient air samples. This strategy does not comprise identification of compounds as a primary step but includes several preprocessing steps and a discriminant analysis. Data size is significantly reduced in three steps. Wavelet transform, mask construction, and sparse-partial least squares-discriminant analysis (s-PLS-DA) allow data size reduction with down to 50 variables relevant to the goal of analysis. The influence and compatibility of the data reduction tools are studied by applying different settings of the developed strategy. Loss of information after preprocessing is evaluated, e.g., by comparing the performance of classification models for different classes of samples. Finally, the interpretability of the classification models is evaluated, and regions of spectra that are related to the identification of potential analytical biomarkers are successfully determined. This work will greatly enable the standardization of analytical procedures across different instrumentation types promoting the adoption of MCC-IMS technology in a wide range of diverse application fields.

  12. Ion Mobility-Mass Spectrometry as a Tool for the Structural Characterization of Peptides Bearing Intramolecular Disulfide Bond(s)

    Science.gov (United States)

    Massonnet, Philippe; Haler, Jean R. N.; Upert, Gregory; Degueldre, Michel; Morsa, Denis; Smargiasso, Nicolas; Mourier, Gilles; Gilles, Nicolas; Quinton, Loïc; De Pauw, Edwin

    2016-10-01

    Disulfide bonds are post-translationnal modifications that can be crucial for the stability and the biological activities of natural peptides. Considering the importance of these disulfide bond-containing peptides, the development of new techniques in order to characterize these modifications is of great interest. For this purpose, collision cross cections (CCS) of a large data set of 118 peptides (displaying various sequences) bearing zero, one, two, or three disulfide bond(s) have been measured in this study at different charge states using ion mobility-mass spectrometry. From an experimental point of view, CCS differences (ΔCCS) between peptides bearing various numbers of disulfide bonds and peptides having no disulfide bonds have been calculated. The ΔCCS calculations have also been applied to peptides bearing two disulfide bonds but different cysteine connectivities (Cys1-Cys2/Cys3-Cys4; Cys1-Cys3/Cys2-Cys4; Cys1-Cys4/Cys2-Cys3). The effect of the replacement of a proton by a potassium adduct on a peptidic structure has also been investigated.

  13. Continuous on-line determination of methyl tert-butyl ether in water samples using ion mobility spectrometry.

    Science.gov (United States)

    Borsdorf, H; Rämmler, A

    2005-04-22

    A rapid analytical procedure for the on-line determination of methyl tert-butyl ether (MTBE) in water samples was developed. A new membrane extraction unit was used to extract the MTBE from water samples. The concentration of MTBE was determined using ion mobility spectrometry with 63Ni ionization and corona discharge ionization without chromatographic separation. Both ionization methods permit the sensitive determination of MTBE. A detection limit of 100 microg/L was established for the on-line procedure. Neither the inorganic compounds, humic substances nor gasoline were found to exert a significant influence on the peak intensity of the MTBE. The screening procedure can be used for concentrations of monoaromatic compounds (benzene, toluene, xylene) up to 600 microg/L. No sample preparation is required and the analysis results are available within 5 min. In order to determine concentrations between 10 microg/L and 100 microg/L, a discontinuous procedure was developed on the basis of the same experimental set-up.

  14. Detection of Potato Storage Disease via Gas Analysis: A Pilot Study Using Field Asymmetric Ion Mobility Spectrometry

    Directory of Open Access Journals (Sweden)

    Massimo Rutolo

    2014-08-01

    Full Text Available Soft rot is a commonly occurring potato tuber disease that each year causes substantial losses to the food industry. Here, we explore the possibility of early detection of the disease via gas/vapor analysis, in a laboratory environment, using a recent technology known as FAIMS (Field Asymmetric Ion Mobility Spectrometry. In this work, tubers were inoculated with a bacterium causing the infection, Pectobacterium carotovorum, and stored within set environmental conditions in order to manage disease progression. They were compared with controls stored in the same conditions. Three different inoculation time courses were employed in order to obtain diseased potatoes showing clear signs of advanced infection (for standard detection and diseased potatoes with no apparent evidence of infection (for early detection. A total of 156 samples were processed by PCA (Principal Component Analysis and k-means clustering. Results show a clear discrimination between controls and diseased potatoes for all experiments with no difference among observations from standard and early detection. Further analysis was carried out by means of a statistical model based on LDA (Linear Discriminant Analysis that showed a high classification accuracy of 92.1% on the test set, obtained via a LOOCV (leave-one out cross-validation.

  15. Structure and dynamics of a protein-surfactant assembly studied by ion-mobility mass spectrometry and molecular dynamics simulations.

    Science.gov (United States)

    Borysik, Antoni J

    2015-09-01

    The structure and dynamics of a protein-surfactant assembly studied by ion-mobility mass spectrometry (IMS) and vacuum molecular dynamics (MD) simulations is reported. Direct evidence is provided for the ability of the surfactant dodecyl-β-D-maltoside (DDM) to prevent charge-induced unfolding of the membrane protein (PagP) in the gas-phase. Restraints obtained by IMS are used to map the surfactant positions onto the protein surface. Surfactants occupying more exposed positions at the apexes of the β-barrel structure are most in-line with the experimental observations. MD simulations provide additional evidence for this assembly organization through surfactant inversion and migration on the protein structure in the absence of solvent. Surfactant migration entails a net shift from apolar membrane spanning regions to more polar regions of the protein structure with the DDM molecule remaining attached to the protein via headgroup interactions. These data provide evidence for the role of protein-DDM headgroup interactions in stabilizing membrane protein structure from gas-phase unfolding.

  16. Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host-Guest Complexes Probed by Ion Mobility and Collision-Induced Dissociation.

    Science.gov (United States)

    Carroy, Glenn; Daxhelet, Charlotte; Lemaur, Vincent; De Winter, Julien; De Pauw, Edwin; Cornil, Jérôme; Gerbaux, Pascal

    2016-03-18

    Host-guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion-mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host-guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas-phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para-phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision-induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process.

  17. PIXiE: An Algorithm for Automated Ion Mobility Arrival Time Extraction and Collision Cross Section Calculation using Global Data Association

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Jian; Casey, Cameron P.; Zheng, Xueyun; Ibrahim, Yehia M.; Wilkins, Christopher S.; Renslow, Ryan S.; Thomas, Dennis G.; Payne, Samuel H.; Monroe, Matthew E.; Smith, Richard D.; Teeguarden, Justin G.; Baker, Erin M.; Metz, Thomas O.

    2017-05-15

    Motivation: Drift tube ion mobility spectrometry (DTIMS) is increasingly implemented in high throughput omics workflows, and new informatics approaches are necessary for processing the associated data. To automatically extract arrival times for molecules measured by DTIMS coupled with mass spectrometry and compute their associated collisional cross sections (CCS) we created the PNNL Ion Mobility Cross Section Extractor (PIXiE). The primary application presented for this algorithm is the extraction of information necessary to create a reference library containing accu-rate masses, DTIMS arrival times and CCSs for use in high throughput omics analyses. Results: We demonstrate the utility of this approach by automatically extracting arrival times and calculating the associated CCSs for a set of endogenous metabolites and xenobiotics. The PIXiE-generated CCS values were identical to those calculated by hand and within error of those calcu-lated using commercially available instrument vendor software.

  18. Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry.

    Science.gov (United States)

    Sun, Jianghao; Baker, Andrew; Chen, Pei

    2011-09-30

    An ultra-performance liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry (UPLC/IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine or ajmalicine core structure, plus methylated, oxidized and reduced species, were characterized. Common fragments and mass differences are described. It was shown that the use of IMS could provide another molecular descriptor, i.e. molecular shape by rotationally averaged collision cross-section; this is of great value for identification of constituents when reference materials are usually not available. Using the combination of high resolution (~40000) accurate mass measurement with time-aligned parallel (TAP) fragmentation, MS(E) (where E represents collision energy), ion mobility mass spectrometry (IMS) and UPLC chromatography, a total 55 indole alkaloids were characterized and a few new indole alkaloids are reported for the first time.

  19. Static headspace-multicapillary column with gas chromatography coupled to ion mobility spectrometry as a simple approach for the discrimination of crude and processed traditional Chinese medicines.

    Science.gov (United States)

    Cao, Gang; Shou, Qiyang; Li, Qinglin; Jiang, Jianping; Chen, Xiaocheng

    2014-11-01

    The processing procedure can alter the nature and chemical transformation of traditional Chinese medicine to accommodate different clinical dispensing and preparation requirements. In this study, static headspace-multicapillary column with gas chromatography coupled to ion mobility spectrometry was developed for the rapid and sensitive discrimination of crude and processed traditional Chinese medicine. Using Radix Paeoniae Alba as a traditional Chinese medicine model, the combined power of this approach was illustrated by classifying the crude and processed Radix Paeoniae Alba samples into two main categories. The contents of the main components in Radix Paeoniae Alba varied significantly. The established method could promote the use of ion mobility spectrometry in intrinsic quality control and differentiation of herbal medicines from other processed products or preparations.

  20. Fractal characteristics for binary noise radar waveform

    Science.gov (United States)

    Li, Bing C.

    2016-05-01

    Noise radars have many advantages over conventional radars and receive great attentions recently. The performance of a noise radar is determined by its waveforms. Investigating characteristics of noise radar waveforms has significant value for evaluating noise radar performance. In this paper, we use binomial distribution theory to analyze general characteristics of binary phase coded (BPC) noise waveforms. Focusing on aperiodic autocorrelation function, we demonstrate that the probability distributions of sidelobes for a BPC noise waveform depend on the distances of these sidelobes to the mainlobe. The closer a sidelobe to the mainlobe, the higher the probability for this sidelobe to be a maximum sidelobe. We also develop Monte Carlo framework to explore the characteristics that are difficult to investigate analytically. Through Monte Carlo experiments, we reveal the Fractal relationship between the code length and the maximum sidelobe value for BPC waveforms, and propose using fractal dimension to measure noise waveform performance.

  1. Distinguishing d - and l -aspartic and isoaspartic acids in amyloid β peptides with ultrahigh resolution ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun; Deng, Liulin; Baker, Erin M.; Ibrahim, Yehia M.; Petyuk, Vladislav A.; Smith, Richard D.

    2017-01-01

    Ion mobility spectrometry (IMS) was utilized to separate Aβ peptide variants containing isomeric asparic and isoaspartic acid residues with either al- ord-form. The abundance of each variant is of great interest in Alzheimer's disease studies and also to evaluate how often these modifications are occurring in other environmental and biological samples.

  2. Data Collection and Processing Instrumentation for Time-of-Flight Mass Spectrometry and Ion Mobility Time-of-Flight Mass Spectrometry

    Science.gov (United States)

    Sysoev, Alexey A.; Fomin, O. I.; Poteshin, S. S.; Chernyshev, D. M.; Karpov, A. V.; Sysoev, Alexander A.

    Data processing characteristics can significantly affect reliability of obtained results. Here we discuss two recently developed data collection instruments based on analog-to-digital converters. The first instrument is based on three 500 MHz 12 bit ADC and used for extended dynamic range measurements. Based on 667 MHz 8 bit ADC the second one allows fast 3D data acquisition. The instruments were used for time-of-flight mass spectrometry and ion mobility TOF mass spectrometry fast data acquisition and processing.

  3. Analysis of psilocybin and psilocin in Psilocybe subcubensis Guzmán by ion mobility spectrometry and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Keller, T; Schneider, A; Regenscheit, P; Dirnhofer, R; Rücker, T; Jaspers, J; Kisser, W

    1999-01-11

    A new method has been developed for the rapid analysis of psilocybin and/or psilocin in fungus material using ion mobility spectrometry. Quantitative analysis was performed by gas chromatography-mass spectrometry after a simple one-step extraction involving homogenization of the dried fruit bodies of fungi in chloroform and derivatization with MSTFA. The proposed methods resulted in rapid procedures useful in analyzing psychotropic fungi for psilocybin and psilocin.

  4. Localization of fatty acyl and double bond positions in phosphatidylcholines using a dual stage CID fragmentation coupled with ion mobility mass spectrometry.

    Science.gov (United States)

    Castro-Perez, Jose; Roddy, Thomas P; Nibbering, Nico M M; Shah, Vinit; McLaren, David G; Previs, Stephen; Attygalle, Athula B; Herath, Kithsiri; Chen, Zhu; Wang, Sheng-Ping; Mitnaul, Lyndon; Hubbard, Brian K; Vreeken, Rob J; Johns, Douglas G; Hankemeier, Thomas

    2011-09-01

    A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M + Li](+) was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C(15)H(31)CO(+), m/z 239) or 18:1 (9Z) (C(17)H(33)CO(+), m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H(2)C-HC = CH-CH = CH(2)). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of (13)C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC.

  5. Hooked differential mobility spectrometry apparatus and method therefore

    Science.gov (United States)

    Shvartsburg, Alexandre A [Richland, WA; Tang, Keqi [Richland, WA; Ibrahim, Yehia M [Richland, WA; Smith, Richard D [Richland, WA

    2009-02-17

    Disclosed are a device and method for improved interfacing of differential mobility spectrometry (DMS) or field asymmetric waveform ion mobility spectrometry (FAIMS) analyzers of substantially planar geometry to subsequent or preceding instrument stages. Interfacing is achieved using curved DMS elements, where a thick ion beam emitted by planar DMS analyzers or injected into them for ion filtering is compressed to the gap median by DMS ion focusing effect in a spatially inhomogeneous electric field. Resulting thinner beams are more effectively transmitted through necessarily constrained conductance limit apertures to subsequent instrument stages operated at a pressure lower than DMS, and/or more effectively injected into planar DMS analyzers. The technology is synergetic with slit apertures, slit aperture/ion funnels, and high-pressure ion funnel interfaces known in the art which allow for increasing cross-sectional area of MS inlets. The invention may be used in integrated analytical platforms, including, e.g., DMS/MS, LC/DMS/MS, and DMS/IMS/MS that could replace and/or enhance current LC/MS methods, e.g., for proteomics research.

  6. Mobilities Mobilities

    Directory of Open Access Journals (Sweden)

    César Pompeyo

    2011-12-01

    Full Text Available Urry, John (2007 Mobilities.Oxford: Polity Press.Urry, John (2007 Mobilities.Oxford: Polity Press.John Urry (1946-, profesor en la Universidad de Lancaster, es un sociólogo de sobra conocido y altamente reputado en el panorama internacional de las ciencias sociales. Su dilatada carrera, aparentemente dispersa y diversificada, ha seguido senderos bastante bien definidos dejando tras de sí un catálogo extenso de obras sociológicas de primer nivel. Sus primeros trabajos se centraban en el campo de la teoría social y la filosofía de las ciencias sociales o de la sociología del poder [...

  7. Visualization and analysis of lidar waveform data

    Science.gov (United States)

    Olsen, Richard C.; Metcalf, Jeremy P.

    2017-05-01

    LiDAR waveform analysis is a relatively new activity in the area of laser scanning. The work described here is an exploration of a different approach to visualization and analysis, following the structure that has evolved for the analysis of imaging spectroscopy data (hyperspectral imaging). The waveform data are transformed into 3-dimensional data structures that provide xy position information, and a z-coordinate, which is the digitized waveform. This allows for representation of the data in spatial and waveform space, the extraction of characteristic spectra, and the development of regions of interest. This representation allows for the application of standard spectral classification tools such as the maximum likelihood classifier.

  8. Seismic waveform modeling over cloud

    Science.gov (United States)

    Luo, Cong; Friederich, Wolfgang

    2016-04-01

    With the fast growing computational technologies, numerical simulation of seismic wave propagation achieved huge successes. Obtaining the synthetic waveforms through numerical simulation receives an increasing amount of attention from seismologists. However, computational seismology is a data-intensive research field, and the numerical packages usually come with a steep learning curve. Users are expected to master considerable amount of computer knowledge and data processing skills. Training users to use the numerical packages, correctly access and utilize the computational resources is a troubled task. In addition to that, accessing to HPC is also a common difficulty for many users. To solve these problems, a cloud based solution dedicated on shallow seismic waveform modeling has been developed with the state-of-the-art web technologies. It is a web platform integrating both software and hardware with multilayer architecture: a well designed SQL database serves as the data layer, HPC and dedicated pipeline for it is the business layer. Through this platform, users will no longer need to compile and manipulate various packages on the local machine within local network to perform a simulation. By providing users professional access to the computational code through its interfaces and delivering our computational resources to the users over cloud, users can customize the simulation at expert-level, submit and run the job through it.

  9. Rapid analysis of pesticide residues in drinking water samples by dispersive solid-phase extraction based on multiwalled carbon nanotubes and pulse glow discharge ion source ion mobility spectrometry.

    Science.gov (United States)

    Zou, Nan; Gu, Kejia; Liu, Shaowen; Hou, Yanbing; Zhang, Jialei; Xu, Xiang; Li, Xuesheng; Pan, Canping

    2016-03-01

    An analytical method based on dispersive solid-phase extraction with a multiwalled carbon nanotubes sorbent coupled with positive pulse glow discharge ion mobility spectrometry was developed for analysis of 30 pesticide residues in drinking water samples. Reduced ion mobilities and the mass-mobility correlation of 30 pesticides were measured. The pesticides were divided into five groups to verify the separation capability of pulse glow discharge in mobility spectrometry. The extraction conditions such as desorption solvent, ionic strength, conditions of adsorption and desorption, the amounts of multiwalled carbon nanotubes, and solution pH were optimized. The enrichment factors of pesticides were 5.4- to 48.7-fold (theoretical enrichment factor was 50-fold). The detection limits of pesticides were 0.01∼0.77 μg/kg. The linear range was 0.005-0.2 mg/L for pesticide standard solutions, with determination coefficients from 0.9616 to 0.9999. The method was applied for the analysis of practical and spiked drinking water samples. All results were confirmed by high-performance liquid chromatography with tandem mass spectrometry. The proposed method was proven to be a commendably rapid screening qualitative and semiquantitative technique for the analysis of pesticide residues in drinking water samples on site.

  10. Radar Sensor Networks: Algorithms for Waveform Design and Diversity with Application to ATR with Delay-Doppler Uncertainty

    Directory of Open Access Journals (Sweden)

    Qilian Liang

    2007-01-01

    Full Text Available Automatic target recognition (ATR in target search phase is very challenging because the target range and mobility are not yet perfectly known, which results in delay-Doppler uncertainty. In this paper, we firstly perform some theoretical studies on radar sensor network (RSN design based on linear frequency modulation (LFM waveform: (1 the conditions for waveform coexistence, (2 interferences among waveforms in RSN, (3 waveform diversity in RSN. Then we apply RSN to ATR with delay-Doppler uncertainty and propose maximum-likeihood (ML ATR algorithms for fluctuating targets and nonfluctuating targets. Simulation results show that our RSN vastly reduces the ATR error compared to a single radar system in ATR with delay-Doppler uncertainty. The proposed waveform design and diversity algorithms can also be applied to active RFID sensor networks and underwater acoustic sensor networks.

  11. Determination of Uric Acid in Human Urine by Ion-exclusion Chromatography with UV Detection Using Pure Water as Mobile Phase

    Institute of Scientific and Technical Information of China (English)

    侯升杰; 杨成对; 王辉; 田中一彦; 丁明玉

    2012-01-01

    A simple, rapid and accurate ion-exclusion chromatographic method coupled with a UV detector for the determination of uric acid in human urine samples has been developed. The separation was carried out on an ion-exclusion column using only pure water as mobile phase. The detection wavelength was 254 nm and urine sample was injected directly without any pretreatment. Furthermore, the retention behavior of uric acid on the ion-exclusion column was researched when pure water and 1 mmol·L-1 HCI were used as mobile phase, respectively. The stability of uric acid was also further investigated within 28 days, In this method, the linear range of the calibration curve for uric acid was 0.25--100 mg·L-1, and the detection limit calculated at S/N=3 was 0.02mg·L-1 The proposed ion-exclusion chromatographic method has been used for the determination of uric acid in human urine.

  12. Native mass spectrometry and ion mobility characterization of trastuzumab emtansine, a lysine-linked antibody drug conjugate

    Science.gov (United States)

    Marcoux, Julien; Champion, Thierry; Colas, Olivier; Wagner-Rousset, Elsa; Corvaïa, Nathalie; Van Dorsselaer, Alain; Beck, Alain; Cianférani, Sarah

    2015-01-01

    Antibody–drug conjugates (ADCs) are biochemotherapeutics consisting of a cytotoxic chemical drug linked covalently to a monoclonal antibody. Two main classes of ADCs, namely cysteine and lysine conjugates, are currently available on the market or involved in clinical trials. The complex structure and heterogeneity of ADCs makes their biophysical characterization challenging. For cysteine conjugates, hydrophobic interaction chromatography is the gold standard technique for studying drug distribution, the naked antibody content, and the average drug to antibody ratio (DAR). For lysine ADC conjugates on the other hand, which are not amenable to hydrophobic interaction chromatography because of their higher heterogeneity, denaturing mass spectrometry (MS) and UV/Vis spectroscopy are the most powerful approaches. We report here the use of native MS and ion mobility (IM-MS) for the characterization of trastuzumab emtansine (T-DM1, Kadcyla®). This lysine conjugate is currently being considered for the treatment of human epidermal growth factor receptor 2 (HER2)-positive breast cancer, and combines the anti-HER2 antibody trastuzumab (Herceptin®), with the cytotoxic microtubule-inhibiting maytansine derivative, DM1. We show that native MS combined with high-resolution measurements and/or charge reduction is beneficial in terms of the accurate values it provides of the average DAR and the drug load profiles. The use of spectral deconvolution is discussed in detail. We report furthermore the use of native IM-MS to directly determine DAR distribution profiles and average DAR values, as well as a molecular modeling investigation of positional isomers in T-DM1. PMID:25694334

  13. Trap states induced by reactive ion etching in AlGaN/GaN high-electron-mobility transistors

    Science.gov (United States)

    Luo, Jun; Zhao, Sheng-Lei; Mi, Min-Han; Hou, Bin; Yang, Xiao-Lei; Zhang, Jin-Cheng; Ma, Xiao-Hua; Hao, Yue

    2015-11-01

    Frequency-dependent conductance measurements were carried out to investigate the trap states induced by reactive ion etching in AlGaN/GaN high-electron-mobility transistors (HEMTs) quantitatively. For the non-recessed HEMT, the trap state density decreases from 2.48 × 1013 cm-2·eV-1 at an energy of 0.29 eV to 2.79 × 1012 cm-2·eV-1 at ET = 0.33 eV. In contrast, the trap state density of 2.38 × 1013-1.10 × 1014 cm-2·eV-1 is located at ET in a range of 0.30-0.33 eV for the recessed HEMT. Thus, lots of trap states with shallow energy levels are induced by the gate recess etching. The induced shallow trap states can be changed into deep trap states by 350 °C annealing process. As a result, there are two different types of trap sates, fast and slow, in the annealed HEMT. The parameters of the annealed HEMT are ET = 0.29-0.31 eV and DT = 8.16 × 1012-5.58 × 1013 cm-2·eV-1 for the fast trap states, and ET = 0.37-0.45 eV and DT = 1.84 × 1013 - 8.50 × 1013 cm-2·eV-1 for the slow trap states. The gate leakage currents are changed by the etching and following annealing process, and this change can be explained by the analysis of the trap states. Project supported by the National Natural Science Foundation of China (Grant Nos. 61334002 and 61106106).

  14. Trap states induced by reactive ion etching in AlGaN/GaN high-electron-mobility transistors

    Institute of Scientific and Technical Information of China (English)

    罗俊; 赵胜雷; 宓珉瀚; 侯斌; 杨晓蕾; 张进成; 马晓华; 郝跃

    2015-01-01

    Frequency-dependent conductance measurements were carried out to investigate the trap states induced by reactive ion etching in AlGaN/GaN high-electron-mobility transistors (HEMTs) quantitatively. For the non-recessed HEMT, the trap state density decreases from 2.48 × 1013 cm−2·eV−1 at an energy of 0.29 eV to 2.79 × 1012 cm−2·eV−1 at ET=0.33 eV. In contrast, the trap state density of 2.38 × 1013–1.10 × 1014 cm−2·eV−1 is located at ET in a range of 0.30–0.33 eV for the recessed HEMT. Thus, lots of trap states with shallow energy levels are induced by the gate recess etching. The induced shallow trap states can be changed into deep trap states by 350 ◦C annealing process. As a result, there are two different types of trap sates, fast and slow, in the annealed HEMT. The parameters of the annealed HEMT are ET=0.29–0.31 eV and DT=8.16 × 1012–5.58 × 1013 cm−2·eV−1 for the fast trap states, and ET=0.37–0.45 eV and DT=1.84 × 1013–8.50 × 1013 cm−2·eV−1 for the slow trap states. The gate leakage currents are changed by the etching and following annealing process, and this change can be explained by the analysis of the trap states.

  15. Goldstone Solar System Radar Waveform Generator

    Science.gov (United States)

    Quirk, Kevin J.; Patawaran, Ferze D.; Nguyen, Danh H.; Nguyen, Huy

    2012-01-01

    Due to distances and relative motions among the transmitter, target object, and receiver, the time-base between any transmitted and received signal will undergo distortion. Pre-distortion of the transmitted signal to compensate for this time-base distortion allows reception of an undistorted signal. In most radar applications, an arbitrary waveform generator (AWG) would be used to store the pre-calculated waveform and then play back this waveform during transmission. The Goldstone Solar System Radar (GSSR), however, has transmission durations that exceed the available memory storage of such a device. A waveform generator capable of real-time pre-distortion of a radar waveform to a given time-base distortion function is needed. To pre-distort the transmitted signal, both the baseband radar waveform and the RF carrier must be modified. In the GSSR, this occurs at the up-conversion mixing stage to an intermediate frequency (IF). A programmable oscillator (PO) is used to generate the IF along with a time-varying phase component that matches the time-base distortion of the RF carrier. This serves as the IF input to the waveform generator where it is mixed with a baseband radar waveform whose time-base has been distorted to match the given time-base distortion function producing the modulated IF output. An error control feedback loop is used to precisely control the time-base distortion of the baseband waveform, allowing its real-time generation. The waveform generator produces IF modulated radar waveforms whose time-base has been pre-distorted to match a given arbitrary function. The following waveforms are supported: continuous wave (CW), frequency hopped (FH), binary phase code (BPC), and linear frequency modulation (LFM). The waveform generator takes as input an IF with a time varying phase component that matches the time-base distortion of the carrier. The waveform generator supports interconnection with deep-space network (DSN) timing and frequency standards, and

  16. Differential mobility separation of leukotrienes and protectins.

    Science.gov (United States)

    Jónasdóttir, Hulda S; Papan, Cyrus; Fabritz, Sebastian; Balas, Laurence; Durand, Thierry; Hardardottir, Ingibjorg; Freysdottir, Jona; Giera, Martin

    2015-01-01

    Differential mobility spectrometry (DMS) is capable of separating stereoisomeric molecular ions based on their mobility in an oscillating electrical field with an asymmetric waveform. Thus, it is an "orthogonal" technique to chromatography and (tandem) mass spectrometry. Bioactive lipids, particularly of the eicosanoid and docosanoid class feature numerous stereoisomers, which exhibit a highly specific structure-activity relationship. Moreover, the geometry of these compounds also reflects their biochemical origin. Therefore, the unambiguous characterization of related isomers of the eicosanoid and docosanoid classes is of fundamental importance to the understanding of their origin and function in many biological processes. Here we show, that SelexION DMS technology coupled to μLC-MS/MS is capable of differentiating at least five closely related leukotrienes partially coeluting and (almost) unresolvable using LC-MS/MS only. We applied the developed method to the separation of LTB4 and its coeluting isomer 5S,12S-diHETE in murine peritoneal exudate cells, showing that LTB4 is present only after zymosan A injection while its isomer 5S,12S-diHETE is produced after saline (PBS) administration. Additionally, we show that the SelexION technology can also be applied to the separation of PD1 and PDX (10S,17S-diHDHA), two isomeric protectins.

  17. Highly selective and sensitive phosphate anion sensors based on AlGaN/GaN high electron mobility transistors functionalized by ion imprinted polymer.

    Science.gov (United States)

    Jia, Xiuling; Chen, Dunjun; Bin, Liu; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2016-06-09

    A novel ion-imprinted electrochemical sensor based on AlGaN/GaN high electron mobility transistors (HEMTs) was developed to detect trace amounts of phosphate anion. This sensor combined the advantages of the ion sensitivity of AlGaN/GaN HEMTs and specific recognition of ion imprinted polymers. The current response showed that the fabricated sensor is highly sensitive and selective to phosphate anions. The current change exhibited approximate linear dependence for phosphate concentration from 0.02 mg L(-1) to 2 mg L(-1), the sensitivity and detection limit of the sensor is 3.191 μA/mg L(-1) and 1.97 μg L(-1), respectively. The results indicated that this AlGaN/GaN HEMT-based electrochemical sensor has the potential applications on phosphate anion detection.

  18. Highly selective and sensitive phosphate anion sensors based on AlGaN/GaN high electron mobility transistors functionalized by ion imprinted polymer

    Science.gov (United States)

    Jia, Xiuling; Chen, Dunjun; Bin, Liu; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2016-06-01

    A novel ion-imprinted electrochemical sensor based on AlGaN/GaN high electron mobility transistors (HEMTs) was developed to detect trace amounts of phosphate anion. This sensor combined the advantages of the ion sensitivity of AlGaN/GaN HEMTs and specific recognition of ion imprinted polymers. The current response showed that the fabricated sensor is highly sensitive and selective to phosphate anions. The current change exhibited approximate linear dependence for phosphate concentration from 0.02 mg L-1 to 2 mg L-1, the sensitivity and detection limit of the sensor is 3.191 μA/mg L-1 and 1.97 μg L-1, respectively. The results indicated that this AlGaN/GaN HEMT-based electrochemical sensor has the potential applications on phosphate anion detection.

  19. Optical arbitrary waveform characterization using linear spectrograms.

    Science.gov (United States)

    Jiang, Zhi; Leaird, Daniel E; Long, Christopher M; Boppart, Stephen A; Weiner, Andrew M

    2010-08-01

    We demonstrate the first application of linear spectrogram methods based on electro-optic phase modulation to characterize optical arbitrary waveforms generated under spectral line-by-line control. This approach offers both superior sensitivity and self-referencing capability for retrieval of periodic high repetition rate optical arbitrary waveforms.

  20. Digital Waveform Generator Basedon FPGA

    Directory of Open Access Journals (Sweden)

    Shoucheng Ding

    2012-07-01

    Full Text Available Field Programmable Gate Array (FPGA of the Cyclone II series was as the core processor of frequency meter and the Quartus II was as the development plat form. This article had designed the fully digital signal generator. It use dall-digital frequency synthesizer technology and FPGA programming implemented the three waveforms: sin wave and square wave and triangle wave. The frequency was adjustable through10- bit phase accumulator and the analog multiplier achieved amplitude modulation. Using 51soft nuclear FPGA wrote a C program and realized the in put control word. The 4 × 4 matrix keyboard inputted frequency or amplitude value and the LCD1602displayedthem. The test results show that the system has high precision, distortion and low.

  1. Interpolation in waveform space: enhancing the accuracy of gravitational waveform families using numerical relativity

    CERN Document Server

    Cannon, Kipp; Hanna, Chad; Keppel, Drew; Pfeiffer, Harald

    2012-01-01

    Matched-filtering for the identification of compact object mergers in gravitational-wave antenna data involves the comparison of the data stream to a bank of template gravitational waveforms. Typically the template bank is constructed from phenomenological waveform models since these can be evaluated for an arbitrary choice of physical parameters. Recently it has been proposed that singular value decomposition (SVD) can be used to reduce the number of templates required for detection. As we show here, another benefit of SVD is its removal of biases from the phenomenological templates along with a corresponding improvement in their ability to represent waveform signals obtained from numerical relativity (NR) simulations. Using these ideas, we present a method that calibrates a reduced SVD basis of phenomenological waveforms against NR waveforms in order to construct a new waveform approximant with improved accuracy and faithfulness compared to the original phenomenological model. The new waveform family is giv...

  2. Classification of biodiesel and fuel blends using gas chromatography - differential mobility spectrometry with cluster analysis and isolation of C18:3 me by dual ion filtering.

    Science.gov (United States)

    Pasupuleti, Dedeepya; Eiceman, Gary A; Pierce, Karisa M

    2016-08-01

    Fatty acid alkyl esters (FAAEs) were determined at 10-100mg/L in biodiesel and blends with petrodiesel without sample pre-treatment using gas chromatography with a tandem differential mobility detector. Selectivity was provided through chromatographic separations and atmospheric pressure chemical ionization reactions in the detector with mobility characterization of gas ions. Limits of detection were ~0.5ng with an average of 2.98% RSD for peak area precision, ≤1.3% RSD for retention time precision, and ≤9.2% RSD for compensation voltage precision. Biodiesel blends were classified using principal component analysis (PCA) and hierarchical cluster analysis (HCA). Unsupervised cluster analysis captured 52.72% of variance in a single PC while supervised analysis captured 71.64% of variance using Fisher ratio feature selection. Test set predictions showed successful clustering according to source or feedstock when regressed onto the training set model. Detection of the regulated substance methyl linolenate (C18:3 me) was achieved in 6-10s with a 1m long capillary column using dual ion filtering in the tandem differential mobility detector. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

    Science.gov (United States)

    Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

    2012-04-13

    Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs.

  4. Implementation of Pulse Radar Waveform Based on Software Radio Platform

    OpenAIRE

    Wang Dong; Dong Jian; Xiao Shunping

    2015-01-01

    Based on the frequency and phase modulated signal, the authors design some commonly-used pulse radar baseband waveform, such as linear frequency modulated waveform, nonlinear frequency modulated waveform, Costas waveform, Barker coding waveform and multi-phase coded waveform, and the authors compare their performance, such as the peak side lobe ratio, the Rayleigh resolution in time and distance resolution. Then, based on the software radio platform NI PXIe-5644R, the authors design the timin...

  5. Detection of aqueous phase chemical warfare agent degradation products by negative mode ion mobility time-of-flight mass spectrometry [IM(tof)MS].

    Science.gov (United States)

    Steiner, Wes E; Harden, Charles S; Hong, Feng; Klopsch, Steve J; Hill, Herbert H; McHugh, Vincent M

    2006-02-01

    The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K(o) values, and signal intensities for each of the CWA degradation products are reported.

  6. Bonding, ion mobility, and rate-limiting steps in deintercalation reactions with ThCr2Si2-type KNi2Se2.

    Science.gov (United States)

    Neilson, James R; McQueen, Tyrel M

    2012-05-09

    Here, we study the nature of metal-metal bonding in the ThCr(2)Si(2) structure type by probing the rate-limiting steps in the oxidative deintercalation of KNi(2)Se(2). For low extents of oxidation, alkali ions are removed exclusively to form K(1-x)Ni(2)Se(2). For greater extents of oxidation, the rate of the reaction decreases dramatically, concomitant with the extraction of both potassium and nickel to form K(1-x)Ni(2-y)Se(2). The appreciable mobility of transition metal ions is unexpected, but illustrates the relative energy scales of different defects in the ThCr(2)Si(2) structure type. Furthermore, the fully oxidized compounds, K(0.25)Ni(1.5)Se(2), spontaneously convert from the tetrahedral [NiSe(4)]-containing ThCr(2)Si(2) structure to a vacancy-ordered NiAs structure with [NiSe(6)] octahedra. From analysis of the atom positions and kinetic data, we have determined that this transformation occurs by a continuous, low-energy pathway via subtle displacements of Ni atoms and buckling of the Se sublattice. These results have profound implications for our understanding of the stability, mobility, and reactivity of ions in materials.

  7. Conformational ordering of biomolecules in the gas phase: nitrogen collision cross sections measured on a prototype high resolution drift tube ion mobility-mass spectrometer.

    Science.gov (United States)

    May, Jody C; Goodwin, Cody R; Lareau, Nichole M; Leaptrot, Katrina L; Morris, Caleb B; Kurulugama, Ruwan T; Mordehai, Alex; Klein, Christian; Barry, William; Darland, Ed; Overney, Gregor; Imatani, Kenneth; Stafford, George C; Fjeldsted, John C; McLean, John A

    2014-02-18

    Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid "omni-omic" characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field.

  8. How useful is ion mobility mass spectrometry for structural biology? The relationship between protein crystal structures and their collision cross sections in the gas phase.

    Science.gov (United States)

    Jurneczko, Ewa; Barran, Perdita E

    2011-01-07

    The technique of ion mobility mass spectrometry (IM-MS) has become of increasing interest for rapid analysis of the conformations adopted by biological macromolecules. It is currently used routinely for analysis of explosives and illegal substances in airport and military security. In biophysical research, it can be used to determine the temperature dependent rotationally averaged collision cross section of gas-phase ions of proteins and nucleic acids along with their mass to charge ratios. Nanoelectrospray ionisation allows the gentle transfer of intact biomolecules from solutions in which the native form(s) are present, into the solvent free environment of a mass spectrometer. It is believed by many researchers that the experimental collision cross sections of these molecules should have some relationship to crystal structure coordinates. In this review we outline the different experimental methods that can be used to measure ion mobility; we also describe methods used to calculate collision cross sections from input coordinates. Following this survey of the methodological approaches to IM-MS, we then summarise IM-MS data published to date for some monomeric peptides and small soluble proteins, along with collision cross sections calculated from their crystal structure coordinates. Finally we consider the relationship between experimental gas-phase conformations and those adopted in crystals and give an outlook on the application of IM-MS as a tool for structural biology.

  9. Dopant-assisted negative photoionization Ion mobility spectrometry coupled with on-line cooling inlet for real-time monitoring H2S concentration in sewer gas.

    Science.gov (United States)

    Peng, Liying; Jiang, Dandan; Wang, Zhenxin; Hua, Lei; Li, Haiyang

    2016-06-01

    Malodorous hydrogen sulfide (H2S) gas often exists in the sewer system and associates with the problems of releasing the dangerous odor to the atmosphere and causing sewer pipe to be corroded. A simple method is in demand for real-time measuring H2S level in the sewer gas. In this paper, an innovated method based on dopant-assisted negative photoionization ion mobility spectrometry (DANP-IMS) with on-line semiconductor cooling inlet was put forward and successfully applied for the real-time measurement of H2S in sewer gas. The influence of moisture was effectively reduced via an on-line cooling method and a non-equilibrium dilution with drift gas. The limits of quantitation for the H2S in ≥60% relative humidity air could be obtained at ≤79.0ng L(-1) with linear ranges of 129-2064ng L(-1). The H2S concentration in a sewer manhole was successfully determined while its product ions were identified by an ion-mobility time-of-fight mass spectrometry. Finally, the correlation between sewer H2S concentration and the daily routines and habits of residents was investigated through hourly or real-time monitoring the variation of sewer H2S in manholes, indicating the power of this DANP-IMS method in assessing the H2S concentration in sewer system. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Collision cross section prediction of deprotonated phenolics in a travelling-wave ion mobility spectrometer using molecular descriptors and chemometrics

    Energy Technology Data Exchange (ETDEWEB)

    Gonzales, Gerard Bryan, E-mail: gerard.gonzales@ugent.be [Food Chemistry and Human Nutrition (NutriFOODChem), Department of Food Safety and Food Quality, Faculty of Bioscience Engineering, Ghent University (Belgium); Laboratory of Agrozoology, Department of Crop Protection, Faculty of Bioscience Engineering, Ghent University (Belgium); Department of Applied Biological Science, Faculty of Bioscience Engineering, Ghent University (Belgium); Smagghe, Guy [Laboratory of Agrozoology, Department of Crop Protection, Faculty of Bioscience Engineering, Ghent University (Belgium); Coelus, Sofie; Adriaenssens, Dieter [Food Chemistry and Human Nutrition (NutriFOODChem), Department of Food Safety and Food Quality, Faculty of Bioscience Engineering, Ghent University (Belgium); De Winter, Karel; Desmet, Tom [Center for Industrial Biotechnology and Biocatalysis, Faculty of Bioscience Engineering, Ghent University (Belgium); Raes, Katleen [Department of Applied Biological Science, Faculty of Bioscience Engineering, Ghent University (Belgium); Van Camp, John, E-mail: john.vancamp@ugent.be [Food Chemistry and Human Nutrition (NutriFOODChem), Department of Food Safety and Food Quality, Faculty of Bioscience Engineering, Ghent University (Belgium)

    2016-06-14

    The combination of ion mobility and mass spectrometry (MS) affords significant improvements over conventional MS/MS, especially in the characterization of isomeric metabolites due to the differences in their collision cross sections (CCS). Experimentally obtained CCS values are typically matched with theoretical CCS values from Trajectory Method (TM) and/or Projection Approximation (PA) calculations. In this paper, predictive models for CCS of deprotonated phenolics were developed using molecular descriptors and chemometric tools, stepwise multiple linear regression (SMLR), principal components regression (PCR), and partial least squares regression (PLS). A total of 102 molecular descriptors were generated and reduced to 28 after employing a feature selection tool, composed of mass, topological descriptors, Jurs descriptors and shadow indices. Therefore, the generated models considered the effects of mass, 3D conformation and partial charge distribution on CCS, which are the main parameters for either TM or PA (only 3D conformation) calculations. All three techniques yielded highly predictive models for both the training (R{sup 2}{sub SMLR} = 0.9911; R{sup 2}{sub PCR} = 0.9917; R{sup 2}{sub PLS} = 0.9918) and validation datasets (R{sup 2}{sub SMLR} = 0.9489; R{sup 2}{sub PCR} = 0.9761; R{sup 2}{sub PLS} = 0.9760). Also, the high cross validated R{sup 2} values indicate that the generated models are robust and highly predictive (Q{sup 2}{sub SMLR} = 0.9859; Q{sup 2}{sub PCR} = 0.9748; Q{sup 2}{sub PLS} = 0.9760). The predictions were also very comparable to the results from TM calculations using modified mobcal (N2). Most importantly, this method offered a rapid (<10 min) alternative to TM calculations without compromising predictive ability. These methods could therefore be used in routine analysis and could be easily integrated to metabolite identification platforms. - Highlights: • CCS for deprotonated phenolics were measured using TWIMS.

  11. Comprehensive analysis of fatty alcohol ethoxylates by ultra high pressure hydrophilic interaction chromatography coupled with ion mobility spectrometry mass spectrometry using a custom-designed sub-2 μm column.

    Science.gov (United States)

    Ma, Qiang; Ma, Wei; Chen, Xi; Wang, Ziming; Bai, Hua; Zhang, Lanwei; Li, Wentao; Wang, Chao; Li, Xinshi

    2015-06-01

    Comprehensive analysis of fatty alcohol ethoxylates has been conducted by coupling ultra high pressure hydrophilic interaction chromatography and ion mobility spectrometry mass spectrometry. A custom-designed sub-2 μm column was used for the chromatographic separation of fatty alcohol ethoxylates by hydrophilic interaction chromatography. Ion mobility spectrometry provided a post-ionization resolution during a very short period of 6.4 ms. Distinguishable families of singly, doubly, and triply charged fatty alcohol ethoxylates were clearly observed. By virtue of the combination of hydrophilic interaction chromatography and ion mobility spectrometry, comprehensive resolution based on both hydrophobicity difference and mobility disparity has been achieved for fatty alcohol ethoxylates. The orthogonality of the developed separation and analysis system was evaluated with the correlation coefficient and peak spreading angle of 0.0224 and 88.72°, respectively. The actual peak capacity obtained was individually 40 and 193 times than those when hydrophilic interaction chromatography and ion mobility spectrometry were used alone. The collision cross-sections of fatty alcohol ethoxylates were calculated by calibrating the traveling wave ion mobility device with polyalanine.

  12. Improved retracking algorithm for oceanic altimeter waveforms

    Institute of Scientific and Technical Information of China (English)

    Lifeng Bao; Yang Lu; Yong Wang

    2009-01-01

    Over the deep oceans without land/ice interference, the waveforms created by the return altimeter pulse generally follow the ocean model of Brown, and the corresponding range can be properly determined using the result from an onboard tracker. In the case of com-plex altimeter waveforms corrupted due to a variety of reasons, the processor on the satellite cannot properly determine the center of the leading edge, and range observations can be in error. As an efficacious method to improve the precision of those altimeter observations with complex waveforms, waveform retracking is required to reprocess the original returning pulse. Based on basic altimeter theory and the geometric feature of altimeter waveforms, we developed a new altimeter waveform retracker, which is valid for all altimeter wave-forms once there exists a reasonable returning signal. The performances of the existing Beta-5 retracker, threshold retracker, improved threshold retracker, and the new retracker are assessed in the experimental regions (China Seas and its adjacent regions), and the improvements in the accuracy of sea surface height are investigated by the difference between retracked altimeter observations and ref-erenced geoid. The comparisons denote that the new algorithm gives the best performance in both the open ocean and coastal regions. Also, the new retracker presents a uniform performance in the whole test region. Besides, there is a significant improvement in the short-wavelength precision and the spatial resolution of sea surface height after retracking process.

  13. Microwave dynamic large signal waveform characterization of advanced InGaP HBT for power amplifiers

    Institute of Scientific and Technical Information of China (English)

    Zhao Lixin; Jin Zhi; Liu Xinyu

    2009-01-01

    In wireless mobile communications and wireless local area networks (WLAN), advanced lnGaP HBT with power amplifiers are key components. In this paper, the microwave large signal dynamic waveform characteristics of an advanced InGaP HBT are investigated experimentally for 5.8 GHz power amplifier applications. The microwave large signal waveform distortions at various input power levels, especially at large signal level, are investigated and the reasons are analyzed. The output power saturation is also explained. These analyses will be useful for power amplifier designs.

  14. Waveform Fingerprinting for Efficient Seismic Signal Detection

    Science.gov (United States)

    Yoon, C. E.; OReilly, O. J.; Beroza, G. C.

    2013-12-01

    Cross-correlating an earthquake waveform template with continuous waveform data has proven a powerful approach for detecting events missing from earthquake catalogs. If templates do not exist, it is possible to divide the waveform data into short overlapping time windows, then identify window pairs with similar waveforms. Applying these approaches to earthquake monitoring in seismic networks has tremendous potential to improve the completeness of earthquake catalogs, but because effort scales quadratically with time, it rapidly becomes computationally infeasible. We develop a fingerprinting technique to identify similar waveforms, using only a few compact features of the original data. The concept is similar to human fingerprints, which utilize key diagnostic features to identify people uniquely. Analogous audio-fingerprinting approaches have accurately and efficiently found similar audio clips within large databases; example applications include identifying songs and finding copyrighted content within YouTube videos. In order to fingerprint waveforms, we compute a spectrogram of the time series, and segment it into multiple overlapping windows (spectral images). For each spectral image, we apply a wavelet transform, and retain only the sign of the maximum magnitude wavelet coefficients. This procedure retains just the large-scale structure of the data, providing both robustness to noise and significant dimensionality reduction. Each fingerprint is a high-dimensional, sparse, binary data object that can be stored in a database without significant storage costs. Similar fingerprints within the database are efficiently searched using locality-sensitive hashing. We test this technique on waveform data from the Northern California Seismic Network that contains events not detected in the catalog. We show that this algorithm successfully identifies similar waveforms and detects uncataloged low magnitude events in addition to cataloged events, while running to completion

  15. Study on atomic layer etching of Si in inductively coupled Ar/Cl2 plasmas driven by tailored bias waveforms

    Science.gov (United States)

    Ma, Xiaoqin; Zhang, Saiqian; Dai, Zhongling; Wang, Younian

    2017-08-01

    Plasma atomic layer etching is proposed to attain layer-by-layer etching, as it has atomic-scale resolution, and can etch monolayer materials. In the etching process, ion energy and angular distributions (IEADs) bombarding the wafer placed on the substrate play a critical role in trench profile evolution, thus importantly flexibly controlling IEADs in the process. Tailored bias voltage waveform is an advisable method to modulate the IEADs effectively, and then improve the trench profile. In this paper, a multi-scale model, coupling the reaction chamber model, sheath model, and trench model, is used to research the effects of bias waveforms on the atomic layer etching of Si in Ar/Cl2 inductively coupled plasmas. Results show that different discharge parameters, such as pressure and radio-frequency power influence the trench evolution progress with bias waveforms synergistically. Tailored bias waveforms can provide nearly monoenergetic ions, thereby obtaining more anisotropic trench profile.

  16. Unambiguous range-Doppler LADAR processing using 2 giga-sample-per-second noise waveforms

    Energy Technology Data Exchange (ETDEWEB)

    Cole, Z. [S2 Corporation, 2310 University Way 4-1, Bozeman, MT 59715 (United States)]. E-mail: cole@s2corporation.com; Roos, P.A. [Spectrum Lab, Montana State University, P.O. Box 173510, Bozeman, MT 59717 (United States); Berg, T. [S2 Corporation, 2310 University Way 4-1, Bozeman, MT 59715 (United States); Kaylor, B. [S2 Corporation, 2310 University Way 4-1, Bozeman, MT 59715 (United States); Merkel, K.D. [S2 Corporation, 2310 University Way 4-1, Bozeman, MT 59715 (United States); Babbitt, W.R. [Spectrum Lab, Montana State University, P.O. Box 173510, Bozeman, MT 59717 (United States); Reibel, R.R. [S2 Corporation, 2310 University Way 4-1, Bozeman, MT 59715 (United States)

    2007-11-15

    We demonstrate sub-nanosecond range and unambiguous sub-50-Hz Doppler resolved laser radar (LADAR) measurements using spectral holographic processing in rare-earth ion doped crystals. The demonstration utilizes pseudo-random-noise 2 giga-sample-per-second baseband waveforms modulated onto an optical carrier.

  17. Parallel Algorithm in Surface Wave Waveform Inversion

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In Surface wave waveform inversion, we want to reconstruct 3Dshear wav e velocity structure, which calculation beyond the capability of the powerful pr esent day personal computer or even workstation. So we designed a high parallele d algorithm and carried out the inversion on Parallel computer based on the part itioned waveform inversion (PWI). It partitions the large scale optimization pro blem into a number of independent small scale problems and reduces the computati onal effort by several orders of magnitude. We adopted surface waveform inversio n with a equal block(2°×2°) discretization.

  18. Periodic, pseudonoise waveforms for multifunction coherent ladar.

    Science.gov (United States)

    Dierking, Matthew P; Duncan, Bradley D

    2010-04-01

    We report the use of periodic, pseudonoise waveforms in a multifunction coherent ladar system. We exploit the Doppler sensitivity of these waveforms, as well as agile processing, to enable diverse ladar functions, including high range resolution imaging, macro-Doppler imaging, synthetic aperture ladar, and range-resolved micro-Doppler imaging. We present analytic expressions and simulations demonstrating the utility of pseudonoise waveforms for each of the ladar modes. We also discuss a laboratory pseudonoise ladar system that was developed to demonstrate range compression and range-resolved micro-Doppler imaging, as well as the phase recovery common to each of the coherent modes.

  19. Optimal pseudorandom pulse position modulation ladar waveforms.

    Science.gov (United States)

    Fluckiger, David U; Boland, Brian F; Marcus, Eran

    2015-03-20

    An algorithm for generating optimal pseudorandom pulse position modulation (PRPPM) waveforms for ladar ranging is presented. Bistatic ladar systems using Geiger-mode avalanche photodiodes require detection of several pulses in order to generate sufficient target statistics to satisfy some detection decision rule. For targets with large initial range uncertainty, it becomes convenient to transmit a pulse train with large ambiguity range. One solution is to employ a PRPPM waveform. An optimal PRPPM waveform will have minimal sidelobes: equivalent to 1 or 0 counts after the pulse correlation filter (compression). This can be accomplished by generating PRPPM pulse trains with optimal or minimal sidelobe autocorrelation.

  20. Dynamics of lithium ions in borotellurite mixed former glasses: Correlation between the characteristic length scales of mobile ions and glass network structural units

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, A.; Ghosh, A., E-mail: sspag@iacs.res.in [Department of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2014-10-28

    We have studied the mixed network former effect on the dynamics of lithium ions in borotellurite glasses in wide composition and temperature ranges. The length scales of ion dynamics, such as characteristic mean square displacement and spatial extent of sub-diffusive motion of lithium ions have been determined from the ac conductivity and dielectric spectra, respectively, in the framework of linear response theory. The relative concentrations of different network structural units have been determined from the deconvolution of the FTIR spectra. A direct correlation between the ion dynamics and the characteristic length scales and the relative concentration of BO{sub 4} units has been established for different compositions of the borotellurite glasses.

  1. Control of the RF waveform at the chuck of an industrial oxide-etch reactor

    Energy Technology Data Exchange (ETDEWEB)

    BERRY,LEE; MAYNARD,HELEN; MILLER,PAUL A.; MOORE,TONY; PENDLEY,MICHAEL; RESTA,VICTORIA; SPARKS,DENNIS; YANG,QUINGYUN

    2000-05-04

    Radio frequency (rf) power is applied to the chuck of a high-density plasma reactor in order to extract ions and to control the energy of the ions used for the fabrication of microelectronic devices. In many cases, the temporal shape of the rf waveform largely determines the shape of the spectrum of those extracted ions, thereby strongly affecting feature evolution. Using auxiliary rf circuits the authors successfully made major changes to the rf potential waveform at the chuck of an Applied Materials 5300 HDP Omega reactor without affecting the normal functioning of the reactor's control systems. This work established the practical feasibility of techniques for modifying the ion energy distribution functions of industrial reactors.

  2. Integrating ion mobility spectrometry into mass spectrometry-based exposome measurements: what can it add and how far can it go?

    Energy Technology Data Exchange (ETDEWEB)

    Metz, Thomas O.; Baker, Erin M.; Schymanski, Emma L.; Renslow, Ryan S.; Thomas, Dennis G.; Causon, Tim J.; Webb, Ian K.; Hann, Stephan; Smith, Richard D.; Teeguarden, Justin G.

    2017-01-01

    Measuring the exposome remains a challenge due to the range and number of anthropogenic molecules that are encountered in our daily lives, as well as the complex systemic responses to these exposures. One option for improving the coverage, dynamic range and throughput of measurements is to incorporate ion mobility spectrometry (IMS) into current mass spectrometry (MS)-based analytical methods. In this perspective, we briefly review the state-of-the-art in measuring the exposome, and discuss the potential use for IMS-MS and the physico-chemical property of collisional cross section in both exposure assessment and molecular identification.

  3. Silicon/Carbon Nanotube/BaTiO₃ Nanocomposite Anode: Evidence for Enhanced Lithium-Ion Mobility Induced by the Local Piezoelectric Potential.

    Science.gov (United States)

    Lee, Byoung-Sun; Yoon, Jihyun; Jung, Changhoon; Kim, Dong Young; Jeon, Seung-Yeol; Kim, Ki-Hong; Park, Jun-Ho; Park, Hosang; Lee, Kang Hee; Kang, Yoon-Sok; Park, Jin-Hwan; Jung, Heechul; Yu, Woong-Ryeol; Doo, Seok-Gwang

    2016-02-23

    We report on the synergetic effects of silicon (Si) and BaTiO3 (BTO) for applications as the anode of Li-ion batteries. The large expansion of Si during lithiation was exploited as an energy source via piezoelectric BTO nanoparticles. Si and BTO nanoparticles were dispersed in a matrix consisting of multiwalled carbon nanotubes (CNTs) using a high-energy ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the BTO, which can be poled, so that a piezoelectric potential is generated. We found that this local piezoelectric potential can improve the electrochemical performance of the Si/CNT/BTO nanocomposite anodes. Experimental measurements and simulation results support the increased mobility of Li-ions due to the local piezoelectric potential.

  4. Comparison of Cocaine Detections in Corona Discharge Ionization-Ion Mobility Spectrometry and in Atmospheric Pressure Chemical Ionization-Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Sung Seen; Kim, Yun Ki; Kim, Ok Bae [Sejong University, Seoul (Korea, Republic of); An, Seung Geon; Shin, Myung Won; Maeng, Seug Jin; Choi, Gyu Seop [Wooju Communication and Technology Co., Seoul (Korea, Republic of)

    2010-08-15

    In this study, we determined the detection limit and reproducibility of the new IMS equipped with corona discharge ionization source using cocaine. The sample was injected with liquid solution to compare the results of APCI-MS. Ion mobility spectrometry (IMS) was a technique originally applied for the detection of trace compounds. IMS has been widely used to detect chemical warfare agents, explosives, and illegal drugs since it combines both high sensitivity (detection limits down to the ng/L range to pg/L range, ppb range and ppt range) and relatively low technical expenditure with high-speed data acquisition. The time required to acquire a single spectrum is in the range of several tens ms. The working principle is based on the drift of ions at ambient pressure under the influence of an external electric field.

  5. Electron Attachment Studies for CHCl3 Using Ion Mobility Spectrometry%CHCl3电子吸附速率常数的离子迁移谱

    Institute of Scientific and Technical Information of China (English)

    韩海燕; 冯鸿涛; 李虎; 王鸿梅; 江海河; 储焰南

    2011-01-01

    The dissociative electron attachment process for CHCl3 at different electric field have been studied with nitrogen as drift and carrier gas using corona discharge ionization source ion mobility spectrometry (CD-IMS). The corresponding electron attachment rate constants varied from 1.26×10-8 cm3/(molecules s) to 8.24×10-9 cm3/(molecules s) as the electric field changed from 200 V/cra to 500 V/cm. At a fixed electric field in the drift region,the attachment rate constants are also detected at different sample concentration. The ionmolecule reaction rate constants for the further reaction between C1- and CHC13 are also detected, which indicates that the technique maybe becomes a new method to research the rate constants between ions and neural molecules. And the reaction rate constants between C1- and CHCl3 are the first time detected using CD-IMS.

  6. Effects of drift gas on collision cross sections of a protein standard in linear drift tube and traveling wave ion mobility mass spectrometry.

    Science.gov (United States)

    Jurneczko, Ewa; Kalapothakis, Jason; Campuzano, Iain D G; Morris, Michael; Barran, Perdita E

    2012-10-16

    There has been a significant increase in the use of ion mobility mass spectrometry (IM-MS) to investigate conformations of proteins and protein complexes following electrospray ionization. Investigations which employ traveling wave ion mobility mass spectrometry (TW IM-MS) instrumentation rely on the use of calibrants to convert the arrival times of ions to collision cross sections (CCS) providing "hard numbers" of use to structural biology. It is common to use nitrogen as the buffer gas in TW IM-MS instruments and to calibrate by extrapolating from CCS measured in helium via drift tube (DT) IM-MS. In this work, both DT and TW IM-MS instruments are used to investigate the effects of different drift gases (helium, neon, nitrogen, and argon) on the transport of multiply charged ions of the protein myoglobin, frequently used as a standard in TW IM-MS studies. Irrespective of the drift gas used, recorded mass spectra are found to be highly similar. In contrast, the recorded arrival time distributions and the derived CCS differ greatly. At low charge states (7 ≤ z ≤ 11) where the protein is compact, the CCS scale with the polarizability of the gas; this is also the case for higher charge states (12 ≤ z ≤ 22) where the protein is more unfolded for the heavy gases (neon, argon, and nitrogen) but not the case for helium. This is here interpreted as a different conformational landscape being sampled by the lighter gas and potentially attributable to increased field heating by helium. Under nanoelectrospray ionization (nESI) conditions, where myoglobin is sprayed from an aqueous solution buffered to pH 6.8 with 20 mM ammonium acetate, in the DT IM-MS instrument, each buffer gas can yield a different arrival time distribution (ATD) for any given charge state.

  7. Selection of Carrier Waveforms for PWM Inverter

    Institute of Scientific and Technical Information of China (English)

    陈国呈; 屈克庆; 许春雨; 孙承波

    2003-01-01

    In this paper the influence of different carrier waveforms upon the output characteristics of PWM inverter is described in detail. When a triangular carrier waveform is used in hard-switching PWM inverters, harmonics exist in the neighborhood of the output frequency of the inverter output voltage and current due to the dead time. The triangular carrier waveform used in soft-switching PWM inverter will cause difficulties in controlling resonance-trigger time, higher loss in the resonant circuit, and less utilization of the DC bus voltage. If a sawtooth carrier is used in hard-switching PWM inverter, there will be severe distortion in the current waveform. When sawtooth carriers with alternate positive and negative slopes are used in soft-switching PWM inverters, the resonancetrigger time is easy to control, and distortion in the output voltage and current caused by the dead time will not appear.

  8. Distribution and mobility of phosphates and sodium ions in cheese by solid-state 31P and double-quantum filtered 23Na NMR spectroscopy.

    Science.gov (United States)

    Gobet, Mallory; Rondeau-Mouro, Corinne; Buchin, Solange; Le Quéré, Jean-Luc; Guichard, Elisabeth; Foucat, Loïc; Moreau, Céline

    2010-04-01

    The feasibility of solid-state magic angle spinning (MAS) (31)P nuclear magnetic resonance (NMR) spectroscopy and (23)Na NMR spectroscopy to investigate both phosphates and Na(+) ions distribution in semi-hard cheeses in a non-destructive way was studied. Two semi-hard cheeses of known composition were made with two different salt contents. (31)P Single-pulse excitation and cross-polarization MAS experiments allowed, for the first time, the identification and quantification of soluble and insoluble phosphates in the cheeses. The presence of a relatively 'mobile' fraction of colloidal phosphates was evidenced. The detection by (23)Na single-quantum NMR experiments of all the sodium ions in the cheeses was validated. The presence of a fraction of 'bound' sodium ions was evidenced by (23)Na double-quantum filtered NMR experiments. We demonstrated that NMR is a suitable tool to investigate both phosphates and Na(+) ions distributions in cheeses. The impact of the sodium content on the various phosphorus forms distribution was discussed and results demonstrated that NMR would be an important tool for the cheese industry for the processes controls.

  9. Mechanism of leakage of ion-implantation isolated AlGaN/GaN MIS-high electron mobility transistors on Si substrate

    Science.gov (United States)

    Zhang, Zhili; Song, Liang; Li, Weiyi; Fu, Kai; Yu, Guohao; Zhang, Xiaodong; Fan, Yaming; Deng, Xuguang; Li, Shuiming; Sun, Shichuang; Li, Xiajun; Yuan, Jie; Sun, Qian; Dong, Zhihua; Cai, Yong; Zhang, Baoshun

    2017-08-01

    In this paper, we systematically investigated the leakage mechanism of the ion-implantation isolated AlGaN/GaN metal-insulator-semiconductor high electron mobility transistors (MIS-HEMTs) on Si substrate. By means of combined DC tests at different temperatures and electric field dependence, we demonstrated the following original results: (1) It is proved that gate leakage is the main contribution to OFF-state leakage of ion-implantation isolated AlGaN/GaN MIS-HEMTs, and the gate leakage path is a series connection of the gate dielectric Si3N4 and Si3N4-GaN interface. (2) The dominant mechanisms of the leakage current through LPCVD-Si3N4 gate dielectric and Si3N4-GaN interface are identified to be Frenkel-Poole emission and two-dimensional variable range hopping (2D-VRH), respectively. (3) A certain temperature annealing could reduce the density of the interface state that produced by ion implantation, and consequently suppress the interface leakage transport, which results in a decrease in OFF-state leakage current of ion-implantation isolated AlGaN/GaN MIS-HEMTs.

  10. The influence of size on phase morphology and Li-ion mobility in nanosized lithiated anatase TiO2

    NARCIS (Netherlands)

    Wagemaker, M.; Borghols, W.L.H.; Eck, E.R.H. van; Kentgens, A.P.M.; Kearley, G.L.; Mulder, F.M.

    2007-01-01

    Sustainable energy storage in the form of Li-ion batteries requires new and advanced materials in particular with a higher power density. Nanostructuring appears to be a promising strategy, in which the higher power density in nanosized materials is related to the dramatically shortened Li-ion

  11. GRC GSFC TDRSS Waveform Metrics Report

    Science.gov (United States)

    Mortensen, Dale J.

    2013-01-01

    The report presents software metrics and porting metrics for the GGT Waveform. The porting was from a ground-based COTS SDR, the SDR-3000, to the CoNNeCT JPL SDR. The report does not address any of the Operating Environment (OE) software development, nor the original TDRSS waveform development at GSFC for the COTS SDR. With regard to STRS, the report presents compliance data and lessons learned.

  12. Georgia Tech Catalog of Gravitational Waveforms

    CERN Document Server

    Jani, Karan; Clark, James A; London, Lionel; Laguna, Pablo; Shoemaker, Deirdre

    2016-01-01

    This paper introduces a catalog of gravitational waveforms from the bank of simulations by the numerical relativity effort at Georgia Tech. Currently, the catalog consists of 452 distinct waveforms from more than 600 binary black hole simulations: 128 of the waveforms are from binaries with black hole spins aligned with the orbital angular momentum, and 324 are from precessing binary black hole systems. The waveforms from binaries with non-spinning black holes have mass-ratios $q = m_1/m_2 \\le 15$, and those with precessing, spinning black holes have $q \\le 8$. The waveforms expand a moderate number of orbits in the late inspiral, the burst during coalescence, and the ring-down of the final black hole. Examples of waveforms in the catalog matched against the widely used approximate models are presented. In addition, predictions of the mass and spin of the final black hole by phenomenological fits are tested against the results from the simulation bank. The role of the catalog in interpreting the GW150914 even...

  13. Georgia tech catalog of gravitational waveforms

    Science.gov (United States)

    Jani, Karan; Healy, James; Clark, James A.; London, Lionel; Laguna, Pablo; Shoemaker, Deirdre

    2016-10-01

    This paper introduces a catalog of gravitational waveforms from the bank of simulations by the numerical relativity effort at Georgia Tech. Currently, the catalog consists of 452 distinct waveforms from more than 600 binary black hole simulations: 128 of the waveforms are from binaries with black hole spins aligned with the orbital angular momentum, and 324 are from precessing binary black hole systems. The waveforms from binaries with non-spinning black holes have mass-ratios q = m 1/m 2 ≤ 15, and those with precessing, spinning black holes have q ≤ 8. The waveforms expand a moderate number of orbits in the late inspiral, the burst during coalescence, and the ring-down of the final black hole. Examples of waveforms in the catalog matched against the widely used approximate models are presented. In addition, predictions of the mass and spin of the final black hole by phenomenological fits are tested against the results from the simulation bank. The role of the catalog in interpreting the GW150914 event and future massive binary black-hole search in LIGO is discussed. The Georgia Tech catalog is publicly available at einstein.gatech.edu/catalog.

  14. PIXiE: an algorithm for automated ion mobility arrival time extraction and collision cross section calculation using global data association.

    Science.gov (United States)

    Ma, Jian; Casey, Cameron P; Zheng, Xueyun; Ibrahim, Yehia M; Wilkins, Christopher S; Renslow, Ryan S; Thomas, Dennis G; Payne, Samuel H; Monroe, Matthew E; Smith, Richard D; Teeguarden, Justin G; Baker, Erin S; Metz, Thomas O

    2017-09-01

    Drift tube ion mobility spectrometry coupled with mass spectrometry (DTIMS-MS) is increasingly implemented in high throughput omics workflows, and new informatics approaches are necessary for processing the associated data. To automatically extract arrival times for molecules measured by DTIMS at multiple electric fields and compute their associated collisional cross sections (CCS), we created the PNNL Ion Mobility Cross Section Extractor (PIXiE). The primary application presented for this algorithm is the extraction of data that can then be used to create a reference library of experimental CCS values for use in high throughput omics analyses. We demonstrate the utility of this approach by automatically extracting arrival times and calculating the associated CCSs for a set of endogenous metabolites and xenobiotics. The PIXiE-generated CCS values were within error of those calculated using commercially available instrument vendor software. PIXiE is an open-source tool, freely available on Github. The documentation, source code of the software, and a GUI can be found at https://github.com/PNNL-Comp-Mass-Spec/PIXiE and the source code of the backend workflow library used by PIXiE can be found at https://github.com/PNNL-Comp-Mass-Spec/IMS-Informed-Library . erin.baker@pnnl.gov or thomas.metz@pnnl.gov. Supplementary data are available at Bioinformatics online.

  15. Direct determination of 2,4,6-tricholoroanisole in wines by single-drop ionic liquid microextraction coupled with multicapillary column separation and ion mobility spectrometry detection.

    Science.gov (United States)

    Márquez-Sillero, Isabel; Cárdenas, Soledad; Valcárcel, Miguel

    2011-10-21

    This article evaluates the capability of single drop ionic liquid microextraction coupled with multicapillary column (MCC) and ion mobility spectrometry (IMS) for the determination of 2,4,6-trichloroanisole (2,4,6-TCA) in wines. The proposed methodology permits the direct analysis of the samples without any additional treatment other than dilution. This is achieved thanks to the selectivity provided by the ionic liquid selected as extractant, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, as well as the response of the analyte in the IMS working in negative ionization mode. Moreover, the multicapillary column avoids the interference of ethanol in the ion mobility spectra. The analysis of the sample takes ca. 35 min to be completed. The limit of detection was low as 0.01 ng L(-1) using 2 mL of wine sample. Different calibration curves were constructed using aqueous standards, red and white wines, being the signals comparable, with an RSD similar to the method variability. Finally, a set of samples of different nature and packed in different containers were analysed. It was found than those with cork stoppers presented the highest concentration of 2,4,6-TCA.

  16. Headspace-multicapillary column-ion mobility spectrometry for the direct analysis of 2,4,6-trichloroanisole in wine and cork samples.

    Science.gov (United States)

    Márquez-Sillero, Isabel; Cárdenas, Soledad; Valcárcel, Miguel

    2012-11-23

    Headspace-multicapillary column-ion mobility spectrometry coupling has been evaluated for the direct analysis of wine and cork stopper samples for the determination of 2,4,6-trichloroanisole (2,4,6-TCA). The instrumental configuration permits the sample to be introduced in headspace vials which are placed into the autosampler oven in order to facilitate the transference of the volatile compounds from the sample to its headspace. Further, an aliquot of 200 μL of the homogenized gaseous phase is injected into the multicapillary column in order to separate the target compounds from potential interferents. The detection of 2,4,6-TCA was carried out in an ion mobility spectrometer with a radioactive source and working under negative mode. All the system was computer controlled, including data acquisition and treatment. The limits of detection achieved were 0.012 ng L(-1) for wine and 0.28 ng g(-1) for the cork stopper. The procedure was applied to the analysis of commercial wine samples in different packages and 2,4,6-TCA was found in all of those closed with a cork stopper. The excellent recovery values obtained testify for the goodness of the method as no interference from the sample matrix exits.

  17. The hydrophilicity vs. ion interaction selectivity plot revisited: The effect of mobile phase pH and buffer concentration on hydrophilic interaction liquid chromatography selectivity behavior.

    Science.gov (United States)

    Iverson, Chad D; Gu, Xinyun; Lucy, Charles A

    2016-08-05

    This work systematically investigates the selectivity changes on many HILIC phases from w(w)pH 3.7-6.8, at 5 and 25mM buffer concentrations. Hydrophilicity (kcytosine/kuracil) vs. ion interaction (kBTMA/kuracil) selectivity plots developed by Ibrahim et al. (J. Chromatogr. A 1260 (2012) 126-131) are used to investigate the effect of mobile phase changes on the selectivity of 18 HILIC columns from various classes. "Selectivity change plots" focus on the change in hydrophilicity and ion interaction that the columns exhibit upon changing mobile phase conditions. In general, the selectivity behavior of most HILIC columns is dominated by silanol activity. Minimal changes in selectivity are observed upon changing pH between w(w)pH 5 and 6.8. However, a reduction in ionic interaction is observed when the buffer concentration is increased at w(w)pH≥5.0 due to ionic shielding. Reduction of the w(w)pH to<5.0 results in decreasing cation exchange activity due to silanol protonation. Under all eluent conditions, the majority of phases show little change in their hydrophilicity.

  18. Platform for Postprocessing Waveform-Based NDE

    Science.gov (United States)

    Roth, Don

    2008-01-01

    Taking advantage of the similarities that exist among all waveform-based non-destructive evaluation (NDE) methods, a common software platform has been developed containing multiple- signal and image-processing techniques for waveforms and images. The NASA NDE Signal and Image Processing software has been developed using the latest versions of LabVIEW, and its associated Advanced Signal Processing and Vision Toolkits. The software is useable on a PC with Windows XP and Windows Vista. The software has been designed with a commercial grade interface in which two main windows, Waveform Window and Image Window, are displayed if the user chooses a waveform file to display. Within these two main windows, most actions are chosen through logically conceived run-time menus. The Waveform Window has plots for both the raw time-domain waves and their frequency- domain transformations (fast Fourier transform and power spectral density). The Image Window shows the C-scan image formed from information of the time-domain waveform (such as peak amplitude) or its frequency-domain transformation at each scan location. The user also has the ability to open an image, or series of images, or a simple set of X-Y paired data set in text format. Each of the Waveform and Image Windows contains menus from which to perform many user actions. An option exists to use raw waves obtained directly from scan, or waves after deconvolution if system wave response is provided. Two types of deconvolution, time-based subtraction or inverse-filter, can be performed to arrive at a deconvolved wave set. Additionally, the menu on the Waveform Window allows preprocessing of waveforms prior to image formation, scaling and display of waveforms, formation of different types of images (including non-standard types such as velocity), gating of portions of waves prior to image formation, and several other miscellaneous and specialized operations. The menu available on the Image Window allows many further image

  19. Power supply and impedance matching to drive technological radio-frequency plasmas with customized voltage waveforms.

    Science.gov (United States)

    Franek, James; Brandt, Steven; Berger, Birk; Liese, Martin; Barthel, Matthias; Schüngel, Edmund; Schulze, Julian

    2015-05-01

    We present a novel radio-frequency (RF) power supply and impedance matching to drive technological plasmas with customized voltage waveforms. It is based on a system of phase-locked RF generators that output single frequency voltage waveforms corresponding to multiple consecutive harmonics of a fundamental frequency. These signals are matched individually and combined to drive a RF plasma. Electrical filters are used to prevent parasitic interactions between the matching branches. By adjusting the harmonics' phases and voltage amplitudes individually, any voltage waveform can be approximated as a customized finite Fourier series. This RF supply system is easily adaptable to any technological plasma for industrial applications and allows the commercial utilization of process optimization based on voltage waveform tailoring for the first time. Here, this system is tested on a capacitive discharge based on three consecutive harmonics of 13.56 MHz. According to the Electrical Asymmetry Effect, tuning the phases between the applied harmonics results in an electrical control of the DC self-bias and the mean ion energy at almost constant ion flux. A comparison with the reference case of an electrically asymmetric dual-frequency discharge reveals that the control range of the mean ion energy can be significantly enlarged by using more than two consecutive harmonics.

  20. High-performance ion mobility spectrometry with direct electrospray ionization (ESI-HPIMS) for the detection of additives and contaminants in food

    Energy Technology Data Exchange (ETDEWEB)

    Midey, Anthony J., E-mail: anthony.midey@excellims.com; Camacho, Amanda; Sampathkumaran, Jayanthi; Krueger, Clinton A.; Osgood, Mark A.; Wu, Ching

    2013-12-04

    Graphical abstract: -- Highlights: •A new ESI source was built for direct ionization from syringe. •Phthalates, food dyes, and sweeteners detected with high-performance IMS. •Phthalates directly detected in cola, soy bubble tea matrices with simple treatment. -- Abstract: High-performance ion mobility spectrometry (HPIMS) with an electrospray ionization (ESI) source detected a series of food contaminants and additive compounds identified as critical to monitoring the safety of food samples. These compounds included twelve phthalate plasticizers, legal and illegal food and cosmetic dyes, and artificial sweeteners that were all denoted as detection priorities. HPIMS separated and detected the range of compounds with a resolving power better than 60 in both positive and negative ion modes, comparable to the commonly used high-performance liquid chromatography (HPLC) methods, but with most acquisition times under a minute. The reduced mobilities, K{sub 0}, have been determined, as have the linear response ranges for ESI-HPIMS, which are 1.5–2 orders of magnitude for concentrations down to sub-ng μL{sup −1} levels. At least one unique mobility peak was seen for two subsets of the phthalates grouped by the country where they were banned. Furthermore, ESI-HPIMS successfully detected low nanogram levels of a phthalate at up to 30 times lower concentration than international detection levels in both a cola matrix and a soy-based bubble tea beverage using only a simplified sample treatment. A newly developed direct ESI source (Directspray) was combined with HPIMS to detect food-grade dyes and industrial dye adulterants, as well as the sweeteners sodium saccharin and sodium cyclamate, with the same good performance as with the phthalates. However, the Directspray method eliminated sources of carryover and decreased the time between sample runs. Limits-of-detection (LOD) for the analyte standards were estimated to be sub-ng μL{sup −1} levels without extensive

  1. The enhanced low resistance contacts and boosted mobility in two-dimensional p-type WSe2 transistors through Ar+ ion-beam generated surface defects

    Directory of Open Access Journals (Sweden)

    Dahye Kim

    2016-10-01

    Full Text Available We intentionally generated surface defects in WSe2 using a low energy argon (Ar+ ion-beam. We were unable to detect any changes in lattice structure through Raman spectroscopy as expected through simulation. Meanwhile, atomic force microscopy showed roughened surfaces with a high density of large protruding spots. Defect-activated Photoluminescence (PL revealed a binding energy reduction of the W 4f core level indicating significant amounts of defect generation within the bandgap of WSe2 even at the lowest studied 300 eV ion-beam energy. The intensity ratio increase of direct PL peak demonstrated the decoupling of surface layers, which behave like consecutive defective monolayers. Electrical measurements after post-irradiation showed p-type ohmic contacts regardless of the ion-beam energy. The resulting ohmic contact contributed to an increased on/off current ratio, mobility enhancement of around 350 cm2V-1s-1 from a few cm2V-1s-1 in pristine devices and electron conduction suppression. Further increased ion-beam energy over 700 eV resulted in a high shift of threshold voltage and diminished subthreshold slope due to increased surface roughness and boosted interface scattering. The origin of the ohmic contact behavior in p-type WSe2 is expected to be from chalcogen vacancy defects of a certain size which pins the Fermi level near the valence band minimum. An optimized ion-beam irradiation process could provide solutions for fabricating ohmic contacts to transition metal dichalcogenides.

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

    Science.gov (United States)

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

    2016-07-15

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

  3. Gas-phase structure of amyloid-β (12-28) peptide investigated by infrared spectroscopy, electron capture dissociation and ion mobility mass spectrometry.

    Science.gov (United States)

    Le, Thi Nga; Poully, Jean Christophe; Lecomte, Frédéric; Nieuwjaer, Nicolas; Manil, Bruno; Desfrançois, Charles; Chirot, Fabien; Lemoine, Jerome; Dugourd, Philippe; van der Rest, Guillaume; Grégoire, Gilles

    2013-12-01

    The gas-phase structures of doubly and triply protonated Amyloid-β12-28 peptides have been investigated through the combination of ion mobility (IM), electron capture dissociation (ECD) mass spectrometry, and infrared multi-photon dissociation (IRMPD) spectroscopy together with theoretical modeling. Replica-exchange molecular dynamics simulations were conducted to explore the conformational space of these protonated peptides, from which several classes of structures were found. Among the low-lying conformers, those with predicted diffusion cross-sections consistent with the ion mobility experiment were further selected and their IR spectra simulated using a hybrid quantum mechanical/semiempirical method at the ONIOM DFT/B3LYP/6-31 g(d)/AM1 level. In ECD mass spectrometry, the c/z product ion abundance (PIA) has been analyzed for the two charge states and revealed drastic differences. For the doubly protonated species, N - Cα bond cleavage occurs only on the N and C terminal parts, while a periodic distribution of PIA is clearly observed for the triply charged peptides. These PIA distributions have been rationalized by comparison with the inverse of the distances from the protonated sites to the carbonyl oxygens for the conformations suggested from IR and IM experiments. Structural assignment for the amyloid peptide is then made possible by the combination of these three experimental techniques that provide complementary information on the possible secondary structure adopted by peptides. Although globular conformations are favored for the doubly protonated peptide, incrementing the charge state leads to a conformational transition towards extended structures with 310- and α-helix motifs.

  4. Electrospray Quadrupole Travelling Wave Ion Mobility Time-of-Flight Mass Spectrometry for the Detection of Plasma Metabolome Changes Caused by Xanthohumol in Obese Zucker (fa/fa Rats

    Directory of Open Access Journals (Sweden)

    Claudia S. Maier

    2013-08-01

    Full Text Available This study reports on the use of traveling wave ion mobility quadrupole time-of-flight (ToF mass spectrometry for plasma metabolomics. Plasma metabolite profiles of obese Zucker fa/fa rats were obtained after the administration of different oral doses of Xanthohumol; a hop-derived dietary supplement. Liquid chromatography coupled data independent tandem mass spectrometry (LC-MSE and LC-ion mobility spectrometry (IMS-MSE acquisitions were conducted in both positive and negative modes using a Synapt G2 High Definition Mass Spectrometry (HDMS instrument. This method provides identification of metabolite classes in rat plasma using parallel alternating low energy and high energy collision spectral acquisition modes. Data sets were analyzed using pattern recognition methods. Statistically significant (p 1.5 features were selected to identify the up-/down-regulated metabolite classes. Ion mobility data visualized using drift scope software provided a graphical read-out of differences in metabolite classes.

  5. Ion mobility, conductivity, structure, and phase transitions in K0.7M0.3SbF4 compounds with M=Rb, NH4

    Science.gov (United States)

    Kavun, V. Ya.; Gerasimenko, A. V.; Uvarov, N. F.; Polyantsev, M. M.; Zemnukhova, L. A.

    2016-09-01

    Ion mobility, phase transitions, structure, and conductivity in the K0.7M0.3SbF4 (M=Rb, NH4) compounds were studied by NMR spectroscopy, DSC, X-ray, and conductivity measurements. The predominant form in the ion motions resulting from the phase transition of high modification was diffusion of fluoride and ammonium ions above 450 K. The high-temperature phases of K0.7M0.3SbF4 (M=Rb, NH4) are superionic, while their conductivity attains the values of ~10-2-10-4 S/cm at 450-500 K. The structures of α- and β-modifications of the K0.7Rb0.3SbF4 are monoclinic (space group P21/m). The main structural units in them are statistically substituting each other K+ and Rb+ cations and complex 1[ SbF4 ]- ∞ anions linked into zigzag-like chains by bridge fluorine atoms. The nearest surrounding of each antimony atom contains five fluorine atoms, so that the antimony coordination polyhedron can be described, taking into account the lone electron pair, as a distorted SbF5E octahedron (ψ-octahedron).

  6. AlGaN/GaN metal-insulator-semiconductor high electron mobility transistors with reduced leakage current and enhanced breakdown voltage using aluminum ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Shichuang [Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074 (China); Key Laboratory of Nanodevices and Applications, Suzhou Institute of Nano-Tech and Nano-Bionics, CAS, Suzhou 215123 (China); Fu, Kai, E-mail: kfu2009@sinano.ac.cn, E-mail: cqchen@mail.hust.edu.cn; Yu, Guohao; Zhang, Zhili; Song, Liang; Deng, Xuguang; Li, Shuiming; Sun, Qian; Cai, Yong; Zhang, Baoshun [Key Laboratory of Nanodevices and Applications, Suzhou Institute of Nano-Tech and Nano-Bionics, CAS, Suzhou 215123 (China); Qi, Zhiqiang; Dai, Jiangnan; Chen, Changqing, E-mail: kfu2009@sinano.ac.cn, E-mail: cqchen@mail.hust.edu.cn [Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2016-01-04

    This letter has studied the performance of AlGaN/GaN metal-insulator-semiconductor high electron mobility transistors on silicon substrate with GaN buffer treated by aluminum ion implantation for insulating followed by a channel regrown by metal–organic chemical vapor deposition. For samples with Al ion implantation of multiple energies of 140 keV (dose: 1.4 × 10{sup 14} cm{sup −2}) and 90 keV (dose: 1 × 10{sup 14} cm{sup −2}), the OFF-state leakage current is decreased by more than 3 orders and the breakdown voltage is enhanced by nearly 6 times compared to the samples without Al ion implantation. Besides, little degradation of electrical properties of the 2D electron gas channel is observed where the maximum drain current I{sub DSmax} at a gate voltage of 3 V was 701 mA/mm and the maximum transconductance g{sub mmax} was 83 mS/mm.

  7. Design of pulse waveform for waveform division multiple access UWB wireless communication system.

    Science.gov (United States)

    Yin, Zhendong; Wang, Zhirui; Liu, Xiaohui; Wu, Zhilu

    2014-01-01

    A new multiple access scheme, Waveform Division Multiple Access (WDMA) based on the orthogonal wavelet function, is presented. After studying the correlation properties of different categories of single wavelet functions, the one with the best correlation property will be chosen as the foundation for combined waveform. In the communication system, each user is assigned to different combined orthogonal waveform. Demonstrated by simulation, combined waveform is more suitable than single wavelet function to be a communication medium in WDMA system. Due to the excellent orthogonality, the bit error rate (BER) of multiuser with combined waveforms is so close to that of single user in a synchronous system. That is to say, the multiple access interference (MAI) is almost eliminated. Furthermore, even in an asynchronous system without multiuser detection after matched filters, the result is still pretty ideal and satisfactory by using the third combination mode that will be mentioned in the study.

  8. WFCatalog: A catalogue for seismological waveform data

    Science.gov (United States)

    Trani, Luca; Koymans, Mathijs; Atkinson, Malcolm; Sleeman, Reinoud; Filgueira, Rosa

    2017-09-01

    This paper reports advances in seismic waveform description and discovery leading to a new seismological service and presents the key steps in its design, implementation and adoption. This service, named WFCatalog, which stands for waveform catalogue, accommodates features of seismological waveform data. Therefore, it meets the need for seismologists to be able to select waveform data based on seismic waveform features as well as sensor geolocations and temporal specifications. We describe the collaborative design methods and the technical solution showing the central role of seismic feature catalogues in framing the technical and operational delivery of the new service. Also, we provide an overview of the complex environment wherein this endeavour is scoped and the related challenges discussed. As multi-disciplinary, multi-organisational and global collaboration is necessary to address today's challenges, canonical representations can provide a focus for collaboration and conceptual tools for agreeing directions. Such collaborations can be fostered and formalised by rallying intellectual effort into the design of novel scientific catalogues and the services that support them. This work offers an example of the benefits generated by involving cross-disciplinary skills (e.g. data and domain expertise) from the early stages of design, and by sustaining the engagement with the target community throughout the delivery and deployment process.

  9. SCA Waveform Development for Space Telemetry

    Science.gov (United States)

    Mortensen, Dale J.; Kifle, Multi; Hall, C. Steve; Quinn, Todd M.

    2004-01-01

    The NASA Glenn Research Center is investigating and developing suitable reconfigurable radio architectures for future NASA missions. This effort is examining software-based open-architectures for space based transceivers, as well as common hardware platform architectures. The Joint Tactical Radio System's (JTRS) Software Communications Architecture (SCA) is a candidate for the software approach, but may need modifications or adaptations for use in space. An in-house SCA compliant waveform development focuses on increasing understanding of software defined radio architectures and more specifically the JTRS SCA. Space requirements put a premium on size, mass, and power. This waveform development effort is key to evaluating tradeoffs with the SCA for space applications. Existing NASA telemetry links, as well as Space Exploration Initiative scenarios, are the basis for defining the waveform requirements. Modeling and simulations are being developed to determine signal processing requirements associated with a waveform and a mission-specific computational burden. Implementation of the waveform on a laboratory software defined radio platform is proceeding in an iterative fashion. Parallel top-down and bottom-up design approaches are employed.

  10. Cross sections for Scattering and Mobility of OH- and H3 O+ ions in H2 O

    Science.gov (United States)

    Petrovic, Zoran; Stojanovic, Vladimir; Maric, Dragana; Jovanovic, Jasmina

    2016-05-01

    Modelling of plasmas in liquids and in biological and medical applications requires data for scattering of all charged and energetic particles in water vapour. We present swarm parameters for OH- and H3 O+, as representatives of principal negative and positive ions at low pressures in an attempt to provide the data that are not yet available. We applied Denpoh-Nanbu procedure to calculate cross section sets for collisions of OH- and H3 O+ ions with H2 O molecule. Swarm parameters for OH- and H3 O+ ions in H2 O are calculated by using a well tested Monte Carlo code for a range of E / N(E -electric field, N-gas density) at temperature T = 295 K, in the low pressure limit. Non-conservative processes were shown to strongly influence the transport properties even for OH- ions above the average energy of 0.2 eV(E / N >200 Td). The data are valid for low pressure water vapour or small amounts in mixtures. They will provide a basis for calculating properties of ion-water molecule clusters that are most commonly found at higher pressures and for modelling of discharges in liquids. Acknowledgment to Ministry of Education, Science and Technology of Serbia.

  11. Power coupling mode transitions induced by tailored voltage waveforms in capacitive oxygen discharges

    Science.gov (United States)

    Derzsi, Aranka; Bruneau, Bastien; Gibson, Andrew Robert; Johnson, Erik; O’Connell, Deborah; Gans, Timo; Booth, Jean-Paul; Donkó, Zoltán

    2017-03-01

    Low-pressure capacitively coupled radio frequency discharges operated in O2 and driven by tailored voltage waveforms are investigated experimentally and by means of kinetic simulations. Pulse-type (peaks/valleys) and sawtooth-type voltage waveforms that consist of up to four consecutive harmonics of the fundamental frequency are used to study the amplitude asymmetry effect as well as the slope asymmetry effect at different fundamental frequencies (5, 10, and 15 MHz) and at different pressures (50–700 mTorr). Values of the DC self-bias determined experimentally and spatio-temporal excitation rates derived from phase resolved optical emission spectroscopy measurements are compared with particle-in-cell/Monte Carlo collisions simulations. The spatio-temporal distributions of the excitation rate obtained from experiments are well reproduced by the simulations. Transitions of the discharge electron heating mode from the drift-ambipolar mode to the α-mode are induced by changing the number of consecutive harmonics included in the driving voltage waveform or by changing the gas pressure. Changing the number of harmonics in the waveform has a strong effect on the electronegativity of the discharge, on the generation of the DC self-bias and on the control of ion properties at the electrodes, both for pulse-type, as well as sawtooth-type driving voltage waveforms The effect of the surface quenching rate of oxygen singlet delta metastable molecules on the spatio-temporal excitation patterns is also investigated.

  12. Photonic arbitrary waveform generator based on Taylor synthesis method

    DEFF Research Database (Denmark)

    Liao, Shasha; Ding, Yunhong; Dong, Jianji

    2016-01-01

    Arbitrary waveform generation has been widely used in optical communication, radar system and many other applications. We propose and experimentally demonstrate a silicon-on-insulator (SOI) on chip optical arbitrary waveform generator, which is based on Taylor synthesis method. In our scheme......, a Gaussian pulse is launched to some cascaded microrings to obtain first-, second- and third-order differentiations. By controlling amplitude and phase of the initial pulse and successive differentiations, we can realize an arbitrary waveform generator according to Taylor expansion. We obtain several typical...... waveforms such as square waveform, triangular waveform, flat-top waveform, sawtooth waveform, Gaussian waveform and so on. Unlike other schemes based on Fourier synthesis or frequency-to-time mapping, our scheme is based on Taylor synthesis method. Our scheme does not require any spectral disperser or large...

  13. Photonic arbitrary waveform generator based on Taylor synthesis method.

    Science.gov (United States)

    Liao, Shasha; Ding, Yunhong; Dong, Jianji; Yan, Siqi; Wang, Xu; Zhang, Xinliang

    2016-10-17

    Arbitrary waveform generation has been widely used in optical communication, radar system and many other applications. We propose and experimentally demonstrate a silicon-on-insulator (SOI) on chip optical arbitrary waveform generator, which is based on Taylor synthesis method. In our scheme, a Gaussian pulse is launched to some cascaded microrings to obtain first-, second- and third-order differentiations. By controlling amplitude and phase of the initial pulse and successive differentiations, we can realize an arbitrary waveform generator according to Taylor expansion. We obtain several typical waveforms such as square waveform, triangular waveform, flat-top waveform, sawtooth waveform, Gaussian waveform and so on. Unlike other schemes based on Fourier synthesis or frequency-to-time mapping, our scheme is based on Taylor synthesis method. Our scheme does not require any spectral disperser or large dispersion, which are difficult to fabricate on chip. Our scheme is compact and capable for integration with electronics.

  14. Krylov subspace acceleration of waveform relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Lumsdaine, A.; Wu, Deyun [Univ. of Notre Dame, IN (United States)

    1996-12-31

    Standard solution methods for numerically solving time-dependent problems typically begin by discretizing the problem on a uniform time grid and then sequentially solving for successive time points. The initial time discretization imposes a serialization to the solution process and limits parallel speedup to the speedup available from parallelizing the problem at any given time point. This bottleneck can be circumvented by the use of waveform methods in which multiple time-points of the different components of the solution are computed independently. With the waveform approach, a problem is first spatially decomposed and distributed among the processors of a parallel machine. Each processor then solves its own time-dependent subsystem over the entire interval of interest using previous iterates from other processors as inputs. Synchronization and communication between processors take place infrequently, and communication consists of large packets of information - discretized functions of time (i.e., waveforms).

  15. Wavelet analysis of the impedance cardiogram waveforms

    Science.gov (United States)

    Podtaev, S.; Stepanov, R.; Dumler, A.; Chugainov, S.; Tziberkin, K.

    2012-12-01

    Impedance cardiography has been used for diagnosing atrial and ventricular dysfunctions, valve disorders, aortic stenosis, and vascular diseases. Almost all the applications of impedance cardiography require determination of some of the characteristic points of the ICG waveform. The ICG waveform has a set of characteristic points known as A, B, E ((dZ/dt)max) X, Y, O and Z. These points are related to distinct physiological events in the cardiac cycle. Objective of this work is an approbation of a new method of processing and interpretation of the impedance cardiogram waveforms using wavelet analysis. A method of computer thoracic tetrapolar polyrheocardiography is used for hemodynamic registrations. Use of original wavelet differentiation algorithm allows combining filtration and calculation of the derivatives of rheocardiogram. The proposed approach can be used in clinical practice for early diagnostics of cardiovascular system remodelling in the course of different pathologies.

  16. Waveform information from quantum mechanical entropy

    Science.gov (United States)

    Funkhouser, Scott; Suski, William; Winn, Andrew

    2016-06-01

    Although the entropy of a given signal-type waveform is technically zero, it is nonetheless desirable to use entropic measures to quantify the associated information. Several such prescriptions have been advan