Science.gov

Sample records for ion mobility separations

  1. Ion Mobility Separation of Peptide Isotopomers

    NASA Astrophysics Data System (ADS)

    Kaszycki, Julia L.; Bowman, Andrew P.; Shvartsburg, Alexandre A.

    2016-03-01

    Differential or field asymmetric waveform ion mobility spectrometry (FAIMS) operating at high electric fields fully resolves isotopic isomers for a peptide with labeled residues. The naturally present isotopes, alone and together with targeted labels, also cause spectral shifts that approximately add for multiple heavy atoms. Separation qualitatively depends on the gas composition. These findings may enable novel strategies in proteomic and metabolomic analyses using stable isotope labeling.

  2. Ion Mobility Separation of Peptide Isotopomers.

    PubMed

    Kaszycki, Julia L; Bowman, Andrew P; Shvartsburg, Alexandre A

    2016-05-01

    Differential or field asymmetric waveform ion mobility spectrometry (FAIMS) operating at high electric fields fully resolves isotopic isomers for a peptide with labeled residues. The naturally present isotopes, alone and together with targeted labels, also cause spectral shifts that approximately add for multiple heavy atoms. Separation qualitatively depends on the gas composition. These findings may enable novel strategies in proteomic and metabolomic analyses using stable isotope labeling. Graphical Abstract ᅟ. PMID:26944281

  3. Ion Mobility Separation of Peptide Isotopomers

    NASA Astrophysics Data System (ADS)

    Kaszycki, Julia L.; Bowman, Andrew P.; Shvartsburg, Alexandre A.

    2016-05-01

    Differential or field asymmetric waveform ion mobility spectrometry (FAIMS) operating at high electric fields fully resolves isotopic isomers for a peptide with labeled residues. The naturally present isotopes, alone and together with targeted labels, also cause spectral shifts that approximately add for multiple heavy atoms. Separation qualitatively depends on the gas composition. These findings may enable novel strategies in proteomic and metabolomic analyses using stable isotope labeling.

  4. Ion mobility spectrometer using frequency-domain separation

    DOEpatents

    Martin, Stephen J.; Butler, Michael A.; Frye, Gregory C.; Schubert, W. Kent

    1998-01-01

    An apparatus and method is provided for separating and analyzing chemical species in an ion mobility spectrometer using a frequency-domain technique wherein the ions generated from the chemical species are selectively transported through an ion flow channel having a moving electrical potential therein. The moving electrical potential allows the ions to be selected according to ion mobility, with certain of the ions being transported to an ion detector and other of the ions being effectively discriminated against. The apparatus and method have applications for sensitive chemical detection and analysis for monitoring of exhaust gases, hazardous waste sites, industrial processes, aerospace systems, non-proliferation, and treaty verification. The apparatus can be formed as a microelectromechanical device (i.e. a micromachine).

  5. Ion mobility spectrometer using frequency-domain separation

    DOEpatents

    Martin, S.J.; Butler, M.A.; Frye, G.C.; Schubert, W.K.

    1998-08-04

    An apparatus and method are provided for separating and analyzing chemical species in an ion mobility spectrometer using a frequency-domain technique wherein the ions generated from the chemical species are selectively transported through an ion flow channel having a moving electrical potential therein. The moving electrical potential allows the ions to be selected according to ion mobility, with certain of the ions being transported to an ion detector and other of the ions being effectively discriminated against. The apparatus and method have applications for sensitive chemical detection and analysis for monitoring of exhaust gases, hazardous waste sites, industrial processes, aerospace systems, non-proliferation, and treaty verification. The apparatus can be formed as a microelectromechanical device (i.e. a micromachine). 6 figs.

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

    DOEpatents

    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.

  7. Separation of Variant Methylated Histone Tails by Differential Ion Mobility

    SciTech Connect

    Shvartsburg, Alexandre A.; Zheng, Yupeng; Smith, Richard D.; Kelleher, Neil

    2012-07-18

    Differential ion mobility spectrometry (FAIMS) is emerging as a broadly useful tool for separation of isomeric modified peptides with post-translational modifications (PTMs) attached to alternative residues. Such separations were anticipated to become more challenging for smaller PTMs and longer peptides. Here we show that FAIMS can fully resolve localization variants involving a PTM as minuscule as methylation, even for larger peptides in the middle-down range.

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

    PubMed

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

    2013-10-01

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

  9. Blind Source Separation For Ion Mobility Spectra

    NASA Astrophysics Data System (ADS)

    Marco, S.; Pomareda, V.; Pardo, A.; Kessler, M.; Goebel, J.; Mueller, G.

    2009-05-01

    Miniaturization is a powerful trend for smart chemical instrumentation in a diversity of applications. It is know that miniaturization in IMS leads to a degradation of the system characteristics. For the present work, we are interested in signal processing solutions to mitigate limitations introduced by limited drift tube length that basically involve a loss of chemical selectivity. While blind source separation techniques (BSS) are popular in other domains, their application for smart chemical instrumentation is limited. However, in some conditions, basically linearity, BSS may fully recover the concentration time evolution and the pure spectra with few underlying hypothesis. This is extremely helpful in conditions where non-expected chemical interferents may appear, or unwanted perturbations may pollute the spectra. SIMPLISMA has been advocated by Harrington et al. in several papers. However, more modern methods of BSS for bilinear decomposition with the restriction of positiveness have appeared in the last decade. In order to explore and compare the performances of those methods a series of experiments were performed.

  10. Blind Source Separation For Ion Mobility Spectra

    SciTech Connect

    Marco, S.; Pomareda, V.

    2009-05-23

    Miniaturization is a powerful trend for smart chemical instrumentation in a diversity of applications. It is know that miniaturization in IMS leads to a degradation of the system characteristics. For the present work, we are interested in signal processing solutions to mitigate limitations introduced by limited drift tube length that basically involve a loss of chemical selectivity. While blind source separation techniques (BSS) are popular in other domains, their application for smart chemical instrumentation is limited. However, in some conditions, basically linearity, BSS may fully recover the concentration time evolution and the pure spectra with few underlying hypothesis. This is extremely helpful in conditions where non-expected chemical interferents may appear, or unwanted perturbations may pollute the spectra. SIMPLISMA has been advocated by Harrington et al. in several papers. However, more modern methods of BSS for bilinear decomposition with the restriction of positiveness have appeared in the last decade. In order to explore and compare the performances of those methods a series of experiments were performed.

  11. Accelerated High-Resolution Differential Ion Mobility Separations Using Hydrogen

    PubMed Central

    Shvartsburg, Alexandre A.; Smith, Richard D.

    2011-01-01

    The resolving power of differential ion mobility spectrometry (FAIMS) was dramatically increased recently by carrier gases comprising up to 75% He or various vapors, enabling many new applications. However, the need for resolution of complex mixtures is virtually open-ended and many topical analyses demand yet finer separations. Also, the resolving power gains are often at the expense of speed, in particular making high-resolution FAIMS incompatible with online liquid-phase separations. Here, we report FAIMS employing hydrogen, specifically in mixtures with N2 containing up to 90% H2. Such compositions raise the mobilities of all ions and thus the resolving power beyond that previously feasible, while avoiding the electrical breakdown inevitable in He-rich mixtures. The increases in resolving power and ensuing peak resolution are especially significant at H2 fractions above ~50%. Higher resolution can be exchanged for acceleration of the analyses by up to ~4 times, at least. For more mobile species such as multiply-charged peptides, this exchange is presently forced by the constraints of existing FAIMS devices, but future designs optimized for H2 should consistently improve resolution for all analytes. PMID:22074292

  12. Separation and Classification of Lipids Using Differential Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Shvartsburg, Alexandre A.; Isaac, Giorgis; Leveque, Nathalie; Smith, Richard D.; Metz, Thomas O.

    2011-07-01

    Correlations between the dimensions of a 2-D separation create trend lines that depend on structural or chemical characteristics of the compound class and thus facilitate classification of unknowns. This broadly applies to conventional ion mobility spectrometry (IMS)/mass spectrometry (MS), where the major biomolecular classes (e.g., lipids, peptides, nucleotides) occupy different trend line domains. However, strong correlation between the IMS and MS separations for ions of same charge has impeded finer distinctions. Differential IMS (or FAIMS) is generally less correlated to MS and thus could separate those domains better. We report the first observation of chemical class separation by trend lines using FAIMS, here for lipids. For lipids, FAIMS is indeed more independent of MS than conventional IMS, and subclasses (such as phospho-, glycero-, or sphingolipids) form distinct, often non-overlapping domains. Even finer categories with different functional groups or degrees of unsaturation are often separated. As expected, resolution improves in He-rich gases: at 70% He, glycerolipid isomers with different fatty acid positions can be resolved. These results open the door for application of FAIMS to lipids, particularly in shotgun lipidomics and targeted analyses of bioactive lipids.

  13. Separation and Classification of Lipids Using Differential Ion Mobility Spectrometry

    PubMed Central

    Shvartsburg, Alexandre A.; Isaac, Giorgis; Leveque, Nathalie; Smith, Richard D.; Metz, Thomas O.

    2011-01-01

    Correlations between the dimensions of a 2-D separation create trend lines that depend on structural or chemical characteristics of the compound class and thus facilitate classification of unknowns. This broadly applies to conventional ion mobility spectrometry (IMS)/mass spectrometry (MS), where the major biomolecular classes (e.g., lipids, peptides, nucleotides) occupy different trend line domains. However, strong correlation between the IMS and MS separations for ions of same charge has impeded finer distinctions. Differential IMS (or FAIMS) is generally less correlated to MS and thus could separate those domains better. We report the first observation of chemical class separation by trend lines using FAIMS, here for lipids. For lipids, FAIMS is indeed more independent of MS than conventional IMS, and subclasses (such as phospho-, glycero-, or sphingolipids) form distinct, often non-overlapping domains. Even finer categories with different functional groups or degrees of unsaturation are often separated. As expected, resolution improves in He-rich gases: at 70% He, glycerolipid isomers with different fatty acid positions can be resolved. These results open the door for application of FAIMS to lipids, particularly in shotgun lipidomics and targeted analyses of bioactive lipids. PMID:21953096

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

    SciTech Connect

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

    2015-10-28

    We report on the development and characterization of a new traveling wave-based Structure for Lossless Ion Manipulations (TW-SLIM) 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. In conclusion, 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.

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

    PubMed

    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. PMID:26510005

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

    DOE PAGESBeta

    Hamid, Ahmed M.; Ibrahim, Yehia M.; Garimella, Venkata BS; Webb, Ian K.; Deng, Liulin; Chen, Tsung-Chi; Anderson, Gordon A.; Prost, Spencer A.; Norheim, Randolph V.; Tolmachev, Aleksey V.; et al

    2015-10-28

    We report on the development and characterization of a new traveling wave-based Structure for Lossless Ion Manipulations (TW-SLIM) 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 aremore » 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. In conclusion, 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.« less

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

    PubMed Central

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed

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

    2016-05-01

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

  1. Separation of a Set of Peptide Sequence Isomers Using Differential Ion Mobility Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.; Creese, Andrew J.; Smith, Richard D.; Cooper, Helen J.

    2011-08-15

    Protein identification in bottom-up proteomics requires disentangling isomers of proteolytic peptides, a major class of which are sequence inversions. Separation of sequence isomers using ion mobility spectrometry (IMS) has been reported, but limited to pairs of species. Here we demonstrate baseline separation of all seven sequences for a tryptic peptide with eight residues using differential IMS or FAIMS. Evaluations of peak capacity of the method indicate that even larger libraries should generally be separated for heavier peptides with higher charge states.

  2. Ion mobility sensor

    DOEpatents

    Koo, Jackson C.; Yu, Conrad M.

    2005-08-23

    An ion mobility sensor which can detect both ion and molecules simultaneously. Thus, one can measure the relative arrival times between various ions and molecules. Different ions have different mobility in air, and the ion sensor enables measurement of ion mobility, from which one can identify the various ions and molecules. The ion mobility sensor which utilizes a pair of glow discharge devices may be designed for coupling with an existing gas chromatograph, where various gas molecules are already separated, but numbers of each kind of molecules are relatively small, and in such cases a conventional ion mobility sensor cannot be utilized.

  3. Ion Mobility-Mass Correlation Trend Line Separation of Glycoprotein Digests without Deglycosylation

    PubMed Central

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

    2013-01-01

    A high-throughput ion mobility mass spectrometer (IMMS) was used to rapidly separate and analyze peptides and glycopeptides derived from glycoproteins. Two glycoproteins, human α-1-acid glycoprotein and antithrombin III were digested with trypsin and subjected to electrospray traveling wave IMMS analysis. No deglycosylation steps were performed; samples were complex mixtures of peptides and glycopeptides. Peptides and glycosylated peptides with different charge states (up to 4 charges) were observed and fell on distinguishable trend lines in 2-D IMMS spectra in both positive and negative modes. The trend line separation patterns matched between both modes. Peptide sequence was identified based on the corresponding extracted mass spectra and collision induced dissociated (CID) experiments were performed for selected compounds to prove class identification. The signal-to-noise ratio of the glycopeptides was increased dramatically with ion mobility trend line separation compared to non-trend line separation, primarily due to selection of precursor ion subsets within specific mobility windows. In addition, isomeric mobility peaks were detected for specific glycopeptides. IMMS demonstrated unique capabilities and advantages for investigating and separating glycoprotein digests in this study and suggests a novel strategy for rapid glycoproteomics studies in the future. PMID:23914139

  4. Improved Differential Ion Mobility Separations Using Linked Scans of Carrier Gas Composition and Compensation Field

    NASA Astrophysics Data System (ADS)

    Santiago, Brandon G.; Harris, Rachel A.; Isenberg, Samantha L.; Ridgeway, Mark E.; Pilo, Alice L.; Kaplan, Desmond A.; Glish, Gary L.

    2015-07-01

    Differential ion mobility spectrometry (DIMS) separates ions based on differences in their mobilities in low and high electric fields. When coupled to mass spectrometric analyses, DIMS has the ability to improve signal-to-background by eliminating isobaric and isomeric compounds for analytes in complex mixtures. DIMS separation power, often measured by resolution and peak capacity, can be improved through increasing the fraction of helium in the nitrogen carrier gas. However, because the mobility of ions is higher in helium, a greater number of ions collide with the DIMS electrodes or housing, yielding losses in signal intensity. To take advantage of the benefits of helium addition on DIMS separations and reduce ion losses, linked scans were developed. In a linked scan the helium content of the carrier gas is reduced as the compensation field is increased. Linked scans were compared with conventional compensation field scans with constant helium content for the protein ubiquitin and a tryptic digest of bovine serum albumin (BSA). Linked scans yield better separation of ubiquitin charge states and enhanced peak capacities for the analysis of BSA compared with compensation field scans with constant helium carrier gas percentages. Linked scans also offer improved signal intensity retention in comparison to compensation field scans with constant helium percentages in the carrier gas.

  5. Differential Ion Mobility Separations of Peptides with Resolving Power Exceeding 50

    PubMed Central

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

    2010-01-01

    Differential ion mobility spectrometry (IMS) or field asymmetric waveform IMS (FAIMS) sorts gas-phase ions by mobility differences with respect to the electric field intensity. A major emerging FAIMS application is the fractionation of proteolytic digests. Using a planar FAIMS unit with helium/nitrogen mixtures, we have increased FAIMS resolving powers for peptide analyses from the prior maximum of ~20 – 30 to ~50 – 70. The resolution improved nearly 3-fold, allowing, in particular, separation of previously unresolved conformers. PMID:19938817

  6. Feasibility of Higher-Order Differential Ion Mobility Separations Using New Asymmetric Waveforms

    PubMed Central

    Shvartsburg, Alexandre A.; Mashkevich, Stefan V.; Smith, Richard D.

    2011-01-01

    Technologies for separating and characterizing ions based on their transport properties in gases have been around for three decades. The early method of ion mobility spectrometry (IMS) distinguished ions by absolute mobility that depends on the collision cross section with buffer gas atoms. The more recent technique of field asymmetric waveform IMS (FAIMS) measures the difference between mobilities at high and low electric fields. Coupling IMS and FAIMS to soft ionization sources and mass spectrometry (MS) has greatly expanded their utility, enabling new applications in biomedical and nanomaterials research. Here, we show that time-dependent electric fields comprising more than two intensity levels could, in principle, effect an infinite number of distinct differential separations based on the higher-order terms of expression for ion mobility. These analyses could employ the hardware and operational procedures similar to those utilized in FAIMS. Methods up to the 4th or 5th order (where conventional IMS is 1st order and FAIMS is 2nd order) should be practical at field intensities accessible in ambient air, with still higher orders potentially achievable in insulating gases. Available experimental data suggest that higher-order separations should be largely orthogonal to each other and to FAIMS, IMS, and MS. PMID:16494377

  7. Enhancing Biological Analyses with Three Dimensional Field Asymmetric Ion Mobility, Low Field Drift Time Ion Mobility and Mass Spectrometry (µFAIMS/IMS-MS) Separations

    SciTech Connect

    Zhang, Xing; Ibrahim, Yehia M.; Chen, Tsung-Chi; Kyle, Jennifer E.; Norheim, Randolph V.; Monroe, Matthew E.; Smith, Richard D.; Baker, Erin Shammel

    2015-06-30

    We report the first evaluation of a platform coupling a high speed field asymmetric ion mobility spectrometry microchip (µFAIMS) with drift tube ion mobility and mass spectrometry (IMS-MS). The µFAIMS/IMS-MS platform was used to analyze biological samples and simultaneously acquire multidimensional information of detected features from the measured FAIMS compensation fields and IMS drift times, while also obtaining accurate ion masses. These separations thereby increase the overall separation power, resulting increased information content, and provide more complete characterization of more complex samples. The separation conditions were optimized for sensitivity and resolving power by the selection of gas compositions and pressures in the FAIMS and IMS separation stages. The resulting performance provided three dimensional separations, benefitting both broad complex mixture studies and targeted analyses by e.g. improving isomeric separations and allowing detection of species obscured by “chemical noise” and other interfering peaks.

  8. Ion Mobility Separation of Variant Histone Tails Extending to the “Middle-down” Range

    SciTech Connect

    Shvartsburg, Alexandre A.; Zheng, Yupeng; Smith, Richard D.; Kelleher, Neil

    2012-05-15

    Differential ion mobility spectrometry (FAIMS) can baseline-resolve multiple variants of post-translationally modified peptides extending to the 3 - 4 kDa range, which differ in the localization of a PTM as small as acetylation. Essentially orthogonal separations for different charge states expand the total achievable peak capacity in proportion to the number of observed states that increases for longer polypeptides. This might enable resolving localization variants for even larger peptides and intact proteins.

  9. Separation of Peptide Isomers with Variant Modified Sites by High-Resolution Differential Ion Mobility Spectrometry

    PubMed Central

    Shvartsburg, Alexandre A.; Creese, Andrew J.; Smith, Richard D.; Cooper, Helen J.

    2010-01-01

    Many proteins and proteolytic peptides incorporate the same post-translational modification (PTM) at different sites, creating multiple localization variants with different functions or activities that may coexist in cells. Current analytical methods based on liquid chromatography (LC) followed by tandem mass spectrometry (MS/MS) are challenged by such isomers that often co-elute in LC and/or produce non-unique fragment ions. The application of ion mobility spectrometry (IMS) was explored, but success has been limited by insufficient resolution. We show that high-resolution differential ion mobility spectrometry (FAIMS) employing helium-rich gases can readily separate phosphopeptides with variant modification sites. Use of He/N2 mixtures containing up to 74% He has allowed separating to >95% three monophosphorylated peptides of identical sequence. Similar separation was achieved at 50% He, using an elevated electric field. Bisphosphorylated isomers that differ in only one modification site were separated to the same extent. We anticipate FAIMS capabilities for such separations to extend to other PTMs. PMID:20843012

  10. High-Resolution Differential Ion Mobility Separations Using Planar Analyzers at Elevated Dispersion Field

    PubMed Central

    Prior, David C.; Tang, Keqi; Smith, Richard D.

    2010-01-01

    The ion mobility spectrometry (IMS) methods are grouped into conventional IMS, based on the absolute ion mobility, and differential or field asymmetric waveform IMS (FAIMS), based on the mobility difference in strong and weak electric fields. A key attraction of FAIMS is substantial orthogonality to mass spectrometry (MS). Although several FAIMS/MS platforms were commercialized, their utility was limited by FAIMS resolving power, typically ∼10 - 20. Recently, gas mixtures comprising up to 75% He has enabled resolving power >100 that permits separation of numerous heretofore “co-eluting” isomers. This performance opens major new proteomic and other biological applications. Here, we show that raising the separation field by ∼35% over the previous 21 kV/cm provides similar or better resolution (with resolving powers of >200 for multiply-charged peptides) using only 50% He, which avoids problems due to elevated pressure and He content in the mass spectrometer. The heating of ions by the separation field in this regime exceeds that at higher He content but weaker field, inducing greater izomerization of labile species. PMID:20666414

  11. Enhancing Bottom-up and Top-down Proteomic Measurements with Ion Mobility Separations

    SciTech Connect

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

    2015-07-03

    Proteomic measurements with greater throughput, sensitivity and additional structural information enhance the in-depth characterization of complex mixtures and targeted studies with additional information and higher confidence. While liquid chromatography separation coupled with mass spectrometry (LC-MS) measurements have provided information on thousands of proteins in different sample types, the additional of another rapid separation stage providing structural information has many benefits for analyses. Technical advances in ion funnels and multiplexing have enabled ion mobility separations to be easily and effectively coupled with LC-MS proteomics to enhance the information content of measurements. 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.

  12. Enhancing Bottom-up and Top-down Proteomic Measurements with Ion Mobility Separations

    DOE PAGESBeta

    Baker, Erin Shammel; Burnum-Johnson, Kristin E.; Ibrahim, Yehia M.; Orton, Daniel J.; Monroe, Matthew E.; Kelly, Ryan T.; Moore, Ronald J.; Zhang, Xing; Theberge, Roger; Costello, Catherine E.; et al

    2015-07-03

    Proteomic measurements with greater throughput, sensitivity and additional structural information enhance the in-depth characterization of complex mixtures and targeted studies with additional information and higher confidence. While liquid chromatography separation coupled with mass spectrometry (LC-MS) measurements have provided information on thousands of proteins in different sample types, the additional of another rapid separation stage providing structural information has many benefits for analyses. Technical advances in ion funnels and multiplexing have enabled ion mobility separations to be easily and effectively coupled with LC-MS proteomics to enhance the information content of measurements. Finally, herein, we report on applications illustrating increased sensitivity, throughput,more » and structural information by utilizing IMS-MS and LC-IMS-MS measurements for both bottom-up and top-down proteomics measurements.« less

  13. Enhancing Bottom-up and Top-down Proteomic Measurements with Ion Mobility Separations

    SciTech Connect

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

    2015-07-03

    Proteomic measurements with greater throughput, sensitivity and additional structural information enhance the in-depth characterization of complex mixtures and targeted studies with additional information and higher confidence. While liquid chromatography separation coupled with mass spectrometry (LC-MS) measurements have provided information on thousands of proteins in different sample types, the additional of another rapid separation stage providing structural information has many benefits for analyses. Technical advances in ion funnels and multiplexing have enabled ion mobility separations to be easily and effectively coupled with LC-MS proteomics to enhance the information content of measurements. Finally, 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.

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

    PubMed Central

    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.

    2015-01-01

    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. PMID:26046661

  15. Separation of Protein Conformers by Differential Ion Mobility in Hydrogen-Rich Gases

    PubMed Central

    Shvartsburg, Alexandre A.; Smith, Richard D.

    2013-01-01

    Proteins in solution or the gas phase tend to exhibit multiple conformational families, each comprising distinct structures. Separation methods have generally failed to resolve these, with their convolution producing wide peaks. Here we report full separation of >10 conformers for most ubiquitin charge states by the new approach of differential ion mobility spectrometry (FAIMS) employing H2/N2 gas mixtures with up to 85% H2. The resolving power (up to 400) is five times the highest previously achieved (using He/N2 buffers), greatly increasing the separation specificity. The peak widths match the narrowest obtained by FAIMS for any species under same conditions and scale with the protein charge state (z) and ion residence time (t) as z−1/2 and t−1/2, as prescribed for instrumental (diffusional) broadening. This suggests resolution of specific geometries rather than broader ensembles. PMID:23855890

  16. Separation of Protein Conformers by Differential Ion Mobility in Hydrogen-Rich Gases

    SciTech Connect

    Shvartsburg, Alexandre A.; Smith, Richard D.

    2013-06-25

    Proteins in solution or the gas phase tend to exhibit multiple conformational families, each comprising distinct structures. Separation methods have generally failed to resolve these, with their convolution producing wide peaks. Here we report full separation of >10 conformers for most ubiquitin charge states by the new approach of differential ion mobility spectrometry (FAIMS) employing H2/N2 gas mixtures with up to 85% H2. The resolving power (up to 400) is five times the highest previously achieved (using He/N2 buffers), greatly increasing the separation specificity. The peak widths match the narrowest obtained by FAIMS for any species under same conditions and scale with the protein charge state (z) and ion residence time (t) as z-1/2 and t-1/2, as prescribed for instrumental (diffusional) broadening. This suggests resolution of specific geometries rather than broader ensembles.

  17. Separation of Peptide Isomers with Variant Modified Sites by High-Resolution Differential Ion Mobility Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.; Creese, Andrew; Smith, Richard D.; Cooper, Helen J.

    2010-10-01

    Many proteins and proteolytic peptides incorporate the same post-translational modification (PTM) at different sites, creating multiple localization variants with different functions or activities that may coexist in cells. Current analytical methods based on liquid chromatography (LC) followed by tandem mass spectrometry (MS/MS) are challenged by such isomers that often co-elute in LC and/or produce non-unique fragments. Application of ion mobility spectrometry (IMS) has previously been explored, but success was limited by insufficient resolution. We show that the recently developed high-resolution differential ion mobility spectrometry (FAIMS) using helium-rich gases can readily separate phosphopeptides with variant modified sites. Specifically, use of He/N2 mixtures containing up to 74% He has allowed separating to >95% three monophosphorylated peptides of identical sequence. Similar separation was achieved at 50% He, using an elevated electric field. Bisphosphorylated isomers that differ in only one modification site were separated to the same extent. We anticipate the FAIMS capabilities for such separations to extend to other PTMs.

  18. Characterizing the resolution and accuracy of a second-generation traveling-wave ion mobility separator for biomolecular ions.

    PubMed

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

    2011-09-01

    High-accuracy, high-resolution ion mobility measurements enable a vast array of important contemporary applications in biological chemistry. With the recent advent of both new, widely available commercial instrumentation and also new calibration datasets tailored for the aforementioned commercial instrumentation, the possibilities for extending such high performance measurements to a diverse set of applications have never been greater. Here, we assess the performance characteristics of a second-generation traveling-wave ion mobility separator, focusing on those figures of merit that lead to making measurements of collision cross-section having both high precision and high accuracy. Through performing a comprehensive survey of instrument parameters and settings, we find instrument conditions for optimized drift time resolution, cross-section resolution, and cross-section accuracy for a range of peptide, protein and multi-protein complex ions. Moreover, the conditions for high accuracy IM results are significantly different from those optimized for separation resolution, indicating that a balance between these two metrics must be attained for traveling wave IM separations of biomolecules. We also assess the effect of ion heating during IM separation on instrument performance. PMID:21445388

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

    PubMed Central

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

    2014-01-01

    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. PMID:24402673

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

    SciTech Connect

    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.

  1. Ultrahigh-Resolution Differential Ion Mobility Spectrometry Using Extended Separation Times

    PubMed Central

    Smith, Richard D.

    2010-01-01

    Ion mobility spectrometry (IMS), and particularly differential IMS or FAIMS, is emerging as a versatile tool for separation and identification of gas-phase ions, especially in conjunction with mass spectrometry. For over two decades since its inception, the utility of FAIMS was constrained by resolving power (R) of less than ~20. Stronger electric fields and optimized gas mixtures have recently raised achievable R to ~200, but further progress with such approaches is impeded by electrical breakdown. However, the resolving power of planar FAIMS devices using any gas and field intensity scales as the square root of separation time (t). Here, we extended t from the previous maximum of 0.2 s up to fourfold by reducing the carrier gas flow and increased the resolving power by up to twofold as predicted, to >300 for multiply-charged peptides. The resulting resolution gain has enabled separation of previously “co-eluting” peptide isomers, including folding conformers and localization variants of modified peptides. More broadly, a peak capacity of ~200 has been reached in tryptic digest separations. PMID:21117630

  2. Separation of catechin epimers by complexation using ion mobility mass spectrometry.

    PubMed

    Troć, Anna; Zimnicka, Magdalena; Danikiewicz, Witold

    2015-03-01

    Ion mobility coupled with mass spectrometry provides a fast and repeatable method to separate catechin epimers by previous complexation with selected chiral modifiers and transition metals. Several combinations with chiral ligands such as D- and L-amino acids and/or additional metal cations, chiral crown ethers, tartaric acid and heptakis(2,6-di-O-methyl)-β-cyclodextrin were screened for their ability to affect the separation efficiency. The clusters having the form of [2M + D-amino acid + Cu(2+) - 3H](-) (M stands for (-)-epicatechin or (+)-catechin) showed improvement in stereodifferentiation between two epimeric catechins in comparison to the analysis of pure epimers, where no separation was observed or the separation was hampered by the formation of mixed dimer complexes. Among various examined D-amino acids only those possessing hydrophobic side chains induced the improvement of separation efficiency. The best peak-to-peak resolution (Rp-p) was determined to be 0.71 for [2M + D-Leucine + Cu(2+) - 3H](-) clusters. PMID:25800190

  3. Using a Buffer Gas Modifier to Change Separation Selectivity in Ion Mobility Spectrometry

    PubMed Central

    Fernández-Maestre, Roberto; Wu, Ching; Hill, Herbert H.

    2010-01-01

    The mobilities of a set of common α-amino acids, four tetraalkylammonium ions, 2,4-dimethyl pyridine (2,4-lutidine), 2,6-di-tert-butyl pyridine (DTBP), and valinol were determined using electrospray ionization-ion mobility spectrometry-quadrupole mass spectrometry (ESI-IMS-QMS) while introducing 2-butanol into the buffer gas. The mobilities of the test compounds decreased by varying extents with 2-butanol concentration in the mobility spectrometer. When the concentration of 2-butanol increased from 0.0 to 6.8 mmol m−3 (2.5×102 ppmv), percentage reductions in mobilities were: 13.6% (serine), 12.2% (threonine), 10.4% (methionine), 10.3% (tyrosine), 9.8% (valinol), 9.2% (phenylalanine), 7.8% (tryptophan), 5.6% (2,4-lutidine), 2.2% (DTBP), 1.0% (tetramethylammonium ion, TMA, and tetraethylammonium ion, TEA), 0.0% (tetrapropylammonium ion, TPA), and 0.3% (tetrabutylammonium ion, TBA). These variations in mobility depended on the size and steric hindrance on the charge of the ions, and were due to formation of large ion-2-butanol clusters. This selective variation in mobilities was applied to the resolution of a mixture of compounds with similar reduced mobilities such as serine and valinol, which overlapped in N2-only buffer gas in the IMS spectrum. The relative insensitivity of tetraalkylammonium ions and DTBP to the introduction of 2-butanol into the buffer gas was explained by steric hindrance of the four alkyl substituents in tetraalkylammonium ions and the two tert-butyl groups in DTBP, which shielded the positive charge of the ion from the attachment of 2-butanol molecules. Low buffer gas temperatures (100 °C) produced the largest reductions in mobilities by increasing ion-2-butanol interactions and formation of clusters; high temperatures (250 °C) prevented the formation of clusters, and no reduction in ion mobility was obtained with the introduction of 2-butanol into the buffer gas. Low temperatures and high concentrations of 2-butanol produced a series of

  4. The Influence of Drift Gas Composition on the Separation Mechanism in Traveling Wave Ion Mobility Spectrometry: Insight from Electrodynamic Simulations

    PubMed Central

    May, Jody C.; McLean, John A.

    2013-01-01

    The influence of three different drift gases (helium, nitrogen, and argon) on the separation mechanism in traveling wave ion mobility spectrometry is explored through ion trajectory simulations which include considerations for ion diffusion based on kinetic theory and the electrodynamic traveling wave potential. The model developed for this work is an accurate depiction of a second-generation commercial traveling wave instrument. Three ion systems (cocaine, MDMA, and amphetamine) whose reduced mobility values have previously been measured in different drift gases are represented in the simulation model. The simulation results presented here provide a fundamental understanding of the separation mechanism in traveling wave, which is characterized by three regions of ion motion: (1) ions surfing on a single wave, (2) ions exhibiting intermittent roll-over onto subsequent waves, and (3) ions experiencing a steady state roll-over which repeats every few wave cycles. These regions of ion motion are accessed through changes in the gas pressure, wave amplitude, and wave velocity. Resolving power values extracted from simulated arrival times suggest that momentum transfer in helium gas is generally insufficient to access regions (2) and (3) where ion mobility separations occur. Ion mobility separations by traveling wave are predicted to be effectual for both nitrogen and argon, with slightly lower resolving power values observed for argon as a result of band-broadening due to collisional scattering. For the simulation conditions studied here, the resolving power in traveling wave plateaus between regions (2) and (3), with further increases in wave velocity contributing only minor improvements in separations. PMID:23888124

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

    PubMed

    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. PMID:22006241

  6. Separation and characterization of oxidized isomeric lipid-peptide adducts by ion mobility mass spectrometry.

    PubMed

    Milic, Ivana; Kipping, Marc; Hoffmann, Ralf; Fedorova, Maria

    2015-12-01

    Phospholipids are major components of cell membranes and lipoprotein complexes. They are prone to oxidation by endogenous and exogenous reactive oxygen species yielding a large variety of modified lipids including small aliphatic and phospholipid bound aldehydes and ketones. These carbonyls are strong electrophiles that can modify proteins and, thereby, alter their structures and functions triggering various pathophysiological conditions. The analysis of lipid-protein adducts by liquid chromatography-MS is challenged by their mixed chemical nature (polar peptide and hydrophobic lipid), low abundance in biological samples, and formation of multiple isomers. Thus, we investigated traveling wave ion mobility mass spectrometry (TWIMS) to analyze lipid-peptide adducts generated by incubating model peptides corresponding to the amphipathic β1 sheet sequence of apolipoprotein B-100 with 1-palmitoyl-2-(oxo-nonanoyl)-sn-glycerophosphatidylcholine (PONPC). The complex mixture of peptides, lipids, and peptide-lipid adducts was separated by TWIMS, which was especially important for the identification of two mono-PONPC-peptide isomers containing Schiff bases at different lysine residues. Moreover, TWIMS separated structural conformers of one peptide-lipid adduct possessing most likely different orientations of the hydrophobic sn-1 fatty acyl residue and head group of PONPC, relative to the peptide backbone. PMID:26634972

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Ion mobility-mass spectrometry.

    PubMed

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

    2008-01-01

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

  9. Multi-Component Ion Modifiers and Arcing Suppressants to Enhance Differential Mobility Spectrometry for Separation of Peptides and Drug Molecules

    NASA Astrophysics Data System (ADS)

    Blagojevic, Voislav; Koyanagi, Gregory K.; Bohme, Diethard K.

    2014-03-01

    The optimization of ion/molecule chemistry in a differential mobility spectrometer (DMS) is shown to result in improved peak capacity, separation, and sensitivity. We have experimented with a modifier composed of multiple components, where each component accomplishes a specific task on mixtures of peptides and small drug molecules. Use of a higher proton affinity modifier (hexanol) provides increased peak capacity and separation. Analyte ion/modifier proton transfer is suppressed by adding a large excess of low proton affinity modifier (water or methanol), significantly increasing signal intensity and sensitivity for low proton affinity analytes. Finally, addition of an electrical arcing suppressant (chloroform) allows the device to operate reliably at higher separation fields, improving peak capacity and separation. We demonstrate a 20 % increase in the device peak capacity without any loss of sensitivity and estimate that further optimization of the modifier composition can increase this to 50 %. Use of 3-, 4-, or even 5-component modifiers offers the opportunity for the user to fine-tune the modifier performance to maximize the device performance, something not possible with a single component modifier.

  10. Identification and separation of saxitoxins using hydrophilic interaction liquid chromatography coupled to traveling wave ion mobility-mass spectrometry.

    PubMed

    Poyer, Salomé; Loutelier-Bourhis, Corinne; Coadou, Gaël; Mondeguer, Florence; Enche, Julien; Bossée, Anne; Hess, Philipp; Afonso, Carlos

    2015-01-01

    The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non-sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non-sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC-IM-MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non-sulphated analogues were separated in the IM-MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM-MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method. PMID:25601690

  11. Ion mobility sensor system

    DOEpatents

    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.

  12. Separation and Identification of Isomeric Glycans by Selected Accumulation-Trapped Ion Mobility Spectrometry-Electron Activated Dissociation Tandem Mass Spectrometry.

    PubMed

    Pu, Yi; Ridgeway, Mark E; Glaskin, Rebecca S; Park, Melvin A; Costello, Catherine E; Lin, Cheng

    2016-04-01

    One of the major challenges in structural characterization of oligosaccharides is the presence of many structural isomers in most naturally occurring glycan mixtures. Although ion mobility spectrometry (IMS) has shown great promise in glycan isomer separation, conventional IMS separation occurs on the millisecond time scale, largely restricting its implementation to fast time-of-flight (TOF) analyzers which often lack the capability to perform electron activated dissociation (ExD) tandem MS analysis and the resolving power needed to resolve isobaric fragments. The recent development of trapped ion mobility spectrometry (TIMS) provides a promising new tool that offers high mobility resolution and compatibility with high-performance Fourier transform ion cyclotron resonance (FTICR) mass spectrometers when operated under the selected accumulation-TIMS (SA-TIMS) mode. Here, we present our initial results on the application of SA-TIMS-ExD-FTICR MS to the separation and identification of glycan linkage isomers. PMID:26959868

  13. Ultrahigh-Resolution Differential Ion Mobility Separations of Conformers for Proteins above 10 kDa: Onset of Dipole Alignment?

    SciTech Connect

    Shvartsburg, Alexandre A.

    2014-11-04

    Biomacromolecules tend to assume numerous structures in solution or the gas phase. It has been possible to resolve disparate conformational families but not unique geometries within each, and drastic peak broadening has been the bane of protein analyses by chromatography, electrophoresis, and ion mobility spectrometry (IMS). The new differential IMS (FAIMS) approach using hydrogen-rich gases was recently found to separate conformers of a small protein ubiquitin with same peak width and resolving power up to ~400 as for peptides. Present work explores the reach of this approach for larger proteins, exemplified by cytochrome c and myoglobin. Resolution similar to that for ubiquitin was largely achieved with longer separations, while the onset of peak broadening and coalescence with shorter separations suggests the limitation of present technique to proteins under ~20 kDa. This capability may enable distinguishing whole proteins with differing residue sequences or localizations of posttranslational modifications. Small features at negative compensation voltages that markedly grow from cytochrome c to myoglobin indicate the dipole alignment of rare conformers in accord with theory, further supporting the concept of pendular macroions in FAIMS.

  14. SEPARATION OF PLUTONYL IONS

    DOEpatents

    Connick, R.E.; McVey, Wm.H.

    1958-07-15

    A process is described for separating plutonyl ions from the acetate ions with which they are associated in certaln carrier precipitation methods of concentrating plutonium. The method consists in adding alkaline earth metal ions and subsequently alkalizing the solution, causing formation of an alkaltne earth plutonate precipitate. Barium hydroxide is used in a preferred embodiment since it provides alkaline earth metal ion and alkalizes the solution in one step forming insoluble barium platonate.

  15. Correlation ion mobility spectroscopy

    DOEpatents

    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.

  16. Rapid assessment of human amylin aggregation and its inhibition by copper(II) ions by laser ablation electrospray ionization mass spectrometry with ion mobility separation.

    PubMed

    Li, Hang; Ha, Emmeline; Donaldson, Robert P; Jeremic, Aleksandar M; Vertes, Akos

    2015-10-01

    Native electrospray ionization (ESI) mass spectrometry (MS) is often used to monitor noncovalent complex formation between peptides and ligands. The relatively low throughput of this technique, however, is not compatible with extensive screening. Laser ablation electrospray ionization (LAESI) MS combined with ion mobility separation (IMS) can analyze complex formation and provide conformation information within a matter of seconds. Islet amyloid polypeptide (IAPP) or amylin, a 37-amino acid residue peptide, is produced in pancreatic beta-cells through proteolytic cleavage of its prohormone. Both amylin and its precursor can aggregate and produce toxic oligomers and fibrils leading to cell death in the pancreas that can eventually contribute to the development of type 2 diabetes mellitus. The inhibitory effect of the copper(II) ion on amylin aggregation has been recently discovered, but details of the interaction remain unknown. Finding other more physiologically tolerated approaches requires large scale screening of potential inhibitors. Here, we demonstrate that LAESI-IMS-MS can reveal the binding stoichiometry, copper oxidation state, and the dissociation constant of human amylin-copper(II) complex. The conformations of hIAPP in the presence of copper(II) ions were also analyzed by IMS, and preferential association between the β-hairpin amylin monomer and the metal ion was found. The copper(II) ion exhibited strong association with the -HSSNN- residues of the amylin. In the absence of copper(II), amylin dimers were detected with collision cross sections consistent with monomers of β-hairpin conformation. When copper(II) was present in the solution, no dimers were detected. Thus, the copper(II) ions disrupt the association pathway to the formation of β-sheet rich amylin fibrils. Using LAESI-IMS-MS for the assessment of amylin-copper(II) interactions demonstrates the utility of this technique for the high-throughput screening of potential inhibitors of amylin

  17. Rapid Assessment of Human Amylin Aggregation and Its Inhibition by Copper(II) Ions by Laser Ablation Electrospray Ionization Mass Spectrometry with Ion Mobility Separation

    PubMed Central

    Donaldson, Robert P.; Jeremic, Aleksandar M.; Vertes, Akos

    2015-01-01

    Native electrospray ionization (ESI) mass spectrometry (MS) is often used to monitor noncovalent complex formation between peptides and ligands. The relatively low throughput of this technique, however, is not compatible with extensive screening. Laser ablation electrospray ionization (LAESI) MS combined with ion mobility separation (IMS) can analyze complex formation and provide conformation information within a matter of seconds. Islet amyloid polypeptide (IAPP) or amylin, a 37-amino acid residue peptide, is produced in pancreatic beta-cells through proteolytic cleavage of its prohormone. Both amylin and its precursor can aggregate and produce toxic oligomers and fibrils leading to cell death in the pancreas that can eventually contribute to the development of type 2 diabetes mellitus. The inhibitory effect of the copper(II) ion on amylin aggregation has been recently discovered, but details of the interaction remain unknown. Finding other more physiologically tolerated approaches requires large scale screening of potential inhibitors. Here, we demonstrate that LAESI-IMS-MS can reveal the binding stoichiometry, copper oxidation state, and the dissociation constant of human amylin–copper(II) complex. The conformations of hIAPP in the presence of copper(II) ions were also analyzed by IMS, and preferential association between the β-hairpin amylin monomer and the metal ion was found. The copper(II) ion exhibited strong association with the –HSSNN– residues of the amylin. In the absence of copper(II), amylin dimers were detected with collision cross sections consistent with monomers of β-hairpin conformation. When copper(II) was present in the solution, no dimers were detected. Thus, the copper(II) ions disrupt the association pathway to the formation of β-sheet rich amylin fibrils. Using LAESI-IMS-MS for the assessment of amylin–copper(II) interactions demonstrates the utility of this technique for the high-throughput screening of potential inhibitors of

  18. Miniaturized Ion Mobility Spectrometer

    NASA Technical Reports Server (NTRS)

    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.

  19. Gas-phase separation of drugs and metabolites using modifier-assisted differential ion mobility spectrometry hyphenated to liquid extraction surface analysis and mass spectrometry.

    PubMed

    Porta, Tiffany; Varesio, Emmanuel; Hopfgartner, Gérard

    2013-12-17

    The present work describes an alternative generic approach to LC-MS for the analysis of drugs of abuse as well as their metabolites in post-mortem tissue samples. The platform integrates liquid extraction surface analysis (LESA) for analytes tissue extraction followed by differential ion mobility spectrometry (DMS) mass spectrometry for analytes gas phase separation. Detection is performed on a triple quadrupole linear ion trap using the selected reaction monitoring mode for quantification as well as product ion scan mode for structural confirmatory analyses. The major advantages of the platform are that neither chromatographic separation nor extensive sample preparation are required. In DMS the combination of a high separation voltage (i.e., up to 4 kV) together with organic modifiers (e.g., alcohols, acetonitrile, acetone) added in the drift gas is required to achieve the separation of isomeric metabolites, such as the ones of cocaine and tramadol. DMS also separates morphine from its glucuronide metabolites, which allows for preventing the overestimation of morphine in case of fragmentation of the glucuronides in the atmospheric-to-vacuum interface of the mass spectrometer. Cocaine, opiates, opioids, amphetamines, benzodiazepines and several of their metabolites could be identified in post-mortem human kidney and muscle tissue based on simultaneous screening and confirmatory analysis in data-dependent acquisition mode using an analyte-dependent compensation voltage to selectively transmit ions through the DMS cell to the mass analyzer. Quantitative performance of the LESA-DMS-MS platform was evaluated for cocaine and two of its metabolites spotted onto a tissue section using deuterated internal standard. Analyte's responses were linear from 2 to 1000 pg on tissue corresponding to a limit of detection in the order of nanograms of analyte per gram of tissue. Accuracy and precision based on QC sample was found to be less than 10%. Replicate analyses of cocaine and

  20. Ion dynamics in a trapped ion mobility spectrometer†

    PubMed Central

    Hernandez, Diana Rosa; DeBord, John Daniel; Ridgeway, Mark E.; Kaplan, Desmond A.; Park, Melvin A.; Fernandez-Lima, Francisco

    2014-01-01

    In the present paper, theoretical simulations and experimental observations are used to describe the ion dynamics in a trapped ion mobility spectrometer. In particular, the ion motion, ion transmission and mobility separation are discussed as a function of the bath gas velocity, radial confinement, analysis time and speed. Mobility analysis and calibration procedure are reported for the case of sphere-like molecules for positive and negative ion modes. Results showed that a maximal mobility resolution can be achieved by optimizing the gas velocity, radial confinement (RF amplitude) and ramp speed (voltage range and ramp time). The mobility resolution scales with the electric field and gas velocity and R = 100–250 can be routinely obtained at room temperature. PMID:24571000

  1. Coulomb Repulsion in Miniature Ion Mobility Spectrometry

    SciTech Connect

    Xu, J.; Whitten, W.B.; Ramsey, J.M.

    1999-08-08

    We have undertaken a study of ion mobility resolution in a miniature ion mobility spectrometer with a drift channel 1.7 mm in diameter and 35 mm in length. The device attained a maximum resolution of 14 in separating ions of NO, O{sub 2}, and methyl iodine. The ions were generated by pulses from a frequency-quadrupled Nd:YAG laser. Broadening due to Coulomb repulsion was modeled theoretically and shown experimentally to have a major effect on the resolution of the miniature device.

  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.

    PubMed

    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. PMID:26922843

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

    NASA Technical Reports Server (NTRS)

    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. Fundamentals of Trapped Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Michelmann, Karsten; Silveira, Joshua A.; Ridgeway, Mark E.; Park, Melvin A.

    2015-01-01

    Trapped ion mobility spectrometry (TIMS) is a relatively new gas-phase separation method that has been coupled to quadrupole orthogonal acceleration time-of-flight mass spectrometry. The TIMS analyzer is a segmented rf ion guide wherein ions are mobility-analyzed using an electric field that holds ions stationary against a moving gas, unlike conventional drift tube ion mobility spectrometry where the gas is stationary. Ions are initially trapped, and subsequently eluted from the TIMS analyzer over time according to their mobility ( K). Though TIMS has achieved a high level of performance ( R > 250) in a small device (<5 cm) using modest operating potentials (<300 V), a proper theory has yet to be produced. Here, we develop a quantitative theory for TIMS via mathematical derivation and simulations. A one-dimensional analytical model, used to predict the transit time and theoretical resolving power, is described. Theoretical trends are in agreement with experimental measurements performed as a function of K, pressure, and the axial electric field scan rate. The linear dependence of the transit time with 1/ K provides a fundamental basis for determination of reduced mobility or collision cross section values by calibration. The quantitative description of TIMS provides an operational understanding of the analyzer, outlines the current performance capabilities, and provides insight into future avenues for improvement.

  5. Structural characterization of synthetic polymers and copolymers using multidimensional mass spectrometry interfaced with thermal degradation, liquid chromatography and/or ion mobility separation

    NASA Astrophysics Data System (ADS)

    Alawani, Nadrah

    This dissertation focuses on coupling mass spectrometry (MS) and tandem mass spectrometry (MS/MS) to thermal degradation, liquid chromatography (LC) and/or ion mobility (IM) spectrometry for the characterization of complex mixtures. In chapter II, an introduction of the history and the principles of MS and LC are discussed. Chapter III illustrates the materials and instrumentation used to complete this dissertation. Polyethers have been characterized utilizing MS/MS, as presented in Chapter IV and Chapter VI. Diblock copolymers of polyethylene oxide and polycaprolactone, PEO-b-PCL, have been characterized by matrix-assisted laser desorption/ionization quadrupole/time-of-flight mass spectrometry (MALDI-Q/ToF) and LC-MS/MS (Chapter V). Thermoplastic elastomers have been characterized by thermal degradation using an atmospheric solids analysis probe (ASAP) and ion mobility mass spectrometry (IM-MS), as discussed in Chapter VII. Interfacing separation techniques with mass spectrometry permitted the detection of species present with low concentration in complex materials and improved the sensitivity of MS. In chapter IV, the fragmentation mechanisms in MS/MS experiments of cyclic and linear poly(ethylene oxide) macroinitiators are discussed. This study aimed at determining the influence of end groups on the fragmentation pathways. In the study reported in Chapter V, ultra high performance liquid chromatography (UHPLC) was interfaced with MS and MS/MS to achieve the separation and in-depth characterization and separation of amphiphilic diblock copolymers (PEO- b-PCL) in which the architecture of the PEO block is linear or cyclic. Applying UPLC-MS and UPLC-MS/MS provides fast accurate information about the number and type of the blocks in the copolymers. Chapter VI reports MS/MS and IM-MS analyses which were performed to elucidate the influence of molecular size and collision energy on the fragmentation pathways of polyethers subjected to collisionally activated

  6. Ion mobility spectrometers and methods for ion mobility spectrometry

    SciTech Connect

    Dahl, David A; Scott, Jill R; Appelhans, Anthony D; McJunkin, Timothy R; Olson, John E

    2009-04-14

    An ion mobility spectrometer may include an inner electrode and an outer electrode arranged so that at least a portion of the outer electrode surrounds at least a portion of the inner electrode and defines a drift space therebetween. The inner and outer electrodes are electrically insulated from one another so that a non-linear electric field is created in the drift space when an electric potential is placed on the inner and outer electrodes. An ion source operatively associated with the ion mobility spectrometer releases ions to the drift space defined between the inner and outer electrodes. A detector operatively associated with at least a portion of the outer electrode detects ions from the drift space.

  7. Ion Mobility Spectrometry (IMS) and Mass Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.

    2010-04-20

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

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

    PubMed

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

    2015-10-21

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

  9. One sign ion mobile approximation

    NASA Astrophysics Data System (ADS)

    Barbero, G.

    2011-12-01

    The electrical response of an electrolytic cell to an external excitation is discussed in the simple case where only one group of positive and negative ions is present. The particular case where the diffusion coefficients of the negative ions, Dm, is very small with respect to that of the positive ions, Dp, is considered. In this framework, it is discussed under what conditions the one mobile approximation, in which the negative ions are assumed fixed, works well. The analysis is performed by assuming that the external excitation is sinusoidal with circular frequency ω, as that used in the impedance spectroscopy technique. In this framework, we show that there exists a circular frequency, ω*, such that for ω > ω*, the one mobile ion approximation works well. We also show that for Dm ≪ Dp, ω* is independent of Dm.

  10. Material review of Li ion battery separators

    SciTech Connect

    Weber, Christoph J. Geiger, Sigrid; Falusi, Sandra; Roth, Michael

    2014-06-16

    Separators for Li Ion batteries have a strong impact on cell production, cell performance, life, as well as reliability and safety. The separator market volume is about 500 million m{sup 2} mainly based on consumer applications. It is expected to grow strongly over the next decade for mobile and stationary applications using large cells. At present, the market is essentially served by polyolefine membranes. Such membranes have some technological limitations, such as wettability, porosity, penetration resistance, shrinkage and meltdown. The development of a cell failure due to internal short circuit is potentially closely related to separator material properties. Consequently, advanced separators became an intense area of worldwide research and development activity in academia and industry. New separator technologies are being developed especially to address safety and reliability related property improvements.

  11. Material review of Li ion battery separators

    NASA Astrophysics Data System (ADS)

    Weber, Christoph J.; Geiger, Sigrid; Falusi, Sandra; Roth, Michael

    2014-06-01

    Separators for Li Ion batteries have a strong impact on cell production, cell performance, life, as well as reliability and safety. The separator market volume is about 500 million m2 mainly based on consumer applications. It is expected to grow strongly over the next decade for mobile and stationary applications using large cells. At present, the market is essentially served by polyolefine membranes. Such membranes have some technological limitations, such as wettability, porosity, penetration resistance, shrinkage and meltdown. The development of a cell failure due to internal short circuit is potentially closely related to separator material properties. Consequently, advanced separators became an intense area of worldwide research and development activity in academia and industry. New separator technologies are being developed especially to address safety and reliability related property improvements.

  12. Mobile ions on carbonate surfaces

    NASA Astrophysics Data System (ADS)

    Kendall, Treavor A.; Martin, Scot T.

    2005-07-01

    Surface ions move during the dissolution and growth of minerals. The present study investigates the density and the mobility of surface ions and the structure of the adsorbed water layer with changes in relative humidity (RH). The time evolution of the polarization force, which is induced by an electrically biased tip of an atomic force microscope, shows that the density and the mobility of surface ions increase with rising humidity, a finding which is consistent with increasing surface hydration. A marked change in the observations above 55% RH indicates a transition from a water layer formed by heteroepitaxial two-dimensional growth at low RH to one formed by multilayer three-dimensional growth at high RH. A comparison of the results of several rhombohedral carbonates ( viz. CaCO 3, FeCO 3, ZnCO 3, MgCO 3, and MnCO 3) shows that a long relaxation time of the polarization force at high RH is predictive of a rapid dissolution rate. This finding is rationalized by long lifetimes in terrace positions and hence greater opportunities for detachment of the ion to aqueous solution (i.e., dissolution). Our findings on the density and the mobility of surface ions therefore help to better constrain mechanistic models of hydration, ion exchange, and dissolution/growth.

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

    SciTech Connect

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

    2014-12-15

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

  14. Using differential mobility spectrometry to measure ion solvation: an examination of the roles of solvents and ionic structures in separating quinoline-based drugs.

    PubMed

    Liu, Chang; Le Blanc, J C Yves; Shields, Jefry; Janiszewski, John S; Ieritano, Christian; Ye, Gene F; Hawes, Gillian F; Hopkins, W Scott; Campbell, J Larry

    2015-10-21

    Understanding the mechanisms and energetics of ion solvation is critical in many scientific areas. Here, we present a methodlogy for studying ion solvation using differential mobility spectrometry (DMS) coupled to mass spectrometry. While in the DMS cell, ions experience electric fields established by a high frequency asymmetric waveform in the presence of a desired pressure of water vapor. By observing how a specific ion's behavior changes between the high- and low-field parts of the waveform, we gain knowledge about the aqueous microsolvation of that ion. In this study, we applied DMS to investigate the aqueous microsolvation of protonated quinoline-based drug candidates. Owing to their low binding energies with water, the clustering propensity of 8-substituted quinolinium ions was less than that of the 6- or 7-substituted analogues. We attribute these differences to the steric hinderance presented by subtituents in the 8-position. In addition, these experimental DMS results were complemented by extensive computational studies that determined cluster structures and relative thermodynamic stabilities. PMID:26165786

  15. Coulombic Effects in Ion Mobility Spectrometry

    PubMed Central

    Tolmachev, Aleksey V.; Clowers, Brian H.; Belov, Mikhail E.; Smith, Richard D.

    2009-01-01

    Ion mobility spectrometry (IMS) has been increasingly employed in a number of applications. When coupled to mass spectrometry (MS), IMS becomes a powerful analytical tool for separating complex samples and investigating molecular structure. Therefore, improvements in IMS-MS instrumentation, e.g. IMS resolving power and sensitivity, are highly desirable. Implementation of an ion trap for accumulation and pulsed ion injection to IMS based on the ion funnel has provided considerably increased ion currents, and thus a basis for improved sensitivity and measurement throughput. However, large ion populations may manifest Coulombic effects contributing to the spatial dispersion of ions traveling in the IMS drift tube, and reduction in the IMS resolving power. In this study, we present an analysis of Coulombic effects on IMS resolution. Basic relationships have been obtained for the spatial evolution of ion packets due to Coulombic repulsion. The analytical relationships were compared with results of a computer model that simulates IMS operation based on a first principles approach. Initial experimental results reported here are consistent with the computer modeling. A noticeable decrease in the IMS resolving power was observed for ion populations of >10,000 elementary charges. The optimum IMS operation conditions which would minimize the Coulombic effects are discussed. PMID:19438247

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

    PubMed Central

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

    2015-01-01

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

  17. Miniature Ion-Mobility Spectrometer

    NASA Technical Reports Server (NTRS)

    Hartley, Frank T.

    2006-01-01

    The figure depicts a proposed miniature ion-mobility spectrometer that would be fabricated by micromachining. Unlike prior ion-mobility spectrometers, the proposed instrument would not be based on a time-of-flight principle and, consequently, would not have some of the disadvantageous characteristics of prior time-of-flight ion-mobility spectrometers. For example, one of these characteristics is the need for a bulky carrier-gas-feeding subsystem that includes a shutter gate to provide short pulses of gas in order to generate short pulses of ions. For another example, there is need for a complex device to generate pulses of ions from the pulses of gas and the device is capable of ionizing only a fraction of the incoming gas molecules; these characteristics preclude miniaturization. In contrast, the proposed instrument would not require a carrier-gas-feeding subsystem and would include a simple, highly compact device that would ionize all the molecules passing through it. The ionization device in the proposed instrument would be a 0.1-micron-thick dielectric membrane with metal electrodes on both sides. Small conical holes would be micromachined through the membrane and electrodes. An electric potential of the order of a volt applied between the membrane electrodes would give rise to an electric field of the order of several megavolts per meter in the submicron gap between the electrodes. An electric field of this magnitude would be sufficient to ionize all the molecules that enter the holes. Ionization (but not avalanche arcing) would occur because the distance between the ionizing electrodes would be less than the mean free path of gas molecules at the operating pressure of instrument. An accelerating grid would be located inside the instrument, downstream from the ionizing membrane. The electric potential applied to this grid would be negative relative to the potential on the inside electrode of the ionizing membrane and would be of a magnitude sufficient to

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

    PubMed

    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. PMID:25068446

  19. Characterization of a new mobility separation tool: HRIMS as differential mobility analyzer.

    PubMed

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

    2014-12-01

    High resolution ion mobility spectrometer (HRIMS) is a new instrument that uses parallel plate Differential Mobility Analysis as principle of separation. Gas phase analysis of volatile organic compounds (VOCs) has been performed for the characterization of this new mobility system using an UV-lamp for ionization. Studies of the effect of temperature and the presence of a desiccant are detailed. Identification of the different peaks obtained with an electrometer was successfully carried out for a group of alcohols, aromatic compounds and ketones (ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-heptanol, acetone, 2-butanone, 2-pentanone, 2-octanone, benzene, toluene, xylene and bromobenzene) following a modified Millikan equation. Moreover, the investigation of the discrimination capabilities within the different VOCs families as well as the mobility dependence with molecular mass was successfully achieved. PMID:25159427

  20. Using Ion Exchange Chromatography to Separate and Quantify Complex Ions

    ERIC Educational Resources Information Center

    Johnson, Brian J.

    2014-01-01

    Ion exchange chromatography is an important technique in the separation of charged species, particularly in biological, inorganic, and environmental samples. In this experiment, students are supplied with a mixture of two substitution-inert complex ions. They separate the complexes by ion exchange chromatography using a "flash"…

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

    SciTech Connect

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

    2014-10-07

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

  2. Developing liquid chromatography ion mobility mass spectometry techniques.

    PubMed

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

    2005-08-01

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

  3. Chemical Standards in Ion Mobility Spectrometry

    PubMed Central

    Fernández-Maestre, Roberto; Harden, Charles Steve; Ewing, Robert Gordon; Crawford, Christina Lynn; Hill, Herbert Henderson

    2010-01-01

    In ion mobility spectrometry (IMS), reduced mobility values (K0) are used as a qualitative measure of gas phase ions, and are reported in the literature as absolute values. Unfortunately, these values do not always match those collected in the field. One reason for this discrepancy is that the buffer gas may be contaminated with moisture or other volatile compounds. In this study, the effect of moisture and organic contaminants in the buffer gas on the mobility of IMS standards and analytes was investigated for the first time using IMS directly coupled to mass spectrometry. 2,4-dimethylpyridine, 2,6-di-tert-butyl pyridine (DTBP), and tetrabutylammonium, tetrapropylammonium, tetraethylammonium, and tetramethylammonium chlorides were used as chemical standards. In general, the mobility of IMS standard product ions was not affected by small amounts of contamination while the mobilities of many analytes were affected. In the presence of contaminants in the buffer gas, the mobility of analyte ions is often decreased by forming ion-molecule clusters with the contaminant. To ensure the measurement of accurate reduced mobility values, two IMS standards are required: an instrument and a mobility standard. An instrument standard is not affected by contaminants in the buffer gas, and provides an accurate measurement of the instrumental parameters, such as voltage, drift length, pressure, and temperature. The mobility standard behaves like an analyte ion in that the compound’s mobility is affected by low levels of contamination in the buffer gas. Prudent use of both of these standards can lead to improved measurement of accurate reduced mobility values. PMID:20369157

  4. Ion separations based on electrical potentials nanoporous and microporous membranes

    NASA Astrophysics Data System (ADS)

    Armstrong, Jason

    This dissertation examines several types of ion separations in nanometer to micrometer pores in membranes. Membranes provide an attractive platform for ion separations, primarily because they operate continuously (i.e. not in a batch mode), and small pores offer the potential for ion separation based on charge and electrophoretic mobility differences. Initial studies employed charged, nanoporous membranes to separate monovalent and divalent ions. Adsorption of polyelectrolyte multilayers in nanoporous membranes afforded control over the surface charge and pore radii in track-etched membranes, and electrostatic ion-exclusion, particularly for divalent ions, occurred in these membranes because the electrical double layer filled the entire nanopore. Initial experiments employed adsorption of (PSS/PAH) multilayers in the 50-nm diameter pores of PCTE membranes to give a K+/Mg2+ selectivity of ~10 in pressure-driven dead-end filtration. Adsorption of (PSS/PAH) 1 films in 30-nm pores gave a similar K+/Mg2+ selectivity with a simpler modification procedure. Separations utilizing (PSS/PAH)1 films in 30-nm pores showed the lowest ion rejections with high ion concentrations, consistent with enhanced screening of the electrical double layer at high ionic strength. However, solutions with < 5 mM ionic strength exhibited essentially 100% Mg2+ rejections (the Mg2+ concentration in the permeate was below the method detection limit). Moreover, K+ rejections increased in the presence of Mg2+, which may stem from Mg2+-adsorption within the PEM and increased surface charge. Finally, separation of Br- and SO42- with a PSS1-modified, 30-nm PCTE membrane validated the exclusion mechanism for anions. The average Br-/SO42- selectivity was 3.4 +/- 0.8 for a solution containing 0.5 mM NaBr and 0.5 mM Na2SO4. The low selectivity in this case likely stems from a relatively large pore. The membranes used for the separation of monovalent and divalent ions also facilitated separation of

  5. Chemical standards in ion mobility spectrometry

    SciTech Connect

    Fernandez-Maestre, Robert; Harden, Charles S.; Ewing, Robert G.; Crawford, Christina L.; Hill, Jr, Herbert H.

    2010-08-01

    In ion mobility spectrometry (IMS), reduced mobility values (K0) are used as a qualitative measure of gas phase ions, and are reported in the literature as absolute values. Unfortunately, these values do not always match with those collected in the field. One reason for this discrepancy is that the buffer gas may be contaminated with moisture or other volatile compounds. In this study, the effect of moisture and organic contaminants in the buffer gas on the mobility of IMS standards and analytes was investigated for the first time using IMS directly coupled to mass spectrometry. 2,4-Dimethylpyridine, 2,6-di- tertbutylpyridine (DTBP), and tetrabutylammonium, tetrapropylammonium, tetraethylammonium, and tetramethylammonium chlorides were used as chemical standards. In general, the mobility of IMS standard product ions was not affected by small amounts of contamination while the mobilities of many analytes were affected. In the presence of contaminants in the buffer gas, the mobility of analyte ions is often decreased by forming ion–molecule clusters with the contaminant. To ensure the measurement of accurate reduced mobility values, two IMS standards are required: an instrument and a mobility standard. An instrument standard is not affected by contaminants in the buffer as, and provides an accurate measurement of the instrumental parameters, such as voltage, drift length, pressure, and temperature. The mobility standard behaves like an analyte ion in that the compound’s mobility is affected by low levels of contamination in the buffer gas. Prudent use of both of these standards can lead to improved measurement of accurate reduced mobility values.

  6. Ion mobility spectrometer with virtual aperture grid

    DOEpatents

    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.

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-03-01

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

  9. ICR Heating in Ion Separation Systems

    SciTech Connect

    Timofeev, A.V.

    2005-12-15

    A systematic procedure for analyzing the physical processes that govern ICR heating in systems for ion separation is developed. The procedure is based on an analytic model of an rf antenna generating rf fields within a plasma column in a magnetic field and includes such issues as the calculation of rf fields, examination of the ICR interaction of ions with these fields, and determination of the distribution function of the ion flow at the exit from the ICR heating system. It is shown that, even in ICR heating systems with easily achievable parameter values, ions with appreciably different masses can be efficiently separated by energy.

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

    PubMed Central

    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.

    2016-01-01

    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 (i.e. peaks) in a selected mobility window are simultaneously subjected to such fields, there is ion packet compression, i.e., a reduction in peak widths for all species. This peak compression occurs with only a modest reduction of resolution, and 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. 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. PMID:27052738

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

    NASA Astrophysics Data System (ADS)

    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.

    2016-06-01

    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 a 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 (i.e., peaks) in a selected mobility window are simultaneously subjected to such fields, there is ion packet compression (i.e., a reduction in peak widths for all species). This peak compression occurs with only a modest reduction of resolution, 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. Ion mobility peak compression can be particularly useful for mitigating diffusion-driven peak broadening 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.

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

    PubMed

    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

    2016-06-01

    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 a 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 (i.e., peaks) in a selected mobility window are simultaneously subjected to such fields, there is ion packet compression (i.e., a reduction in peak widths for all species). This peak compression occurs with only a modest reduction of resolution, 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. Ion mobility peak compression can be particularly useful for mitigating diffusion-driven peak broadening 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. Graphical Abstract ᅟ. PMID:27052738

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

    NASA Astrophysics Data System (ADS)

    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.

    2016-04-01

    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 a 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 (i.e., peaks) in a selected mobility window are simultaneously subjected to such fields, there is ion packet compression (i.e., a reduction in peak widths for all species). This peak compression occurs with only a modest reduction of resolution, 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. Ion mobility peak compression can be particularly useful for mitigating diffusion-driven peak broadening 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. Travelling-wave ion mobility and negative ion fragmentation of high-mannose N-glycans.

    PubMed

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

    2016-03-01

    The isomeric structure of high-mannose N-glycans can significantly impact biological recognition events. Here, the utility of travelling-wave ion mobility mass spectrometry for isomer separation of high-mannose N-glycans is investigated. Negative ion fragmentation using collision-induced dissociation gave more informative spectra than positive ion spectra with mass-different fragment ions characterizing many of the isomers. Isomer separation by ion mobility in both ionization modes was generally limited, with the arrival time distributions (ATD) often showing little sign of isomers. However, isomers could be partially resolved by plotting extracted fragment ATDs of the diagnostic fragment ions from the negative ion spectra, and the fragmentation spectra of the isomers could be extracted by using ions from limited areas of the ATD peak. In some cases, asymmetric ATDs were observed, but no isomers could be detected by fragmentation. In these cases, it was assumed that conformers or anomers were being separated. Collision cross sections of the isomers in positive and negative fragmentation mode were estimated from travelling-wave ion mobility mass spectrometry data using dextran glycans as calibrant. More complete collision cross section data were achieved in negative ion mode by utilizing the diagnostic fragment ions. Examples of isomer separations are shown for N-glycans released from the well-characterized glycoproteins chicken ovalbumin, porcine thyroglobulin and gp120 from the human immunodeficiency virus. In addition to the cross-sectional data, details of the negative ion collision-induced dissociation spectra of all resolved isomers are discussed. PMID:26956389

  15. Pure inorganic separator for lithium ion batteries.

    PubMed

    He, Meinan; Zhang, Xinjie; Jiang, Kuiyang; Wang, Joe; Wang, Yan

    2015-01-14

    Battery safety is critical for many applications including portable electronics, hybrid and electric vehicles, and grid storage. For lithium ion batteries, the conventional polymer based separator is unstable at 120 °C and above. In this research, we have developed a pure aluminum oxide nanowire based separator; this separator does not contain any polymer additives or binders; additionally, it is a bendable ceramic. The physical and electrochemical properties of the separator are investigated. The separator has a pore size of about 100 nm, and it shows excellent electrochemical properties under both room and high temperatures. At room temperature, the ceramic separator shows a higher rate capability compared to the conventional Celgard 2500 separator and life cycle performance does not show any degradation. At 120 °C, the cell with the ceramic separator showed a much better cycle performance than the conventional Celgard 2500 separator. Therefore, we believe that this research is really an exciting scientific breakthrough for ceramic separators and lithium ion batteries and could be potentially used in the next generation lithium ion batteries requiring high safety and reliability. PMID:25459154

  16. Separation of metal ions from aqueous solutions

    DOEpatents

    Almon, Amy C.

    1994-01-01

    A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

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

    DOE PAGESBeta

    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.; et al

    2016-01-11

    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 a more reliable and cost-effective manner, while opening opportunities for much 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 isolationmore » 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. Lastly, we observed a linear increase in ion intensity with the number of trapping/accumulation events using the SLIM trap, illustrating its potential for enhancing the sensitivity of low abundance or targeted species.« less

  18. Capillary electrokinetic separations: Influence of mobile phase composition on performance

    SciTech Connect

    Sepaniak, M.J.; Swaile, D.F.; Powell, A.C.; Cole, R.O.

    1990-01-01

    The composition of the mobile phase employed in capillary zone electrophoresis and the related technique, micellar electrokinetic capillary chromatography, is an important factor in determining separation performance. The influences of ionic salt, surfactant, and organic solvent mobile phase additives on separation efficiency, retention, and elution range are discussed and demonstrated. 23 refs., 2 figs., 2 tabs.

  19. Chemical Effects in the Separation Process of a Differential Mobility / Mass Spectrometer System

    PubMed Central

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

    2013-01-01

    In differential mobility spectrometry (DMS, also referred to as high field asymmetric waveform ion mobility spectrometry, FAIMS), ions are separated on the basis of the difference in their mobility under high and low electric fields. The addition of polar modifiers to the gas transporting the ions through a DMS enhances the formation of clusters in a field-dependent way and thus amplifies the high and low field mobility difference resulting in increased peak capacity and separation power. Observations of the increase in mobility field dependence are consistent with a cluster formation model, also referred to as the dynamic cluster-decluster model. The uniqueness of chemical interactions that occur between an ion and cluster-forming neutrals increases the selectivity of the separation and the depression of low-field mobility relative to high-field mobility increases the compensation voltage and peak capacity. The effect of polar modifiers on the peak capacity across a broad range of chemicals has been investigated. We discuss the theoretical underpinnings which explain the observed effects. In contrast to the result from polar modifiers, we find that using mixtures of inert gases as the transport gas improve resolution by reducing peak width but has very little effect on peak capacity or selectivity. Inert gases do not cluster and thus do not reduce low field mobility relative to high-field mobility. The observed changes in the differential mobility α parameter exhibited by different classes of compounds when the transport gas contains polar modifiers or has a significant fraction of inert gas can be explained on the basis of the physical mechanisms involved in the separation processes. PMID:20121077

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

    DOEpatents

    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.

  1. Third International Workshop on Ion Mobility Spectrometry

    NASA Technical Reports Server (NTRS)

    Cross, John H. (Editor)

    1995-01-01

    Basic research in ion mobility spectrometry has given rise to rapid advancement in hardware development and applications. The Third International Workshop on Ion Mobility Spectrometry (IMS) was held October 16-19, 1994, at Johnson Space Center to provide a forum for investigators to present the most recent results of both basic and applied IMS research. Presenters included manufacturers and various users, including military research organizations and drug enforcement agencies. Thirty papers were given in the following five sessions: Fundamental IMS Studies, Instrument Development, Hyphenated IMS Techniques, Applications, and Data Reduction and Signal Processing. Advances in hardware development, software development, and user applications are described.

  2. Cesium Separation Using Electrically Switched Ion Exchange

    SciTech Connect

    Lilga, Michael A.); Orth, Rick J.); Sukamto, Johanes H.); Rassat, Scot D.); Genders, J D.; Gopal, R

    2001-09-01

    Electrically Switched Ion Exchange (ESIX) is a separation technology being developed at Pacific Northwest National Laboratory as an alternative to conventional ion exchange for removing metal ions from wastewater. In ESIX, which combines ion exchange and electro-chemistry, ion uptake and elution can be controlled directly by modulating the potential of an ion exchange film that has been electrochemically deposited onto an electrode. This paper presents the results of experiments on high surface area electrodes and the development of a flow system for cesium ion separation. Bench-scale flow system studies showed no change in capacity or performance of the ESIX films at a flow rate up to 113 BV/h, the maxi-mum flow rate tested, and breakthrough curves supported once-through waste processing. A comparison of results for a stacked 5-electrode cell versus a single-electrode cell showed enhanced breakthrough performance. In the stacked configuration, break-through began at about 120 BV for a feed containing 0.2 ppm cesium at a flow rate of 13 BV/h. A case study for the KE Basin (a spent nuclear fuel storage basin) on the Hanford Site demonstrated that KE Basin wastewater could be processed continuously with minimal waste generation, reduced disposal costs, and lower capital expenditures.

  3. Counterion Effects on Ion Mobility and Mobile Ion Concentration of Doped Polyphosphazenes and Polyphosphazene Ionomers

    NASA Astrophysics Data System (ADS)

    Runt, Jim; Klein, Robert

    2007-03-01

    Previous investigations have shed some light on the ion conduction process in polymer electrolytes, yet ion transport is still not well understood. Here, upon the application of a physical model of electrode polarization to two systems with nearly identical chemical structure, one composed of an ionomer (MI) with a single mobile cation, and the other a salt-doped polymer (M+S) with mobile cation and mobile anion, quantitative comparison of the conductivity parameters is achieved. The polymer electrolyte chemistries of both MI and M+S are based on poly(methoxyethoxy-ethoxy phosphazene) (MEEP). The glass transition was found to be an important factor governing the conductivity and ion mobility. However, even accounting for the glass transition, the mobility of ions in the M+S system is 10 times larger than that in the MI system, which must arise from faster diffusion of the anion than the cation. Values for mobile ion concentration are also approximately 10 times higher in M+S than MI. These differences originate from free volume available for diffusion and local environment surrounding the ion pairs, demonstrating that the location of the ion pairs in the polymer matrix has a crucial effect on both conductivity parameters. Research supported by NSF Polymers Program.

  4. Ion mobility analysis of lipoproteins

    DOEpatents

    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.

  5. Device for two-dimensional gas-phase separation and characterization of ion mixtures

    DOEpatents

    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.

  6. Pendular proteins in gases and new avenues for characterization of macromolecules by ion mobility spectrometry

    PubMed Central

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

    2009-01-01

    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 that 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. The exceptional sensitivity of that difference to ion geometry and charge distribution holds the potential for a powerful 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 that depends on the ion mobility, gas pressure, and temperature. At ambient conditions used in current FAIMS systems, 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. As expected for the dipole-aligned regime, FAIMS analyses of protein ions and complexes of ≈30–130 kDa show an order-of-magnitude expansion of separation space compared with smaller proteins and other ions. PMID:19351899

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

    SciTech Connect

    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.

  8. Organic ion exchange resin separation methods evaluation

    SciTech Connect

    Witwer, K.S.

    1998-05-27

    This document describes testing to find effective methods to separate Organic Ion Exchange Resin (OIER) from a sludge simulant. This task supports a comprehensive strategy for treatment and processing of K-Basin sludge. The simulant to be used resembles sludge that has accumulated in the 105KE and 105KW Basins in the 1OOK area of the Hanford Site. The sludge is an accumulation of fuel element corrosion products, organic and inorganic ion exchange materials, canister gasket materials, iron and aluminum corrosion products, sand, dirt, and other minor amounts of organic matter.

  9. Process analysis using ion mobility spectrometry.

    PubMed

    Baumbach, J I

    2006-03-01

    Ion mobility spectrometry, originally used to detect chemical warfare agents, explosives and illegal drugs, is now frequently applied in the field of process analytics. The method combines both high sensitivity (detection limits down to the ng to pg per liter and ppb(v)/ppt(v) ranges) and relatively low technical expenditure with a high-speed data acquisition. In this paper, the working principles of IMS are summarized with respect to the advantages and disadvantages of the technique. Different ionization techniques, sample introduction methods and preseparation methods are considered. Proven applications of different types of ion mobility spectrometer (IMS) used at ISAS will be discussed in detail: monitoring of gas insulated substations, contamination in water, odoration of natural gas, human breath composition and metabolites of bacteria. The example applications discussed relate to purity (gas insulated substations), ecology (contamination of water resources), plants and person safety (odoration of natural gas), food quality control (molds and bacteria) and human health (breath analysis). PMID:16132133

  10. Environment applications for ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Ritchie, Robert K.; Rudolph, Andreas

    1995-01-01

    The detection of environmentally important polychlorinated aromatics by ion mobility spectrometry (IMS) was investigated. Single polychlorinated biphenyl (PCB) isomers (congeners) having five or more chlorine atoms were reliably detected in isooctane solution at levels of 35 ng with a Barringer IONSCAN ion mobility spectrometer operating in negative mode; limits of detection (LOD) were extrapolated to be in the low ng region. Mixtures of up to four PCB congeners, showing characteristic multiple peaks, and complex commercial mixtures of PCBs (Aroclors) were also detected. Detection of Aroclors in transformer oil was suppressed by the presence of the antioxidant BHT (2,6-di-t-butyl4-methylphenol) in the oil. The wood preservative pentachlorophenol (PCP) was easily detected in recycled wood shavings at levels of 52 ppm with the IONSCAN; the LOD was extrapolated to be in the low ppm region.

  11. Review on ion mobility spectrometry. Part 1: current instrumentation.

    PubMed

    Cumeras, R; Figueras, E; Davis, C E; Baumbach, J I; Gràcia, I

    2015-03-01

    Ion Mobility Spectrometry (IMS) is a widely used and 'well-known' technique of ion separation in the gaseous phase based on the differences in ion mobilities under an electric field. All IMS instruments operate with an electric field that provides space separation, but some IMS instruments also operate with a drift gas flow that provides also a temporal separation. In this review we will summarize the current IMS instrumentation. IMS techniques have received an increased interest as new instrumentation and have become available to be coupled with mass spectrometry (MS). For each of the eight types of IMS instruments reviewed it is mentioned whether they can be hyphenated with MS and whether they are commercially available. Finally, out of the described devices, the six most-consolidated ones are compared. The current review article is followed by a companion review article which details the IMS hyphenated techniques (mainly gas chromatography and mass spectrometry) and the factors that make the data from an IMS device change as a function of device parameters and sampling conditions. These reviews will provide the reader with an insightful view of the main characteristics and aspects of the IMS technique. PMID:25465076

  12. Review on Ion Mobility Spectrometry. Part 1: Current Instrumentation

    PubMed Central

    Cumeras, R.; Figueras, E.; Davis, C.E.; Baumbach, J.I.; Gràcia, I.

    2014-01-01

    Ion Mobility Spectrometry (IMS) is a widely used and ‘well-known’ technique of ion separation in gaseous phase based on the differences of ion mobilities under an electric field. All IMS instruments operate with an electric field that provides space separation, but some IMS instruments also operate with a drift gas flow which provides also a temporal separation. In this review we will summarize the current IMS instrumentation. IMS techniques have received an increased interest as new instrumentation has become available to be coupled with mass spectrometry (MS). For each of the eight types of IMS instruments reviewed it is mentioned whether they can be hyphenated with MS and whether they are commercially available. Finally, out of the described devices, the six most-consolidated ones are compared. The current review article is followed by a companion review article which details the IMS hyphenated techniques (mainly gas chromatography and mass spectrometry) and the factors that make the data from an IMS device change as function of device parameters and sampling conditions. These reviews will provide the reader with an insightful view of the main characteristics and aspects of the IMS technique. PMID:25465076

  13. Block copolymer ion gels for gas separation

    NASA Astrophysics Data System (ADS)

    Gu, Yuanyan; Lodge, Timothy

    2012-02-01

    Carbon dioxide removal from light gases (eg. N2, CH4, and H2) is a very important technology for industrial applications such as natural gas sweetening, CO2 capture from coal-fire power plant exhausts and hydrogen production. Current CO2 separation method uses amine-absorption, which is energy-intensive and requires frequent maintenance. Membrane separation is a cost-effective solution to this problem, especially in small-scale applications. Ionic liquids have recently received increasing interest in this area because of their selective solubility for CO2 and non-volatility. However, ionic liquid itself lacks the persistent structure and mechanical integrity to withstand the high pressure for gas separation. Here, we report the development and gas separation performances of physically crosslinked ion gels based on self-assembly of ABA-triblock copolymers in ionic liquids. Three different types of polymers was used to achieve gelation in ionic liquids. Specifically, a triblock copolymer ion gel with a polymerized ionic liquid mid-block shows performances higher than the upper bound of well-known ``Robeson Plot'' for CO2/N2.

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

    PubMed Central

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

    2007-01-01

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

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

    SciTech Connect

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

    2005-05-15

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

  16. Differential mobility spectrometry of isomeric protonated dipeptides: modifier and field effects on ion mobility and stability.

    PubMed

    Blagojevic, Voislav; Chramow, Alexander; Schneider, Bradley B; Covey, Thomas R; Bohme, Diethard K

    2011-05-01

    The ability to resolve isomeric protonated dipeptides was investigated with the new technique of differential ion mobility mass spectrometry that uses "modifier" molecules to enhance differential mobility. Two pairs of protonated peptides [glycine-alanine (GlyAla) and alanine-glycine (AlaGly), glycine-serine (GlySer) and serine-glycine (SerGly)] and eight different modifiers (water, 2-propanol, 1,5-hexadiene, 2-chloropropane, chlorobenzene, dichloromethane, acetonitrile, and cyclohexane) were used in the initial study. Separation of the protonated peptides was found to be dependent on the mass and proton affinity of the modifier and combinations of functionalities present in the modifier and the analyte ion. Six of the eight modifiers (water, 2-propanol, chlorobenzene, cyclohexane, dichloromethane, and acetonitrile) were able to separate the protonated isomeric peptide pairs, and generally, modifiers with electron-rich groups performed the best. In the presence of some modifiers, a reduction of ion current was observed under the highest field conditions (>115 Td). Dopant-catalyzed isomerization, likely by proton-transport catalysis, and field-induced fragmentation may have contributed to these losses. Two high vapor pressure modifiers, 1,5-hexadiene and 2-chloropropane, significantly influenced ion formation leading to the formation of stable cluster populations that could be observed in the mass spectrometer. Although not a major concern, both fragmentation and influence of modifier evaporation warrant further studies in order to fully understand and possibly eliminate them. PMID:21504141

  17. Toward an Intelligent Ion Mobility Spectrometer (IMS)

    SciTech Connect

    Timothy R. McJunkin; Jill R. Scott; Carla J. Miller

    2003-07-01

    The ultimate goal is to design and build a very smart ion mobility spectrometer (IMS) that can operate autonomously. To accomplish this, software capable of interpreting spectra so that it can be used in control loops for data interpretation as well as adjusting instrument parameters is being developed. Fuzzy logic and fuzzy numbers are used in this IMS spectra classification scheme. Fuzzy logic provides a straight forward method for developing a classification/detection system, whenever rules for classifying the spectra can be described linguistically. Instead of using 'max' and 'min' values, the product of the truth values is used to determine class membership. Using the product allows rule-bases that utilize the AND function to allow each condition to discount truth value in determining membership, while rule-bases with an OR function are allowed to accumulate membership. Fuzzy numbers allow encapsulation of the uncertainties due to ion mobility peak widths as well as measured instrumental parameters, such as pressure and temperature. Associating a peak with a value of uncertainty, in addition to making adjustments to the mobility calculation based on variations in measured parameters, enables unexpected shifts to be more reliably detected and accounted for; thereby, reducing the opportunity for 'false negative' results. The measure of uncertainty is anticipated to serve the additional purpose of diagnosing the operational conditions of the IMS instrument.

  18. Dielectric Properties and Ion Mobility in Erythrocytes

    PubMed Central

    Pauly, H.; Schwan, H. P.

    1966-01-01

    The impedance of erythrocytes of man, cattle, sheep, dog, cat, rabbit, and chicken was measured in the range from 0.5 to 250 Mc. The dielectric constant of the red cell interior is 50 at 250 Mc, varies but little with species, and can readily be accounted for by the cells' hemoglobin content. The electrical conductivity of the red cell interior was determined between 70 and 100 Mc. The values differ from species to species within the rather limited range from 4.4 to 5.3 mmho/cm. Removal of the cell membranes does not affect the conductivity. Hence, the cell interior behaves, from an electrical point of view, like a highly concentrated hemoglobin solution. A theoretical value for the electrical conductivity of erythrocyte interiors, which is calculated on the basis of the salt content of the cell, ion mobility, and the volume concentration of the hemoglobin, is roughly twice as large as the measured value. This discrepancy is typical not only of the red blood cell. Pertinent measurements show that it is probably caused by hydrodynamic and possibly by electrostatic effects also, which lower the mobility of the ions. From the lower electrical mobility it appears that a lowered diffusion constant of the electrolytes and nonelectrolytes within the cell is indicated. PMID:5970566

  19. Trying to detect gas-phase ions? Understanding Ion Mobility Spectrometry

    PubMed Central

    Cumeras, R.; Figueras, E.; Davis, C.E.; Baumbach, J.I.; Gràcia, I.

    2014-01-01

    Ion Mobility Spectrometry (IMS) is a widely used and ‘well-known’ technique of ion separation in gaseous phase based on the differences of ion mobilities under an electric field. This technique has received increased interest over the last several decades as evidenced by the pace and advances of new IMS devices available. In this review we explore the hyphenated techniques that are used with IMS, especially mass spectrometry as identification approach and multi-capillary column as pre-separation approach. Also, we will pay special attention to the key figures of merit of the ion mobility spectrum and how data is treated, and the influences of the experimental parameters in both a conventional drift time IMS (DTIMS) and a miniaturized IMS also known as high Field Asymmetric IMS (FAIMS) in the planar configuration. The current review article is preceded by a companion review article which details the current instrumentation and to the sections that configures both a conventional DTIMS and FAIMS devices. Those reviews will give the reader an insightful view of the main characteristics and aspects of the IMS technique. PMID:25465248

  20. Rapid profiling and identification of anthocyanins in fruits with Hadamard transform ion mobility mass spectrometry.

    PubMed

    Liu, Wenjie; Zhang, Xing; Siems, William F; Hill, Herbert H; Yin, Dulin

    2015-06-15

    The use of Hadamard transform ion mobility mass spectrometry (HT-IMMS) in the profiling of anthocyanins from different fruits is presented. Samples extracted with acidic methanol and purified with solid phase extraction were analyzed with direct IMMS infusion. The separation of various anthocyanins was achieved within 30s with resolving powers up to 110. The ion mobility drift times correlated with their mass-to-charge ratios with a correlation coefficient of 0.979 to produce a trend line that was characteristic for anthocyanins. Isomers with the same anthocyanidin but different hexoses were differentiated by ion mobility spectrometry. Furthermore, mobility separated ions underwent collision induced dissociation at the IMMS interface to provide MS/MS spectra. These fragmentation spectra aided in the identification of anthocyanidins via the loss of the saccharide groups. IMMS appears to be a rapid and efficient approach for profiling and identifying anthocyanins. PMID:25660880

  1. Mixed oxygen ion/electron-conducting ceramics for oxygen separation

    SciTech Connect

    Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L.

    1996-08-01

    Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

  2. Ion mobility spectrometry for detection of skin volatiles

    PubMed Central

    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 may contribute to elucidating some physiological processes occurring in the human skin. PMID:23217311

  3. ION EXCHANGE ADSORPTION PROCESS FOR PLUTONIUM SEPARATION

    DOEpatents

    Boyd, G.E.; Russell, E.R.; Taylor, M.D.

    1961-07-11

    Ion exchange processes for the separation of plutonium from fission products are described. In accordance with these processes an aqueous solution containing plutonium and fission products is contacted with a cation exchange resin under conditions favoring adsorption of plutonium and fission products on the resin. A portion of the fission product is then eluted with a solution containing 0.05 to 1% by weight of a carboxylic acid. Plutonium is next eluted with a solution containing 2 to 8 per cent by weight of the same carboxylic acid, and the remaining fission products on the resin are eluted with an aqueous solution containing over 10 per cent by weight of sodium bisulfate.

  4. Proton-bound cluster ions in ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

    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.

  5. Signal processing for ION mobility spectrometers

    NASA Technical Reports Server (NTRS)

    Taylor, S.; Hinton, M.; Turner, R.

    1995-01-01

    Signal processing techniques for systems based upon Ion Mobility Spectrometry will be discussed in the light of 10 years of experience in the design of real-time IMS. Among the topics to be covered are compensation techniques for variations in the number density of the gas - the use of an internal standard (a reference peak) or pressure and temperature sensors. Sources of noise and methods for noise reduction will be discussed together with resolution limitations and the ability of deconvolution techniques to improve resolving power. The use of neural networks (either by themselves or as a component part of a processing system) will be reviewed.

  6. Fundamentals of Trapped Ion Mobility Spectrometry Part II: Fluid Dynamics

    NASA Astrophysics Data System (ADS)

    Silveira, Joshua A.; Michelmann, Karsten; Ridgeway, Mark E.; Park, Melvin A.

    2016-04-01

    Trapped ion mobility spectrometry (TIMS) is a new high resolution (R up to ~300) separation technique that utilizes an electric field to hold ions stationary against a moving gas. Recently, an analytical model for TIMS was derived and, in part, experimentally verified. A central, but not yet fully explored, component of the model involves the fluid dynamics at work. The present study characterizes the fluid dynamics in TIMS using simulations and ion mobility experiments. Results indicate that subsonic laminar flow develops in the analyzer, with pressure-dependent gas velocities between ~120 and 170 m/s measured at the position of ion elution. One of the key philosophical questions addressed is: how can mobility be measured in a dynamic system wherein the gas is expanding and its velocity is changing? We noted previously that the analytically useful work is primarily done on ions as they traverse the electric field gradient plateau in the analyzer. In the present work, we show that the position-dependent change in gas velocity on the plateau is balanced by a change in pressure and temperature, ultimately resulting in near position-independent drag force. That the drag force, and related variables, are nearly constant allows for the use of relatively simple equations to describe TIMS behavior. Nonetheless, we derive a more comprehensive model, which accounts for the spatial dependence of the flow variables. Experimental resolving power trends were found to be in close agreement with the theoretical dependence of the drag force, thus validating another principal component of TIMS theory.

  7. Fundamentals of Trapped Ion Mobility Spectrometry Part II: Fluid Dynamics.

    PubMed

    Silveira, Joshua A; Michelmann, Karsten; Ridgeway, Mark E; Park, Melvin A

    2016-04-01

    Trapped ion mobility spectrometry (TIMS) is a new high resolution (R up to ~300) separation technique that utilizes an electric field to hold ions stationary against a moving gas. Recently, an analytical model for TIMS was derived and, in part, experimentally verified. A central, but not yet fully explored, component of the model involves the fluid dynamics at work. The present study characterizes the fluid dynamics in TIMS using simulations and ion mobility experiments. Results indicate that subsonic laminar flow develops in the analyzer, with pressure-dependent gas velocities between ~120 and 170 m/s measured at the position of ion elution. One of the key philosophical questions addressed is: how can mobility be measured in a dynamic system wherein the gas is expanding and its velocity is changing? We noted previously that the analytically useful work is primarily done on ions as they traverse the electric field gradient plateau in the analyzer. In the present work, we show that the position-dependent change in gas velocity on the plateau is balanced by a change in pressure and temperature, ultimately resulting in near position-independent drag force. That the drag force, and related variables, are nearly constant allows for the use of relatively simple equations to describe TIMS behavior. Nonetheless, we derive a more comprehensive model, which accounts for the spatial dependence of the flow variables. Experimental resolving power trends were found to be in close agreement with the theoretical dependence of the drag force, thus validating another principal component of TIMS theory. Graphical Abstract ᅟ. PMID:26864793

  8. Ion mobility spectrometry after supercritical fluid chromatography

    SciTech Connect

    Morrissey, M.A.

    1988-01-01

    In this work, a Fourier transform ion mobility spectrometer (FT-IMS) was constructed and evaluated as a detector for supercritical fluid chromatography (SFC). The FT-IMS provides both quantitative and qualitative data of a wide range of compounds, selective and nonselective modes of chromatographic detection, and it is compatible with a wide range of SFC mobile phases. Drift spectra are presented for a number of samples, including polymers, lipids, herbicides, antibiotics, and pharmaceuticals. The unique properties of supercritical fluids made it possible to introduce these compounds into the spectrometer. While the drift spectra presented are generally simple, showing only a quasi-molecular ion, a few are surprising complex. Examples of selective and non-selective detection demonstrate the usefulness of the detector. Examples are presented for fish oil concentrate, bacon grease extract, soil extract, and polymer mixtures. In the case of Triton X-100, a non-ionic surfactant, the FT-IMS was able to selectively detect individual oligomers in the polymer mixture. In the case of a polydimethylsilicone mixture the detector isolated a contaminant in the mixture.

  9. A novel electrospray-based ion mobility spectrometer

    NASA Astrophysics Data System (ADS)

    Bathgate, Ben; Cheong, Eric C. S.; Backhouse, Christopher J.

    2004-08-01

    We present a design for a low-cost ion mobility spectrometer that can be built using the equipment on hand in many electronics-oriented undergraduate laboratories. The construction of this system is based upon the use of printed circuit boards and does not require the specialized drift and sheath gases, vacuum pumps, heater assemblies, high voltage pulsers, or precision pumps that are characteristic of the systems generally reported in the literature. We demonstrate the system in the separation of ions of methanol and water in air. Despite the low cost of this system it has a performance comparable to more complex systems, with a sensitivity of approximately 100 ppm for the protein cytochrome c. This system is suitable for use as an electronics or signal-processing project, or even a biotechnology demonstration.

  10. Reduction of air ion mobility to standard conditions

    NASA Astrophysics Data System (ADS)

    Tammet, H.

    1998-06-01

    The Langevin rule of the reduction of air ion mobility is adequate in case of zero-size ions. An alternative is the Stokes-Millikan equation that is adequate in the limit of macroscopic charged particles. The temperature variation of air ion mobility predicted by the Stokes-Millikan equation radically contradicts the Langevin rule. The temperature and pressure variation of air ion mobility is examined by using a new semiempirical model that describes the transition from the kinetic theory to the Stokes-Millikan equation. The model is valid in full mobility range. It allows to calculate at first the size of an ion according to the measured mobility and then the standard mobility according to the size. The ascent of the temperature-mobility curve on a logarithmic chart approaches the Langevin value of 1 only at very high mobilities not found in the atmosphere. The value of the ascent is 0.6 in the case of small ions of the mobility of 1.5 cm2 V-1 s-1 which brings about a considerable error when using the Langevin rule. It is recommended to store the natural values of the mobility in databases together with the values of temperature and pressure and to definitely indicate the method when the reduced mobilities are presented in publications.

  11. Observation of separate cation and anion electrophoretic mobilities in pure ionic liquids

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyang; Madsen, Louis A.

    2014-02-01

    Ionic liquids (ILs) continue to show relevance in many fields, from battery electrolytes, to carbon capture, to advanced separations. These highly ion-dense fluids present unique challenges in understanding their electrochemical properties due to deviations in behavior from existing electrolyte theories. Here we present a novel characterization of ILs using electrophoretic NMR (ENMR) to determine separate cation and anion mobilities. This method uses an applied electric field coincident with a pulsed magnetic field gradient to encode the E-field driven flow into NMR signals for cations (1H) and anions (19F). We describe the detailed design of these experiments, including quantitative analysis of artifact mitigation and necessary control experiments. We then explore mobilities and diffusion coefficients for two representative ILs: 1-ethyl-3-methyl imidazolium tetrafluoroborate ([C2mim][BF4]) and 1-ethyl-3-methyl imidazolium trifluoromethanesulfonate ([C2mim][TfO]). We further use the individual ion mobilities to calculate the bulk net conductivity, which closely agrees with bulk conductivity measurements obtained using impedance spectroscopy. These observations represent the first reliable measurements of cation and anion mobilities in pure ILs, with errors of ±7%. We discuss this advanced experimental methodology in detail, as well as implications of these sensitive measurements for understanding conduction mechanisms in ion-dense electrolytes.

  12. Observation of separate cation and anion electrophoretic mobilities in pure ionic liquids.

    PubMed

    Zhang, Zhiyang; Madsen, Louis A

    2014-02-28

    Ionic liquids (ILs) continue to show relevance in many fields, from battery electrolytes, to carbon capture, to advanced separations. These highly ion-dense fluids present unique challenges in understanding their electrochemical properties due to deviations in behavior from existing electrolyte theories. Here we present a novel characterization of ILs using electrophoretic NMR (ENMR) to determine separate cation and anion mobilities. This method uses an applied electric field coincident with a pulsed magnetic field gradient to encode the E-field driven flow into NMR signals for cations ((1)H) and anions ((19)F). We describe the detailed design of these experiments, including quantitative analysis of artifact mitigation and necessary control experiments. We then explore mobilities and diffusion coefficients for two representative ILs: 1-ethyl-3-methyl imidazolium tetrafluoroborate ([C2mim][BF4]) and 1-ethyl-3-methyl imidazolium trifluoromethanesulfonate ([C2mim][TfO]). We further use the individual ion mobilities to calculate the bulk net conductivity, which closely agrees with bulk conductivity measurements obtained using impedance spectroscopy. These observations represent the first reliable measurements of cation and anion mobilities in pure ILs, with errors of ±7%. We discuss this advanced experimental methodology in detail, as well as implications of these sensitive measurements for understanding conduction mechanisms in ion-dense electrolytes. PMID:24588161

  13. Resolving Structural Isomers of Monosaccharide Methyl Glycosides Using Drift Tube and Traveling Wave Ion Mobility Mass Spectrometry

    PubMed Central

    Li, Hongli; Giles, Kevin; Bendiak, Brad; Kaplan, Kimberly; Siems, William F.; Hill, Herbert H.

    2013-01-01

    Monosaccharide structural isomers including sixteen methyl-D-glycopyranosides and four methyl-N-acetylhexosamines were subjected to ion mobility measurements by electrospray ion mobility mass spectrometry. Two ion mobility-MS systems were employed: atmospheric pressure drift tube ion mobility time-of-flight mass spectrometry and a Synapt G2 HDMS system which incorporates a low pressure traveling wave ion mobility separator. All the compounds were investigated as [M+Na]+ ions in the positive mode. A majority of the monosaccharide structural isomers exhibited different mobility drift times in either system, depending on differences in their anomeric and stereochemical configurations. In general, drift time patterns (relative drift times of isomers) matched between the two instruments. Higher resolving power was observed using the atmospheric pressure drift tube. Collision cross section values of monosaccharide structural isomers were directly calculated from the atmospheric pressure ion mobility experiments and a collision cross section calibration curve was made for the traveling wave ion mobility instrument. Overall, it was demonstrated that ion mobility-mass spectrometry using either drift tube or traveling wave ion mobility is a valuable technique for resolving subtle variations in stereochemistry among the sodium adducts of monosaccharide methyl glycosides. PMID:22339760

  14. Ion mobility spectrometer for online monitoring of trace compounds1

    NASA Astrophysics Data System (ADS)

    Li, F.; Xie, Z.; Schmidt, H.; Sielemann, S.; Baumbach, J. I.

    2002-10-01

    The principle, character and developments of the instrumentation of ion mobility spectrometry are reviewed. The application of ion mobility spectrometers in monitoring chemical warfare agents, explosives, drugs, environmental hazardous compounds and industrial process control are discussed. Process applications with respect to miniaturization of the instrument are presented.

  15. Mobility spectrum of air ions at Tahkuse Observatory

    NASA Astrophysics Data System (ADS)

    Horrak, U.; Iher, H.; Luts, A.; Salm, J.; Tammet, H.

    1994-05-01

    Mobility spectra of air ions have been measured at a rural site in Estonia during several periods. The annual average mobility spectrum of natural small air ions is presented. The concentrations of two groups of air ions with mobilities 0.32-0.5 sq cm/(V s) and 0.5-2.5 sq cm/(V s) are not correlated; this fact indicates the different nature of the ions of the two groups. The air ions with mobilities 0.5-2.5 sq cm/(V s) are interpreted as cluster ions and the air ions with mobilities 0.32-0.5 sq cm/(V s) as charged aerosol particles that can be created in the process of ion-induced nucleation. A half-year average mobility spectrum of the large ions with mobilities 3.2 x 10(exp -4) - 1.5/(V s) is presented. The spectrum is well interpreted on the basis of the average size distribution of aerosol particles and on the theory of diffusion charging of the particles.

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

    SciTech Connect

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

    2007-11-03

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

  17. Ion Mobility Spectrometry of Heavy Metals.

    PubMed

    Ilbeigi, Vahideh; Valadbeigi, Younes; Tabrizchi, Mahmoud

    2016-07-19

    A simple, fast, and inexpensive method was developed for detecting heavy metals via the ion mobility spectrometry (IMS) in the negative mode. In this method, Cl(-) ion produced by the thermal ionization of NaCl is employed as the dopant or the ionizing reagent to ionize heavy metals. In practice, a solution of mixed heavy metals and NaCl salts was directly deposited on a Nichrome filament and electrically heated to vaporize the salts. This produced the IMS spectra of several heavy-metal salts, including CdCl2, ZnSO4, NiCl2, HgSO4, HgCl2, PbI2, and Pb(Ac)2. For each heavy metal (M), one or two major peaks were observed, which were attributed to M·Cl(-) or [M·NaCl]Cl(-)complexes. The method proved to be useful for the analysis of mixed heavy metals. The absolute detection limits measured for ZnSO4 and HgSO4 were 0.1 and 0.05 μg, respectively. PMID:27321408

  18. Ion mobility spectrometry for food quality and safety.

    PubMed

    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

  19. Diffusion and Coulomb separation of ions in dense matter.

    PubMed

    Beznogov, M V; Yakovlev, D G

    2013-10-18

    We analyze diffusion equations in strongly coupled Coulomb mixtures of ions in dense stellar matter. Strong coupling of ions in the presence of gravitational forces and electric fields (induced by plasma polarization in the presence of gravity) produces a specific diffusion current which can separate ions with the same A/Z (mass to charge number) ratios but different Z. This Coulomb separation of ions can be important for the evolution of white dwarfs and neutron stars. PMID:24182248

  20. Diffusion and Coulomb Separation of Ions in Dense Matter

    NASA Astrophysics Data System (ADS)

    Beznogov, M. V.; Yakovlev, D. G.

    2013-10-01

    We analyze diffusion equations in strongly coupled Coulomb mixtures of ions in dense stellar matter. Strong coupling of ions in the presence of gravitational forces and electric fields (induced by plasma polarization in the presence of gravity) produces a specific diffusion current which can separate ions with the same A/Z (mass to charge number) ratios but different Z. This Coulomb separation of ions can be important for the evolution of white dwarfs and neutron stars.

  1. Ion concentration polarization-based continuous separation device using electrical repulsion in the depletion region

    NASA Astrophysics Data System (ADS)

    Jeon, Hyungkook; Lee, Horim; Kang, Kwan Hyoung; Lim, Geunbae

    2013-12-01

    We proposed a novel separation method, which is the first report using ion concentration polarization (ICP) to separate particles continuously. We analyzed the electrical forces that cause the repulsion of particles in the depletion region formed by ICP. Using the electrical repulsion, micro- and nano-sized particles were separated based on their electrophoretic mobilities. Because the separation of particles was performed using a strong electric field in the depletion region without the use of internal electrodes, it offers the advantages of simple, low-cost device fabrication and bubble-free operation compared with conventional continuous electrophoretic separation methods, such as miniaturizing free-flow electrophoresis (μ-FFE). This separation device is expected to be a useful tool for separating various biochemical samples, including cells, proteins, DNAs and even ions.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  3. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    SciTech Connect

    Manuel J. Manard, Stephan Weeks, Kevin Kyle

    2010-05-27

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

  4. Travelling wave ion mobility and negative ion fragmentation for the structural determination of N-linked glycans.

    PubMed

    Harvey, David J; Scarff, Charlotte A; Edgeworth, Matthew; Crispin, Max; Scanlan, Christopher N; Sobott, Frank; Allman, Sarah; Baruah, Kavitha; Pritchard, Laura; Scrivens, James H

    2013-08-01

    Travelling wave ion mobility was investigated for its ability to separate N-glycans from other compounds and for resolution of isomers. Charged glycans, exemplified by sialylated complex N-glycans released from bovine fetuin and ionised by electrospray, could be separated from residual glycopeptides allowing the minor, more highly sialylated compounds to be detected where their ions were obscured by ions from other compounds in different charge states. This technique was also found to be excellent for extracting the N-glycan profiles from contaminated samples. Structural identification of the glycans was performed by negative ion CID fragmentation, a method that provides a wealth of structurally diagnostic ions. However, fragment ions can also appear in the glycan profiles where they can be mistaken for glycan molecular ions. Fragments and molecular ions were frequently shown to have different drift time profiles, allowing them to be differentiated. Some separation of isomers was found but only for the smallest compounds. Differentiation from conformers was achieved by plotting drift time profiles of the fragments; these profiles matched those of the precursor ions where conformers were present. The techniques were applied to investigations of N-glycans released from the fungus Piptoporus betulinus where the technique was used to separate different carbohydrate types present in biological extracts. PMID:23712623

  5. Field applications of ion-mobility spectrometry

    NASA Astrophysics Data System (ADS)

    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.

  6. Anomerization of Acrylated Glucose During Traveling Wave Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Chendo, Christophe; Moreira, Guillaume; Tintaru, Aura; Posocco, Paola; Laurini, Erik; Lefay, Catherine; Gigmes, Didier; Viel, Stéphane; Pricl, Sabrina; Charles, Laurence

    2015-09-01

    Anomerization of simple sugars in the liquid phase is known as an acid- and base-catalyzed process, which highly depends on solvent polarity. This reaction is reported here to occur in the gas phase, during traveling wave ion mobility spectrometry (TWIMS) experiments aimed at separating α- and β-anomers of penta-acrylated glucose generated as ammonium adducts in electrospray ionization. This compound was available in two samples prepared from glucose dissolved in solvents of different polarity, namely tetrahydrofuran (THF) and N,N-dimethylacetamide (DMAC), and analyzed by electrospray tandem mass spectrometry (ESI-MS/MS) as well as traveling wave ion mobility (ESI-TWIMS-MS). In MS/MS, an anchimerically-assisted process was found to be unique to the electrosprayed α-anomer, and was only observed for the THF sample. In ESI-TWIMS-MS, a signal was measured at the drift time expected for the α-anomer for both the THF and DMAC samples, in apparent contradiction to the MS/MS results, which indicated that the α-anomer was not present in the DMAC sample. However, MS/MS experiments performed after TWIMS separation revealed that ammonium adducts of the α-anomer produced from each sample, although exhibiting the same collision cross section, were clearly different. Indeed, while the α-anomer actually present in the THF sample was electrosprayed with the ammonium adducted at the C2 acrylate, its homologue only observed when the DMAC sample was subjected to TWIMS hold the adducted ammonium at the C1 acrylate. These findings were explained by a β/α inter-conversion upon injection in the TWIMS cell, as supported by theoretical calculation and dynamic molecular modeling.

  7. A compact high resolution electrospray ionization ion mobility spectrometer.

    PubMed

    Reinecke, T; Kirk, A T; Ahrens, A; Raddatz, C-R; Thoben, C; Zimmermann, S

    2016-04-01

    Electrospray is a commonly used ionization method for the analysis of liquids. An electrospray is a dispersed nebular of charged droplets produced under the influence of a strong electrical field. Subsequently, ions are produced in a complex process initiated by evaporation of neutral solvent molecules from these droplets. We coupled an electrospray ionization source to our previously described high resolution ion mobility spectrometer with 75mm drift tube length and a drift voltage of 5kV. When using a tritium source for chemical gas phase ionization, a resolving power of R=100 was reported for this setup. We replaced the tritium source and the field switching shutter by an electrospray needle, a desolvation region with variable length and a three-grid shutter for injecting ions into the drift region. Preliminary measurements with tetraalkylammonium halides show that the current configuration with the electrospray ionization source maintains the resolving power of R=100. In this work, we present the characterization of our setup. One major advantage of our setup is that the desolvation region can be heated separately from the drift region so that the temperature in the drift region stays at room temperature even up to desolvation region temperatures of 100°C. We perform parametric studies for the investigation of the influence of temperature on solvent evaporation with different ratios of water and methanol in the solvent for different analyte substances. Furthermore, the setup is operated in negative mode and spectra of bentazon with different solvents are presented. PMID:26838374

  8. Progress in metal ion separation and preconcentration : an overview.

    SciTech Connect

    Bond, A. H.

    1998-05-19

    A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented.

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

    PubMed Central

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

    2010-01-01

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

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

    PubMed

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

    2008-08-01

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

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

    SciTech Connect

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

    2008-08-01

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

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

    PubMed

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  15. Analysis of Ultra-Pure Gases by Ion Mobility Spectrometry

    NASA Technical Reports Server (NTRS)

    Stimac, Robert M.; Wernlund, Roger F.; Cohen, Martin J.

    1995-01-01

    Work has continued with the evaluation of the Ion Mobility Spectrometer (IMS) for the analysis of gases having low parts-per-billion (10(exp -9)) water concentration. A modified PCP, inc. MMS-160 Mobility Mass Spectrometer System was used for the analysis of ultra-pure argon and nitrogen. The MMS-160 system permits the mass-identification of unique reactant and product ions observed in the reduced-water host gases. When the water is removed to low ppb levels, higher energy reactant ions are observed. In nitrogen, distinct odd- and even-numbered nitrogen cluster ion mobility peaks are observed, as well as adduct ion peaks from the trace contaminants in the gas. Argon also produces a cluster ion mobility peak and adduct ion peaks from trace components in the gas. Levels of contaminants in these ultra-pure gases can be determined from the ion mobility spectra. A calibrated source was used to provide variable known quantities of water to the pure gas supply of the IMS.

  16. Total hydrocarbon analysis by ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Cross, John H.; Limero, Thomas F.; James, John T.

    1994-01-01

    Astronauts must be alerted quickly to chemical leaks that compromise their health and the success of their missions. An ideal leak detector would be equally sensitive to all compounds that might constitute a hazard and insensitive to nontoxic compounds. No ideal sensor exists; thus, selection of a methodology is a series of compromises. The commonly used methods are either insensitive at the low exposure levels set by OSHA, NASA, and other organizations or are selectively insensitive to important classes of chemicals such as Freons. After extensive study and experience, the Toxicology Group at JSC has selected ion mobility spectrometry (IMS) for development into a broad range, sensitive detector. In addition to the sensing method, signal processing is important leak detection because a background signal can be expected at all times. The leak-detecting instrument must be programmed to discriminate between authentic leaks and background fluctuations caused by routine operations. The results of an evaluation of the prototype THA is presented in terms related to spacecraft operations. The evaluation included determination of instrumental parameters such as stability and response times. We also included responses to some common components of spacecraft atmospheres in pure form and in binary and ternary mixtures. The output of the four algorithms to the mixtures was found to be noticeably different. These responses are compared on the basis of their utility for signaling a chemical leak. As a means of evaluating its resistance to a falsely positive response, the THA was challenged with carbon dioxide and methane, compounds whose concentrations normally increase in spacecraft air during human habitation. The instrument showed virtually no response to these interferences. Although the prototype THA is designed for space flight, this detector is expected to be useful for field screening at chemical waste dumps and other environmentally sensitive locations.

  17. Ion Mobility-Mass Spectrometry Analysis of Serum N-linked Glycans from Esophageal Adenocarcinoma Phenotypes

    PubMed Central

    Gaye, M. M.; Valentine, S. J.; Hu, Y.; Mirjankar, N.; Hammoud, Z. T.; Mechref, Y.; Lavine, B. K.; Clemmer, D. E.

    2012-01-01

    Three disease phenotypes, Barrett’s esophagus (BE), high-grade dysplasia (HGD), esophageal adenocarcinoma (EAC), and a set of normal control (NC) serum samples are examined using a combination of ion mobility spectrometry (IMS), mass spectrometry (MS) and principal component analysis (PCA) techniques. Samples from a total of 136 individuals were examined, including: 7 characterized as BE, 12 as HGD, 56 as EAC and 61 as NC. In typical datasets it was possible to assign ~20 to 30 glycan ions based on MS measurements. Ion mobility distributions for these ions show multiple features. In some cases, such as the [S1H5N4+3Na]3+ and [S1F1H5N4+3Na]3+ glycan ions, the ratio of intensities of high-mobility features to low-mobility features vary significantly for different groups. The degree to which such variations in mobility profiles can be used to distinguish phenotypes is evaluated for eleven N-linked glycan ions. An outlier analysis on each sample class followed by an unsupervised PCA using a genetic algorithm for pattern recognition reveals that EAC samples are separated from NC samples based on 46 features originating from the 11-glycan composite IMS distribution. PMID:23126309

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

    NASA Astrophysics Data System (ADS)

    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

    PubMed Central

    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. Control of Chemical Effects in the Separation Process of a Differential Mobility / Mass Spectrometer System

    PubMed Central

    Schneider, Bradley B.; Coy, Stephen L.; Krylov, Evgeny V.; Nazarov, Erkinjon G.

    2013-01-01

    Differential mobility spectrometry (DMS) separates ions on the basis of the difference in their migration rates under high versus low electric fields. Several models describing the physical nature of this field mobility dependence have been proposed but emerging as a dominant effect is the clusterization model sometimes referred to as the dynamic cluster-decluster model. DMS resolution and peak capacity is strongly influenced by the addition of modifiers which results in the formation and dissociation of clusters. This process increases selectivity due to the unique chemical interactions that occur between an ion and neutral gas phase molecules. It is thus imperative to bring the parameters influencing the chemical interactions under control and find ways to exploit them in order to improve the analytical utility of the device. In this paper we describe three important areas that need consideration in order to stabilize and capitalize on the chemical processes that dominate a DMS separation. The first involves means of controlling the dynamic equilibrium of the clustering reactions with high concentrations of specific reagents. The second area involves a means to deal with the unwanted heterogeneous cluster ion populations emitted from the electrospray ionization process that degrade resolution and sensitivity. The third involves fine control of parameters that affect the fundamental collision processes, temperature and pressure. PMID:20065515

  1. Sizing Large Proteins and Protein Complexes by Electrospray Ionization Mass Spectrometry and Ion Mobility

    PubMed Central

    Kaddis, Catherine S.; Lomeli, Shirley H.; Yin, Sheng; Berhane, Beniam; Apostol, Marcin I.; Kickhoefer, Valerie A.; Rome, Leonard H.; Loo, Joseph A.

    2009-01-01

    Mass spectrometry (MS) and ion mobility with electrospray ionization (ESI) have the capability to measure and detect large noncovalent protein-ligand and protein-protein complexes. Using an ion mobility method termed GEMMA (Gas-Phase Electrophoretic Mobility Molecular Analysis), protein particles representing a range of sizes can be separated by their electrophoretic mobility in air. Highly charged particles produced from a protein complex solution using electrospray can be manipulated to produce singly charged ions which can be separated and quantified by their electrophoretic mobility. Results from ESI-GEMMA analysis from our laboratory and others were compared to other experimental and theoretically determined parameters, such as molecular mass and cryoelectron microscopy and x-ray crystal structure dimensions. There is a strong correlation between the electrophoretic mobility diameter determined from GEMMA analysis and the molecular mass for protein complexes up to 12 MDa, including the 93 kDa enolase dimer, the 480 kDa ferritin 24-mer complex, the 4.6 MDa cowpea chlorotic mottle virus (CCMV), and the 9 MDa MVP-vault assembly. ESI-GEMMA is used to differentiate a number of similarly sized vault complexes that are composed of different N-terminal protein tags on the MVP subunit. The average effective density of the proteins and protein complexes studied was 0.6 g/cm3. Moreover, there is evidence that proteins and protein complexes collapse or become more compact in the gas phase in the absence of water. PMID:17434746

  2. Traveling Wave Ion Mobility Mass Spectrometry and Ab Initio Calculations of Phosphoric Acid Clusters

    NASA Astrophysics Data System (ADS)

    Lavanant, Hélène; Tognetti, Vincent; Afonso, Carlos

    2014-04-01

    Positive and negative ion electrospray mass spectra obtained from 50 mM phosphoric acid solutions presented a large number of phosphoric acid clusters: [(H3PO4)n + zH] z+ or [(H3PO4)n - zH] z- , with n up to 200 and z up to 4 for positively charged clusters, and n up to 270 and z up to 7 for negatively charged cluster ions. Ion mobility experiments allowed very explicit separation of the different charge states. Because of the increased pressures involved in ion mobility experiments, dissociation to smaller clusters was observed both in the trap and transfer areas. Voltages along the ion path could be optimized so as to minimize this effect, which can be directly associated with the cleavage of hydrogen bonds. Having excluded the ion mobility times that resulted from dissociated ions, each cluster ion appeared at a single drift time. These drift times showed a linear progression with the number of phosphoric atoms for cluster ions of the same charge state. Cross section calculations were carried out with MOBCAL on DFT optimized geometries with different hydrogen locations and with three types of atomic charges. DFT geometry optimizations yielded roughly spherical structures. Our results for nitrogen gas interaction cross sections showed that values were dependent on the atomic charges definition used in the MOBCAL calculation. This pinpointed the necessity to define a clear theoretical framework before any comparative interpretations can be attempted with uncharacterized compounds.

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

    PubMed Central

    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

  4. Mass spectrometric characterization of a high-field asymmetric waveform ion mobility spectrometer

    NASA Astrophysics Data System (ADS)

    Purves, Randy W.; Guevremont, Roger; Day, Stephen; Pipich, Charles W.; Matyjaszczyk, Matthew S.

    1998-12-01

    Ion mobility spectrometry (IMS) has become an important method for the detection of many compounds because of its high sensitivity and amenability to miniaturization for field-portable monitoring; applications include detection of narcotics, explosives, and chemical warfare agents. High-field asymmetric waveform ion mobility spectrometry (FAIMS) differs from IMS in that the electric fields are applied using a high-frequency periodic asymmetric waveform, rather than a dc voltage. Furthermore, in FAIMS the compounds are separated by the difference in the mobility of ions at high electric field relative to low field, rather than by compound to compound differences in mobility at low electric field (IMS). We report here the first cylindrical-geometry-FAIMS interface with mass spectrometry (FAIMS-MS) and the MS identification of the peaks observed in a FAIMS compensation voltage (CV) spectrum. Using both an electrometer-based-FAIMS (FAIMS-E) and FAIMS-MS, several variables that affect the sensitivity of ion detection were examined for two (polarity reversed) asymmetric waveforms (modes 1 and 2) each of which yields a unique spectrum. An increase in the dispersion voltage (DV) was found to improve the sensitivity and separation observed in the FAIMS CV spectrum. This increase in sensitivity and the unexpected dissimilarity in modes 1 and 2 suggest that atmospheric pressure ion focusing is occurring in the FAIMS analyzer. The sensitivity and peak locations in the CV spectra were affected by temperature, gas flow rates, operating pressure, and analyte concentration.

  5. Increasing Confidence of LC-MS Identifications by Utilizing Ion Mobility Spectrometry

    SciTech Connect

    Crowell, Kevin L.; Baker, Erin Shammel; Payne, Samuel H.; Ibrahim, Yehia M.; Monroe, Matthew E.; Slysz, Gordon W.; Lamarche, Brian L.; Petyuk, Vladislav A.; Piehowski, Paul D.; Danielson, William F.; Anderson, Gordon A.; Smith, Richard D.

    2013-09-05

    Ion mobility spectrometry in conjunction with liquid chromatography separations and mass spectrometry offers a range of new possibilities for analyzing complex biological samples. To fully utilize the information obtained from these three measurement dimensions, informatics tools based on the accurate mass and time tag methodology were modified to incorporate ion mobility spectrometry drift times for peptides observed in human serum. A reference human serum database was created using 12,139 peptides, tracking the monoisotopic mass, liquid chromatography normalized elution time, and ion mobility spectrometry drift time(s) for each peptide. We demonstrate that the use of three dimensions for peak matching during the peptide identification process resulted in increased numbers of identifications and lower false discovery rates relative to the use of only the mass and normalized elution time dimensions.

  6. Direct measurement of ion mobility in a conducting polymer.

    PubMed

    Stavrinidou, Eleni; Leleux, Pierre; Rajaona, Harizo; Khodagholy, Dion; Rivnay, Jonathan; Lindau, Manfred; Sanaur, Sébastien; Malliaras, George G

    2013-08-27

    Using planar junctions between the conducting polymer PEDOT:PSS and various electrolytes, it is possible to inject common ions and directly observe their transit through the film. The 1D geometry of the experiment allows a straightforward estimate of the ion drift mobilities. PMID:23784809

  7. 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.

    PubMed

    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. PMID:27194523

  8. Pushing the Frontier of High-Definition Ion Mobility Spectrometry Using FAIMS

    PubMed Central

    A. Shvartsburg, Alexandre; A. Anderson, Gordon; D. Smith, Richard

    2013-01-01

    Differential ion mobility spectrometry (FAIMS) separates ions in gases based on the difference between their mobilities in strong and weak electric fields, captured directly employing a periodic waveform with dissimilar profiles in opposite polarities. As that difference is not tightly correlated with the ion size or mass, FAIMS separations are generally quite orthogonal to both conventional IMS (based on the absolute ion mobility that reflects the physical ion size) and mass spectrometry (based on mass). Until a few years ago, that advantage was largely offset by poor FAIMS resolving power (∼10–20), an order of magnitude below that achieved with conventional (drift-tube) IMS. This article summarizes the major recent technical developments that have raised FAIMS resolving power up to ∼500. These include use of higher and more stable voltages provided by new waveform generators, novel buffer gas compositions comprising high helium or hydrogen fractions, and extended filtering times up to ∼1 s. These advances have enabled previously unthinkable analyses such as broad baseline separations of peptide sequence inversions, localization variants (post-translationally modified peptides with differing PTM attachment sites) even for the larger “middle-down” peptides and smallest PTMs, and lipid regioisomers. PMID:24349930

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

    PubMed

    Ferguson, Carly N; Gucinski-Ruth, Ashley C

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  11. Micro-machined planar field asymmetric ion mobility spectrometer as a gas chromatographic detector

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Nazarov, E. G.; Miller, R. A.; Krylov, E. V.; Zapata, A. M.

    2002-01-01

    A planar high field asymmetric waveform ion mobility spectrometer (PFAIMS) with a micro-machined drift tube was characterized as a detector for capillary gas chromatography. The performance of the PFAIMS was compared directly to that of a flame ionization detector (FID) for the separation of a ketone mixture from butanone to decanone. Effluent from the column was continuously sampled by the detector and mobility scans could be obtained throughout the chromatographic analysis providing chemical inforrmation in mobility scans orthogonal to retention time. Limits of detection were approximately I ng for measurement of positive ions and were comparable or slightly better than those for the FID. Direct comparison of calibration curves for the FAIMS and the FID was possible over four orders of magnitude with a semi-log plot. The concentration dependence of the PFAIMS mobility scans showed the dependence between ion intensity and ion clustering, evident in other mobility spectrometers and atmospheric pressure ionization technologies. Ions were identified using mass spectrometry as the protonated monomer and the proton bound dimer of the ketones. Residence time for column effluent in the PFAIMS was calculated as approximately 1 ms and a 36% increase in extra-column broadening versus the FID occurred with the PFAIMS.

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

    PubMed

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

    2016-06-01

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

  13. Mobilities of negative halogen ions in various gases

    NASA Astrophysics Data System (ADS)

    Fujii, T.; Meisels, G. G.

    1981-11-01

    The mobilities of SF6(-) in He and of F(-), Cl(-), Br(-), and I(-) in Ar, Xe, H2, N2, CO, and CH4, have been investigated over the field-strength (E/P) range of 5 to 25 V/cm Torr using time-resolved high pressure mass spectrometry and an ion source with coaxial electron entrance and ion drift fields. The reduced mobilities obtained by this method are in good agreement with those obtained in drift tubes when comparison is possible. Results are compared with Langevin polarization limits and with the drift properties of isoelectronic positive alkali ions measured previously.

  14. Method of multiplexed analysis using ion mobility spectrometer

    DOEpatents

    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.

  15. Realizing Synchronous Energy Harvesting and Ion Separation with Graphene Oxide Membranes

    PubMed Central

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Zhu, Hongwei

    2014-01-01

    A synchronous ion separation and electricity generation process has been developed using G-O membranes. In addition to the size effect proposed prevsiouly, the separation of ions can be attributed to the different interactions between ions and G-O membranes; the generation of electricity is due to the confinement of G-O membranes, and the mobility difference of ions. Efficient energy transduction has been achieved with G-O membranes, converting magnetic, thermal and osmotic energy to electricity, distinguishing this material from other commercial semi-permeable membranes. Our study indicated that G-O membranes could find potential applications in the purification of wastewater, while producing electricity simultaneously. With G-O membranes, industrial magnetic leakage and waste heat could also be used to produce electricity, affording a superior approach for energy recovery. PMID:24984782

  16. Realizing Synchronous Energy Harvesting and Ion Separation with Graphene Oxide Membranes

    NASA Astrophysics Data System (ADS)

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Zhu, Hongwei

    2014-07-01

    A synchronous ion separation and electricity generation process has been developed using G-O membranes. In addition to the size effect proposed prevsiouly, the separation of ions can be attributed to the different interactions between ions and G-O membranes; the generation of electricity is due to the confinement of G-O membranes, and the mobility difference of ions. Efficient energy transduction has been achieved with G-O membranes, converting magnetic, thermal and osmotic energy to electricity, distinguishing this material from other commercial semi-permeable membranes. Our study indicated that G-O membranes could find potential applications in the purification of wastewater, while producing electricity simultaneously. With G-O membranes, industrial magnetic leakage and waste heat could also be used to produce electricity, affording a superior approach for energy recovery.

  17. Realizing synchronous energy harvesting and ion separation with graphene oxide membranes.

    PubMed

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Zhu, Hongwei

    2014-01-01

    A synchronous ion separation and electricity generation process has been developed using G-O membranes. In addition to the size effect proposed prevsiouly, the separation of ions can be attributed to the different interactions between ions and G-O membranes; the generation of electricity is due to the confinement of G-O membranes, and the mobility difference of ions. Efficient energy transduction has been achieved with G-O membranes, converting magnetic, thermal and osmotic energy to electricity, distinguishing this material from other commercial semi-permeable membranes. Our study indicated that G-O membranes could find potential applications in the purification of wastewater, while producing electricity simultaneously. With G-O membranes, industrial magnetic leakage and waste heat could also be used to produce electricity, affording a superior approach for energy recovery. PMID:24984782

  18. Ion Exchange Separation of the Oxidation State of Vanadium.

    ERIC Educational Resources Information Center

    Cornelius, Richard

    1980-01-01

    Describes an experiment that emphasizes the discrete nature of the different oxidation states of vanadium by the separation of ammonium metavanadate into all four species by ion exchange chromatography. (CS)

  19. Detection of gunpowder stabilizers with ion mobility spectrometry.

    PubMed

    West, C; Baron, G; Minet, J-J

    2007-03-01

    This study is the first reported ion mobility detection of ethyl centralite and diphenylamine (DPA) smokeless gunpowder stabilizers, together with the nitroso and nitro derivatives of diphenylamine. First, the applicability of the ion mobility spectrometry (IMS) for the substances of interest was determined. The existence of numerous peaks, both in positive and negative modes, clearly demonstrates the success of these experiments. All mono and di-nitro derivatives of DPA tested were detected with this method. Unfortunately, many of the ions generated were not accurately identified. However, reduced mobility constants representative of each ion generated under defined operating conditions could be used for purpose of compound identification. The method was then successfully tested on real gunpowder samples. By the use of IMS, we managed to establish a rapid, simple and sensitive screening method for the detection and identification of smokeless gunpowder organic components. PMID:16828537

  20. Mineral Separation in a CELSS by Ion-exchange Chromatography

    NASA Technical Reports Server (NTRS)

    Ballou, E. V.; Spitze, L. A.; Wong, F. W.; Wydeven, T.; Johnson, C. C.

    1982-01-01

    Operational parameters pertinent to ion exchange chromatography separation were identified. The experiments were performed with 9 mm diameter ion exchange columns and conventional column accessories. The cation separation beds were packed with AG 50W-X2 strong acid cation exchange resin in H(+) form and 200-400 dry mesh particle size. The stripper beds used in some experiments were packed with AG 1-XB strong base cation exchange resin in OH(-) form and 200-400 dry mesh particle size.

  1. Tandem ion mobility spectrometry coupled to laser excitation

    SciTech Connect

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

    2015-09-15

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Entropic Electrokinetics: Recirculation, Particle Separation, and Negative Mobility

    NASA Astrophysics Data System (ADS)

    Malgaretti, Paolo; Pagonabarraga, Ignacio; Rubi, J. Miguel

    2014-09-01

    We show that when particles are suspended in an electrolyte confined between corrugated charged surfaces, electrokinetic flows lead to a new set of phenomena such as particle separation, mixing for low-Reynolds micro- and nanometric devices, and negative mobility. Our analysis shows that such phenomena arise, for incompressible fluids, due to the interplay between the electrostatic double layer and the corrugated geometrical confinement and that they are magnified when the width of the channel is comparable to the Debye length. Our characterization allows us to understand the physical origin of such phenomena, therefore, shedding light on their possible relevance in a wide variety of situations ranging from nano- and microfluidic devices to biological systems.

  4. Ion mobility spectrometry of hydrazine, monomethylhydrazine, and ammonia in air with 5-nonanone reagent gas

    NASA Technical Reports Server (NTRS)

    Eiceman, G. A.; Salazar, M. R.; Rodriguez, M. R.; Limero, T. F.; Beck, S. W.; Cross, J. H.; Young, R.; James, J. T.

    1993-01-01

    Hydrazine (HZ) and monomethylhydrazine (MMH) in air were monitored continuously using a hand-held ion mobility spectrometer equipped with membrane inlet, 63Ni ion source, acetone reagent gas, and ambient temperature drift tube. Response characteristics included detection limit, 6 ppb; linear range, 10-600 ppb; saturated response, >2 ppm; and stable response after 15-30 min. Ammonia interfered in hydrazines detection through a product ion with the same drift time as that for MMH and HZ. Acetone reagent gas was replaced with 5-nonanone to alter drift times of product ions and separate ammonia from MMH and HZ. Patterns in mobility spectra, ion identifications from mass spectra, and fragmentation cross-sections from collisional-induced dissociations suggest that drift times are governed by ion-cluster equilibria in the drift region of the mobility spectrometer. Practical aspects including calibration, stability, and reproducibility are reported from the use of a hand-held mobility spectrometer on the space shuttle Atlantis during mission STS-37.

  5. Ion Mobility Spectrometry Reveals Duplex DNA Dissociation Intermediates

    NASA Astrophysics Data System (ADS)

    Burmistrova, Anastasia; Gabelica, Valérie; Duwez, Anne-Sophie; De Pauw, Edwin

    2013-11-01

    Electrospray ionization (ESI) soft desolvation is widely used to investigate fragile species such as nucleic acids. Tandem mass spectrometry (MS/MS) gives access to the gas phase energetics of the intermolecular interactions in the absence of solvent, by following the dissociation of mass-selected ions. Ion mobility mass spectrometry (IMS) provides indications on the tridimensional oligonucleotide structure by attributing a collision cross section (CCS) to the studied ion. Electrosprayed duplexes longer than eight bases pairs retain their helical structure in a solvent-free environment. However, the question of conformational changes under activation in MS/MS studies remains open. The objective of this study is to probe binding energetics and characterize the unfolding steps occurring prior to oligonucleotide duplex dissociation. Comparing the evolution of CCS with collision energy and breakdown curves, we characterize dissociation pathways involved in CID-activated DNA duplex separation into single strands, and we demonstrate here the existence of stable dissociation intermediates. At fixed duplex length, dissociation pathways were found to depend on the percentage of GC base pairs and on their position in the duplex. Our results show that pure GC sequences undergo a gradual compaction until reaching the dissociation intermediate: A-helix. Mixed AT-GC sequences were found to present at least two conformers: a classic B-helix and an extended structure where the GC tract is a B-helix and the AT tract(s) fray. The dissociation in single strands takes place from both conformers when the AT base pairs are enclosed between two GC tracts or only from the extended conformer when the AT tract is situated at the end(s) of the sequence.

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

    SciTech Connect

    Hunka, Deborah E; Austin, Daniel

    2005-10-01

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

  7. Separation of platinum group metal ions by Donnan dialysis

    SciTech Connect

    Brajter, K.; Slonawska, K.; Cox, J.A.

    1985-10-01

    Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.

  8. Separation of ions in acidic solution by capillary electrophoresis

    SciTech Connect

    Thornton, M.

    1997-10-08

    Capillary electrophoresis (CE) is an effective method for separating ionic species according to differences in their electrophoretic mobilities. CE separations of amino acids by direct detection are difficult due to their similar electrophoretic mobilities and low absorbances. However, native amino acids can be separated by CE as cations at a low pH by adding an alkanesulfonic acid to the electrolyte carrier which imparts selectivity to the system. Derivatization is unnecessary when direct UV detection is used at 185 nm. Simultaneous speciation of metal cations such as vanadium (IV) and vanadium (V) can easily be performed without complexation prior to analysis. An indirect UV detection scheme for acidic conditions was also developed using guanidine as the background carrier electrolyte (BCE) for the indirect detection of metal cations. Three chapters have been removed for separate processing. This report contains introductory material, references, and general conclusions. 80 refs.

  9. Separation of organic ion exchange resins from sludge -- engineering study

    SciTech Connect

    Duncan, J.B.

    1998-08-25

    This engineering study evaluates the use of physical separation technologies to separate organic ion exchange resin from KE Basin sludge prior to nitric acid dissolution. This separation is necessitate to prevent nitration of the organics in the acid dissolver. The technologies under consideration are: screening, sedimentation, elutriation. The recommended approach is to first screen the Sludge and resin 300 microns then subject the 300 microns plus material to elutriation.

  10. Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.

    2011-04-28

    The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm{sup 2}V{sup -1}s{sup -1} across the temperature range from 60 to 140 C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.

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

    SciTech Connect

    Hunka Deborah Elaine; Austin, Daniel E.

    2005-07-01

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

  12. Online deuterium hydrogen exchange and protein digestion coupled with ion mobility spectrometry and tandem mass spectrometry.

    PubMed

    Donohoe, Gregory C; Arndt, James R; Valentine, Stephen J

    2015-05-19

    Online deuterium hydrogen exchange (DHX) and pepsin digestion (PD) is demonstrated using drift tube ion mobility spectrometry (DTIMS) coupled with linear ion trap (LTQ) mass spectrometry (MS) with electron transfer dissociation (ETD) capabilities. DHX of deuterated ubiquitin, followed by subsequent quenching and digestion, is performed within ∼60 s, yielding 100% peptide sequence coverage. The high reproducibility of the IMS separation allows spectral feature matching between two-dimensional IMS-MS datasets (undeuterated and deuterated) without the need for dataset alignment. Extracted ion drift time distributions (XIDTDs) of deuterated peptic peptides are mobility-matched to corresponding XIDTDs of undeuterated peptic peptides that were identified using collision-induced dissociation (CID). Matching XIDTDs allows a straightforward identification and deuterium retention evaluation for labeled peptides. Aside from the mobility separation, the ion trapping capabilities of the LTQ, combined with ETD, are demonstrated to provide single-residue resolution. Deuterium retention for the c- series ions across residues M(1)-L(15) and N(25)-R(42) are in good agreement with the known secondary structural elements within ubiquitin. PMID:25893550

  13. Electrodialytic separation of alkali-element ions with the aid of ion-exchange membranes

    SciTech Connect

    Gurskii, V.S.; Moskvin, L.N.

    1988-03-20

    Electrodialytic separation of ions bearing charges of the same sign with the aid of ion-exchange membranes has been examined in the literature in relation to the so-called ideal membranes, which do not exhibit selectivity with respect to one ion type in ion exchange. It has been shown that separation on such membranes is effective only for counterions differing in size of charge. A matter of greater importance from the practical standpoint is the possibility of using electrodialysis for separating ions bearing like charges and having similar properties, including ionic forms of isotopes of the same element. In this paper they report a comparative study of ion separation, with reference to the Cs-Na pair, by electrodialysis through various types of cation-exchange membranes. Changes of the solution concentration in the cathode compartment were monitored by measurement of /sup 22/Na and /sup 137/Cs activities.

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

    PubMed

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

    2016-03-15

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

  15. Ion current detector for high pressure ion sources for monitoring separations

    DOEpatents

    Smith, Richard D.; Wahl, Jon H.; Hofstadler, Steven A.

    1996-01-01

    The present invention relates generally to any application involving the monitoring of signal arising from ions produced by electrospray or other high pressure (>100 torr) ion sources. The present invention relates specifically to an apparatus and method for the detection of ions emitted from a capillary electrophoresis (CE) system, liquid chromatography, or other small-scale separation methods. And further, the invention provides a very simple diagnostic as to the quality of the separation and the operation of an electrospray source.

  16. Alkaline Anion-Exchange Membranes Containing Mobile Ion Shuttles.

    PubMed

    Ge, Xiaolin; He, Yubin; Guiver, Michael D; Wu, Liang; Ran, Jin; Yang, Zhengjin; Xu, Tongwen

    2016-05-01

    A new class of alkaline anion-exchange membranes containing mobile ion shuttles is developed. It is achieved by threading ionic linear guests into poly(crown ether) hosts via host-guest molecular interaction. The thermal- and pH-triggered shuttling of ionic linear guests remarkably increases the solvation-shell fluctuations in inactive hydrated hydroxide ion complexes (OH(-) (H2 O)4 ) and accelerates the OH(-) transport. PMID:26972938

  17. Resolution of Ion Mobility Spectra for the Detection of Hazardous Substances in Real Sampling Conditions

    SciTech Connect

    Montoliu, I.; Kalms, A.; Pardo, A.; Pomareda, V.; Marco, S.; Goebel, J.; Kessler, M.; Mueller, G.

    2009-05-23

    This work presents the possibilities offered by a blind source separation method such Multivariate Curve Resolution- Alternating Least Squares (MCR-ALS) in the analysis of Ion Mobility Spectra (IMS). Two security applications are analyzed in this context: the detection of TNT both in synthetic and real samples. Results obtained show the possibilities offered by the direct analysis of the drift time spectra when an appropriate resolution method is used.

  18. New, high-efficiency ion trap mobility detection system for narcotics and explosives

    NASA Astrophysics Data System (ADS)

    McGann, William J.; Bradley, V.; Borsody, A.; Lepine, S.

    1994-10-01

    A new patented Ion Trap Mobility Spectrometer (ITMS) design is presented. Conventional IMS designs typically operate below 0.1% efficiency. This is due primarily to electric field driven, sample ion discharge on a shutter grid. Since 99.9% of the sample ions generated in the reaction region are lost in this discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an `ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a `field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. Many applications for this new detector are now being considered including the detection of narcotics and explosives. Preliminary ion spectra, reduced mobility data and sensitivity data are presented for fifteen narcotics, including cocaine, THC and LSD are reported.

  19. New high-efficiency ion trap mobility detection system for narcotics and explosives

    NASA Astrophysics Data System (ADS)

    McGann, William J.; Jenkins, Anthony; Ribiero, K.; Napoli, J.

    1994-03-01

    A new patented ion trap mobility spectrometer design is presented. Conventional IMS designs typically operate below 0.1% efficiency. This is due primarily to electrical-field-driven, sample ion discharge on a shutter grid. Since 99.9% of the sample ions generated in the reaction region are lost in this discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an `ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a `field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. Many applications for this new detector are now being considered including the detection of narcotics and explosives. Preliminary ion spectra, reduced mobility data and sensitivity data are presented for fifteen narcotics, including cocaine, THC, and LSD are reported.

  20. Cryogenic molecular separation system for radioactive 11C ion acceleration

    NASA Astrophysics Data System (ADS)

    Katagiri, K.; Noda, A.; Suzuki, K.; Nagatsu, K.; Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.; Donets, E. E.; Ramzdorf, A. Yu.; Nakao, M.; Hojo, S.; Wakui, T.; Noda, K.

    2015-12-01

    A 11C molecular production/separation system (CMPS) has been developed as part of an isotope separation on line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive 11C ion beams. In the ISOL system, 11CH4 molecules will be produced by proton irradiation and separated from residual air impurities and impurities produced during the irradiation. The CMPS includes two cryogenic traps to separate specific molecules selectively from impurities by using vapor pressure differences among the molecular species. To investigate the fundamental performance of the CMPS, we performed separation experiments with non-radioactive 12CH4 gases, which can simulate the chemical characteristics of 11CH4 gases. We investigated the separation of CH4 molecules from impurities, which will be present as residual gases and are expected to be difficult to separate because the vapor pressure of air molecules is close to that of CH4. We determined the collection/separation efficiencies of the CMPS for various amounts of air impurities and found desirable operating conditions for the CMPS to be used as a molecular separation device in our ISOL system.

  1. Experimental ion mobility measurements in Ar-CO2 mixtures

    NASA Astrophysics Data System (ADS)

    Encarnação, P. M. C. C.; Cortez, A. F. V.; Pinto, M. G. A.; Neves, P. N. B.; Trindade, A. M. F.; Escada, J.; Santos, F. P.; Borges, F. I. G. M.; Barata, J. A. S.; Conde, C. A. N.

    2015-01-01

    In this paper we present the experimental results for the mobility of ions in argon-carbon dioxide gaseous mixtures (Ar-CO2) for pressures ranging from 6 to 10 Torr and for reduced electric fields in the 10 Td to 25 Td range, at room temperature.The time-of-arrival spectra of the several mixture ratios studied revealed that the relative abundance of the ions and their mobilities depend on the mixture ratio. For Ar concentrations below 80% only one peak was observed in the spectra which was attributed to CO2+, while for Ar concentrations above 80% a second peak appears at the left side of the main peak, which may be due to impurities, probably H2O+. In this work, the time-of-arrival spectra from which reduced mobilities were obtained for Ar concentrations of 20% (K0 = 1.141±0.004 cm2V-1s-1), 50% (K0 = 1.385±0.009 cm2V-1s-1), 85% (K0 = 1.690±0.022 cm2V-1s-1) and 95% (K0 = 1.954±0.043 cm2V-1s-1) are displayed as well as other reduced mobilities values obtained similarly. The ion mobility study was performed at reduced electric field values typically used in gaseous detectors.

  2. COLUMBIC OXIDE ADSORPTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM IONS

    DOEpatents

    Beaton, R.H.

    1959-07-14

    A process is described for separating plutonium ions from a solution of neutron irradiated uranium in which columbic oxide is used as an adsorbert. According to the invention the plutonium ion is selectively adsorbed by Passing a solution containing the plutonium in a valence state not higher than 4 through a porous bed or column of granules of hydrated columbic oxide. The adsorbed plutonium is then desorbed by elution with 3 N nitric acid.

  3. Preorganized and Immobilized Ligands for Metal Ion Separations

    SciTech Connect

    Paine, Robert T.

    2015-07-01

    The research project, in the period 2003-2015, was focused on the discovery of fundamental new principles in f-element ion coordination chemistry and the application of the new knowledge to the development of advanced detection/separations reagents and methods for these ions. The findings relate to the Nation's efforts to safely and efficiently process nuclear materials. In addition, the project provided training for young scientists needed to maintain the Nation's preeminence in nuclear science.

  4. LABORATORY DETECTION OF PLASTICS IN SEEDCOTTON WITH ION MOBILITY SPECTROMETRY

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The US cotton industry wants to increase market share and value by supplying pure cotton. Removing contamination requires developing a means to detect plastics in seedcotton. This study was conducted to determine if Ion Mobility Spectrometry (IMS) could be used to find small amounts of plastic in ...

  5. Review on ion mobility spectrometry. Part 2: hyphenated methods and effects of experimental parameters.

    PubMed

    Cumeras, R; Figueras, E; Davis, C E; Baumbach, J I; Gràcia, I

    2015-03-01

    Ion Mobility Spectrometry (IMS) is a widely used and 'well-known' technique of ion separation in the gaseous phase based on the differences of ion mobilities under an electric field. This technique has received increased interest over the last several decades as evidenced by the pace and advances of new IMS devices available. In this review we explore the hyphenated techniques that are used with IMS, specifically mass spectrometry as an identification approach and a multi-capillary column as a pre-separation approach. Also, we will pay special attention to the key figures of merit of the ion mobility spectrum and how data sets are treated, and the influences of the experimental parameters on both conventional drift time IMS (DTIMS) and miniaturized IMS also known as high Field Asymmetric IMS (FAIMS) in the planar configuration. The present review article is preceded by a companion review article which details the current instrumentation and contains the sections that configure both conventional DTIMS and FAIMS devices. These reviews will give the reader an insightful view of the main characteristics and aspects of the IMS technique. PMID:25465248

  6. Quantitative ion-exchange separation of plutonium from impurities

    SciTech Connect

    Pietri, C.E.; Freeman, B.P.; Weiss, J.R.

    1981-09-01

    The methods used at the New Brunswick Laboratory for the quantitative ion exchange separation of plutonium from impurities prior to plutonium assay are described. Other ion exchange separation procedures for impurity determination and for isotopic abundance measurements are given. The primary technique used consists of sorption of plutonium(IV) in 8N HNO/sub 3/ on Dowex-1 anion exchange resin and elution of the purified plutonium with 0.3N HCl-0.01N HF. Other methods consist of the anion exchange separation of plutonium(IV) in 12N HCl and the cation exchange separation of plutonium(III) in 0.2 N HNO/sub 3/. The application of these procedures to the subsequent assay of plutonium, isotopic analysis, and impurity determination is described.

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

    PubMed

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

    2016-02-16

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

  8. T-wave Ion Mobility-mass Spectrometry: Basic Experimental Procedures for Protein Complex Analysis

    PubMed Central

    Michaelevski, Izhak; Kirshenbaum, Noam; Sharon, Michal

    2010-01-01

    Ion mobility (IM) is a method that measures the time taken for an ion to travel through a pressurized cell under the influence of a weak electric field. The speed by which the ions traverse the drift region depends on their size: large ions will experience a greater number of collisions with the background inert gas (usually N2) and thus travel more slowly through the IM device than those ions that comprise a smaller cross-section. In general, the time it takes for the ions to migrate though the dense gas phase separates them, according to their collision cross-section (Ω). Recently, IM spectrometry was coupled with mass spectrometry and a traveling-wave (T-wave) Synapt ion mobility mass spectrometer (IM-MS) was released. Integrating mass spectrometry with ion mobility enables an extra dimension of sample separation and definition, yielding a three-dimensional spectrum (mass to charge, intensity, and drift time). This separation technique allows the spectral overlap to decrease, and enables resolution of heterogeneous complexes with very similar mass, or mass-to-charge ratios, but different drift times. Moreover, the drift time measurements provide an important layer of structural information, as Ω is related to the overall shape and topology of the ion. The correlation between the measured drift time values and Ω is calculated using a calibration curve generated from calibrant proteins with defined cross-sections1. The power of the IM-MS approach lies in its ability to define the subunit packing and overall shape of protein assemblies at micromolar concentrations, and near-physiological conditions1. Several recent IM studies of both individual proteins2,3 and non-covalent protein complexes4-9, successfully demonstrated that protein quaternary structure is maintained in the gas phase, and highlighted the potential of this approach in the study of protein assemblies of unknown geometry. Here, we provide a detailed description of IMS-MS analysis of protein

  9. LC-IMS-MS Feature Finder. Detecting Multidimensional Liquid Chromatography, Ion Mobility, and Mass Spectrometry Features in Complex Datasets

    SciTech Connect

    Crowell, Kevin L.; Slysz, Gordon W.; Baker, Erin Shammel; Lamarche, Brian L.; Monroe, Matthew E.; Ibrahim, Yehia M.; Payne, Samuel H.; Anderson, Gordon A.; Smith, Richard D.

    2013-09-05

    We introduce a command line software application LC-IMS-MS Feature Finder that searches for molecular ion signatures in multidimensional liquid chromatography-ion mobility spectrometry-mass spectrometry (LC-IMS-MS) data by clustering deisotoped peaks with similar monoisotopic mass, charge state, LC elution time, and ion mobility drift time values. The software application includes an algorithm for detecting and quantifying co-eluting chemical species, including species that exist in multiple conformations that may have been separated in the IMS dimension.

  10. Statistical characterization of air ion mobility spectra at Tahkuse Observatory: Classification of air ions

    NASA Astrophysics Data System (ADS)

    Hõrrak, U.; Salm, J.; Tammet, H.

    2000-04-01

    A database of 8615 hourly averaged air ion mobility spectra in the range of 0.00041-3.2 cm2 V-1 s-1 was measured at Tahkuse Observatory, Estonia, during 14 months in 1993-1994. The average mobility spectrum over the whole period shows distinct peaks of small and large ions. Intermediate ions with mobilities of 0.034-0.5 cm2 V-1 s-1 are of low concentration of about 50 cm-3 in the average spectrum. They experience occasional bursts of up to about 900 cm-3 during 6-10 hours at daytime. The number of burst events recorded during 14 months was 101, with maximum frequency in spring and minimum frequency in winter. Physically, large and intermediate ions can be called aerosol ions, and small ions can be called cluster ions. The principal component analysis was applied to detect the structure of an air ion mobility spectrum. As a result, the mobility spectrum in the range of 0.00041-3.2 cm2 V-1 s-1 (diameters of 0.36-79 nm) was divided into five classes: small cluster, big cluster, intermediate, light large, and heavy large ions. The boundaries between the classes are 1.3 cm2 V-1 s-1 (diameter of 0.85 nm), 0.5 cm2 V-1 s-1 (1.6 nm), 0.034 cm2 V-1 s-1 (7.4 nm), and 0.0042 cm2 V-1 s-1 (22 nm). The five principal components that are closely correlated with the respective ion classes explain 92% of total variance. The classification of aerosol ions is in accord with the three-modal structure of the size spectrum of submicron aerosol particles.

  11. Utilizing Ion-Mobility Data to Estimate Molecular Masses

    NASA Technical Reports Server (NTRS)

    Duong, Tuan; Kanik, Isik

    2008-01-01

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

  12. Assessing the Peak Capacity of IMS-IMS Separations of Tryptic Peptide Ions in 300 K He

    PubMed Central

    Merenbloom, Samuel I.; Bohrer, Brian C.; Koeniger, Stormy L.; Clemmer, David E.

    2011-01-01

    Two-dimensional ion mobility spectrometry (IMS-IMS) coupled with mass spectrometry is examined as a means of separating mixtures of tryptic peptides (from myoglobin and hemoglobin). In this study we utilize two distinct drift regions that are identical in that each contains He buffer gas at 300 K. The two-dimensional advantage is realized by changing the structures of the ions. As ions arrive at the end of the first drift region, those of a specified mobility are selected, exposed to energizing collisions, and then introduced into a second drift region. Upon collisional activation some ions undergo structural transitions, leading to substantial changes in their mobilities; others undergo only slight (or no) mobility changes. Examination of peak positions and shapes for peptides that are separated in the first IMS dimension indicates experimental peak capacities ranging from ~60 to 80; the peak shapes and range of changes in mobility that are observed in the second drift region (after activation) indicates a capacity enhancement ranging from a factor of ~7 to 17. Thus, experimental (and theoretical) evaluation of the peak capacity of IMS-IMS operated in this fashion indicates that capacities of ~480 to 1360 are accessible for peptides. Molecular modeling techniques are used to simulate the range of structural changes that would be expected for tryptic peptide ions and are consistent with the experimental shifts that are observed. PMID:17222015

  13. Ultrasensitive Identification of Localization Variants of Modified Peptides Using Ion Mobility Spectrometry

    PubMed Central

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

    2011-01-01

    Localization of the modification sites on peptides is challenging, particularly when multiple modifications or mixtures of localization isomers (variants) are involved. Such variants commonly coelute in liquid chromatography and may be undistinguishable in tandem mass spectrometry (MS/MS) for lack of unique fragments. Here, we have resolved the variants of singly and doubly phosphorylated peptides employing drift tube ion mobility spectrometry (IMS) coupled to time-of-flight mass spectrometry. Even with a moderate IMS resolving power of ~80, substantial separation was achieved for both 2+ and 3+ ions normally generated by electrospray ionization, including for the variant indistinguishable by MS/MS. Variants often exhibit a distribution of 3-D conformers, which can be adjusted for optimum IMS separation by prior field heating of ions in a funnel trap. The peak assignments were confirmed using MS/MS after IMS separation, but known species could be identified using just the ion mobility ‘tag”. Avoiding the MS/MS step lowers the detection limit of localization variants to <100 attomoles, an order of magnitude better than that provided by electron transfer dissociation in an Orbitrap MS. PMID:21692493

  14. Ultrasensitive Identification of Localization Variants of Modified Peptides Using Ion Mobility Spectrometry

    SciTech Connect

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

    2011-05-28

    Localization of the modification sites on peptides is challenging, particularly when multiple modifications or mixtures of localization isomers (variants) are involved. Such variants commonly coelute in liquid chromatography and may be undistinguishable in tandem mass spectrometry (MS/MS) for lack of unique fragments. Here, we have resolved the variants of singly and doubly phosphorylated peptides employing drift tube ion mobility spectrometry (IMS) coupled to time-of-flight mass spectrometry. Even with a moderate IMS resolving power of ~80, substantial separation was achieved for both 2+ and 3+ ions normally generated by electrospray ionization, including for the variant indistinguishable by MS/MS. Variants often exhibit a distribution of 3-D conformers, which can be adjusted for optimum IMS separation by prior field heating of ions in a funnel trap. The peak assignments were confirmed using MS/MS after IMS separation, but known species could be identified using just the ion mobility "tag". Avoiding the MS/MS step lowers the detection limit of localization variants to <100 attomoles, an order of magnitude better than provided by electron transfer dissociation in an Orbitrap MS.

  15. Control of Ion Distortion in Field Asymmetric Waveform Ion Mobility Spectrometry via Variation of Dispersion Field and Gas Temperature

    SciTech Connect

    Robinson, Errol W.; Shvartsburg, Alexandre A.; Tang, Keqi; Smith, Richard D.

    2008-10-01

    Field asymmetric waveform ion mobility spectrometry (FAIMS) has emerged as an analytical tool of broad utility, especially in conjunction with mass spectrometry. Of particular promise is the use of FAIMS and 2-D ion mobility methods that combine it with conventional IMS to resolve and characterize protein and other macromolecular conformers. However, FAIMS operation requires high electric fields and ions are inevitably heated by above-thermal collisions with buffer gas molecules. This may induce ion isomerization and dissociation that distort separation properties determined by FAIMS and subsequent stages and/or reduce instrumental sensitivity. As FAIMS employs a periodic waveform, the ion temperature can be characterized at the maximum or average field intensity (E). Which method is most applicable to temperature sensitive ions, such as protein ions, has been debated. Here we address this issue by measuring the unfolding of compact ubiquitin ion geometries as a function of waveform amplitude (dispersion field, ED) and gas temperature, T. The field heating is quantified by matching the dependences of structural transitions on ED and T. Increasing ED from 12 to 16 or from 16 to 20 kV/cm is equivalent to heating the (N2) gas by ~15 - 25 oC. The magnitude of field heating for any E can be calculated using the two-temperature theory, and raising ED by 4 kV/cm augments heating by ~15 - 30 oC for maximum and ~4 - 8 oC for average E in the FAIMS cycle. Hence, isomerization of ions in FAIMS appears to be governed by the maximum internal temperature at waveform peaks.

  16. Determination of boron in silicates after ion exchange separation

    USGS Publications Warehouse

    Kramer, H.

    1955-01-01

    Existing methods for the determination of boron in silicates are not entirely satisfactory. Separation as the methyl ester is lengthy and frequently erratic. An accurate and rapid method applicable to glass, mineral, ore, and water samples uses ion exchange to remove interfering cations, and boron is determined titrimetrically in the presence of mannitol, using a pH meter to indicate the end point.

  17. Separation of Carbon Dioxide from Flue Gas Using Ion Pumping

    SciTech Connect

    Aines, R; Bourcier, W L; Johnson, M R

    2006-04-21

    We are developing a new way of separating carbon dioxide from flue gas based on ionic pumping of carbonate ions dissolved in water. Instead of relying on large temperature or pressure changes to remove carbon dioxide from solvent used to absorb it from flue gas, the ion pump increases the concentration of dissolved carbonate ion in solution. This increases the overlying vapor pressure of carbon dioxide gas, which can be removed from the downstream side of the ion pump as a nearly pure gas. This novel approach to increasing the concentration of the extracted gas permits new approaches to treating flue gas. The slightly basic water used as the extraction medium is impervious to trace acid gases that destroy existing solvents, and no pre-separation is necessary. The simple, robust nature of the process lends itself to small separation plants. Although the energy cost of the ion pump is significant, we anticipate that it will be compete favorably with the current 35% energy penalty of chemical stripping systems in use at power plants. There is the distinct possibility that this simple method could be significantly more efficient than existing processes.

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

    SciTech Connect

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

    2007-04-15

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

  19. A flexible statistical model for alignment of label-free proteomics data – incorporating ion mobility and product ion information

    PubMed Central

    2013-01-01

    Background The goal of many proteomics experiments is to determine the abundance of proteins in biological samples, and the variation thereof in various physiological conditions. High-throughput quantitative proteomics, specifically label-free LC-MS/MS, allows rapid measurement of thousands of proteins, enabling large-scale studies of various biological systems. Prior to analyzing these information-rich datasets, raw data must undergo several computational processing steps. We present a method to address one of the essential steps in proteomics data processing - the matching of peptide measurements across samples. Results We describe a novel method for label-free proteomics data alignment with the ability to incorporate previously unused aspects of the data, particularly ion mobility drift times and product ion information. We compare the results of our alignment method to PEPPeR and OpenMS, and compare alignment accuracy achieved by different versions of our method utilizing various data characteristics. Our method results in increased match recall rates and similar or improved mismatch rates compared to PEPPeR and OpenMS feature-based alignment. We also show that the inclusion of drift time and product ion information results in higher recall rates and more confident matches, without increases in error rates. Conclusions Based on the results presented here, we argue that the incorporation of ion mobility drift time and product ion information are worthy pursuits. Alignment methods should be flexible enough to utilize all available data, particularly with recent advancements in experimental separation methods. PMID:24341404

  20. Separation of americium from curium by oxidation and ion exchange.

    PubMed

    Burns, Jonathan D; Shehee, Thomas C; Clearfield, Abraham; Hobbs, David T

    2012-08-21

    Nuclear energy has the potential to be a clean alternative to fossil fuels, but in order for it to play a major role in the US, many questions about the back end of the fuel cycle must be addressed. One of these questions is the difficult separation of americium from curium. Here, we report the oxidation of Am in two systems, perchloric acid and nitric acid and the affect of changing the acid has on the oxidation. K(d) values were observed and a direct separation factor was calculated and was seen to be as high as 20 for four metal(IV) pillared phosphate phosphonate inorganic organic hybrid ion exchange materials. These ion exchangers are characterized by very low selectivity for cations with low charge but extremely high uptake of ions of high charge. PMID:22827724

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

    PubMed

    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. PMID:25327648

  2. Analysis of biogenic amines using corona discharge ion mobility spectrometry.

    PubMed

    Hashemian, Z; Mardihallaj, A; Khayamian, T

    2010-05-15

    A new method based on corona discharge ion mobility spectrometry (CD-IMS) was developed for the analysis of biogenic amines including spermidine, spermine, putrescine, and cadaverine. The ion mobility spectra of the compounds were obtained with and without n-Nonylamine used as the reagent gas. The high proton affinity of n-Nonylamine prevented ion formation from compounds with a proton affinity lower than that of n-Nonylamine and, therefore, enhanced its selectivity. It was also realized that the ion mobility spectrum of n-Nonylamine varied with its concentration. A sample injection port of a gas chromatograph was modified and used as the sample introduction system into the CD-IMS. The detection limits, dynamic ranges, and analytical parameters of the compounds with and without using the reagent gas were obtained. The detection limits and dynamic ranges of the compounds were about 2ng and 2 orders of magnitude, respectively. The wide dynamic range of CD-IMS originates from the high current of the corona discharge. The results revealed the high capability of the CD-IMS for the analysis of biogenic amines. PMID:20298897

  3. High Performance Ion Mobility Spectrometry Using Hourglass Electrodynamic Funnel And Internal Ion Funnel

    DOEpatents

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

    2005-11-22

    A method and apparatus enabling increased sensitivity in ion mobility spectrometry/mass spectrometry instruments which substantially reduces or eliminates the loss of ions in ion mobility spectrometer drift tubes utilizing a device for transmitting ions from an ion source which allows the transmission of ions without significant delay to an hourglass electrodynamic ion funnel at the entrance to the drift tube and/or an internal ion funnel at the exit of the drift tube. An hourglass electrodynamic funnel is formed of at least an entry element, a center element, and an exit element, wherein the aperture of the center element is smaller than the aperture of the entry element and the aperture of the exit elements. Ions generated in a relatively high pressure region by an ion source at the exterior of the hourglass electrodynamic funnel are transmitted to a relatively low pressure region at the entrance of the hourglass funnel through a conductance limiting orifice. Alternating and direct electrical potentials are applied to the elements of the hourglass electrodynamic funnel thereby drawing ions into and through the hourglass electrodynamic funnel thereby introducing relatively large quantities of ions into the drift tube while maintaining the gas pressure and composition at the interior of the drift tube as distinct from those at the entrance of the electrodynamic funnel and allowing a positive gas pressure to be maintained within the drift tube, if desired. An internal ion funnel is provided within the drift tube and is positioned at the exit of said drift tube. The advantage of the internal ion funnel is that ions that are dispersed away from the exit aperture within the drift tube, such as those that are typically lost in conventional drift tubes to any subsequent analysis or measurement, are instead directed through the exit of the drift tube, vastly increasing the amount of ions exiting the drift tube.

  4. Mesoporous Cladophora cellulose separators for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Pan, Ruijun; Cheung, Ocean; Wang, Zhaohui; Tammela, Petter; Huo, Jinxing; Lindh, Jonas; Edström, Kristina; Strømme, Maria; Nyholm, Leif

    2016-07-01

    Much effort is currently made to develop inexpensive and renewable materials which can replace the polyolefin microporous separators conventionally used in contemporary lithium-ion batteries. In the present work, it is demonstrated that mesoporous Cladophora cellulose (CC) separators constitute very promising alternatives based on their high crystallinity, good thermal stability and straightforward manufacturing. The CC separators, which are fabricated using an undemanding paper-making like process involving vacuum filtration, have a typical thickness of about 35 μm, an average pore size of about 20 nm, a Young's modulus of 5.9 GPa and also exhibit an ionic conductivity of 0.4 mS cm-1 after soaking with 1 M LiPF6 EC: DEC (1/1, v/v) electrolyte. The CC separators are demonstrated to be thermally stable at 150 °C and electrochemically inert in the potential range between 0 and 5 V vs. Li+/Li. A LiFePO4/Li cell containing a CC separator showed good cycling stability with 99.5% discharge capacity retention after 50 cycles at a rate of 0.2 C. These results indicate that the renewable CC separators are well-suited for use in high-performance lithium-ion batteries.

  5. Metabolic Profiling of Human Blood by High Resolution Ion Mobility Mass Spectrometry (IM-MS)

    PubMed Central

    Dwivedi, Prabha; Schultz, Albert J.; Hill, Herbert H.

    2010-01-01

    A high resolution ion mobility time-of-flight mass spectrometer with electrospray ionization source (ESI-IM-MS) was evaluated as an analytical method for rapid analysis of complex biological samples such as human blood metabolome was investigated. The hybrid instrument (IM-MS) provided an average ion mobility resolving power of ~90 and a mass resolution of ~1500 (at m/z 100). A few µL of whole blood was extracted with methanol, centrifuged and infused into the IM-MS via an electrospray ionization source. Upon IM-MS profiling of the human blood metabolome approximately 1,100 metabolite ions were detected and 300 isomeric metabolites separated in short analyses time (30 minutes). Estimated concentration of the metabolites ranged from the low micromolar to the low nanomolar level. Various classes of metabolites (amino acids, organic acids, fatty acids, carbohydrates, purines and pyrimidines etc) were found to form characteristic mobility-mass correlation curves (MMCC) that aided in metabolite identification. Peaks corresponding to various sterol derivatives, estrogen derivatives, phosphocholines, prostaglandins, and cholesterol derivatives detected in the blood extract were found to occupy characteristic two dimensional IM-MS space. Low abundance metabolite peaks that can be lost in MS random noise were resolved from noise peaks by differentiation in mobility space. In addition, the peak capacity of MS increased six fold by coupling IMS prior to MS analysis. PMID:21113320

  6. Description of Gas-Phase Ion/Neutral Interactions in Differential Ion Mobility Spectrometry: CV Prediction Using Calibration Runs

    NASA Astrophysics Data System (ADS)

    Auerbach, David; Aspenleiter, Julia; Volmer, Dietrich A.

    2014-09-01

    Differential ion mobility spectrometry (DMS) coupled to mass spectrometry is increasingly used in both quantitative analyses of biological samples and as a means of removing background interferences for enhanced selectivity and improved quality of mass spectra. However, DMS separation efficiency using dry inert gases often lacks the required selectivity to achieve baseline separation. Polar gas-phase modifiers such as alcohols are therefore frequently employed to improve selectivity via clustering/declustering processes. The choice of an optimal modifier currently relies on trial and error experiments, making method development a tedious activity. It was the goal of this study to establish a means of CV prediction for compounds using a homologous series of alcohols as gas-phase modifiers. This prediction was based on linear regression of compensation voltages of two calibration runs for the alcohols with the lowest and the highest molecular weights and readily available descriptors such as proton affinity and gas phase acidity of the modifier molecules. All experiments were performed on a commercial quadrupole linear ion trap mass spectrometer equipped with a DMS device between electrospray ionization source and entrance quadrupole lens. We evaluated our approach using a homologous series of 4-alkylbenzoic acids and a selection of 23 small molecules of high chemical diversity. Predicted CV values typically deviated from the experimentally determined values by less than 0.5 V. Several test compounds changed their ion mobility behavior for the investigated gas phase modifiers (e.g., from type B to type A) and thus could thus not be evaluated.

  7. The interplay of ion crosslinking, free ion content, and polymer mobility in PEO-based single-ion conductors

    NASA Astrophysics Data System (ADS)

    Lin, Kan-Ju; Maranas, Janna

    2010-03-01

    We use molecular dynamics simulation to study ion clustering and dynamics in ion containing polymers. This PEO based single-ion conducting ionomer serves as a model system for understanding cation transport in solid state polymer electrolytes (SPEs). Although small-angle x-ray scattering does not show an ionomer peak, we observer various cation-anion complexes in the simulation, suggesting ionomer backbones are crosslinked through ion complexes. These crosslinks reduce the adjacent PEO mobility resulting in a symmetric mobility gradient along the PEO chain. We vary the cation-anion interaction in the simulation to observe the interplay of cation-anion association, polymer mobility and cation motion. Cation-anion association controls the number of free ions, which is important in ionic conductivity when these materials are used as SPEs. Polymer mobility controls how fast the free ions are able to move through the SPE. High conductivity requires both a high free ion content and fast polymer motion. To understand the connection between the two, we ``tune'' the force field in order to manipulate the free ion content and observe the influence on PEO dynamics.

  8. Ion Mobility Drift Spectrometer (IMDS) as a flight analytical instrument technique

    NASA Technical Reports Server (NTRS)

    Kojiro, D. R.; Carle, G. C.

    1986-01-01

    A detailed knowledge of the history and abundances of the biogenic elements and their compounds throughout the solar system can provide the exobiologists with a basis for understanding the conditions necessary for chemical evolution and the origin of life. The Ion Mobility Drift Spectrometer is an ion molecule reactor coupled with an ion drift spectrometer. Sample molecules are ionized to form product ions in the reactant region. An electric field moves the ions through a drift region against the flow of a drift gas where they are separated according to their size and structure producing an ion mobility spectrum. These spectra provide the IMDS with virtually universal sample identification capability. To conform to the rigid limits of weight, volume and consumables placed on flight instrumentation, several aspects of the IMDS must be studied and redesigned for flight use. In addition to miniaturization of the instrument, a reduction in the high flow rates used for the drift gas is an obvious necessary consideration. The effect of drastically reduced drift flow rates on IMDS spectra was investigated by lowering flow rates from 500ml/min to 50ml/min. Changes in peak shape, drift time and total spectra were studied at each flow rate.

  9. Structured back gates for high-mobility two-dimensional electron systems using oxygen ion implantation

    NASA Astrophysics Data System (ADS)

    Berl, M.; Tiemann, L.; Dietsche, W.; Karl, H.; Wegscheider, W.

    2016-03-01

    We present a reliable method to obtain patterned back gates compatible with high mobility molecular beam epitaxy via local oxygen ion implantation that suppresses the conductivity of an 80 nm thick silicon doped GaAs epilayer. Our technique was optimized to circumvent several constraints of other gating and implantation methods. The ion-implanted surface remains atomically flat which allows unperturbed epitaxial overgrowth. We demonstrate the practical application of this gating technique by using magneto-transport spectroscopy on a two-dimensional electron system (2DES) with a mobility exceeding 20 × 106 cm2/V s. The back gate was spatially separated from the Ohmic contacts of the 2DES, thus minimizing the probability for electrical shorts or leakage and permitting simple contacting schemes.

  10. Developments in ion mobility spectrometry-mass spectrometry.

    PubMed

    Collins, D C; Lee, M L

    2002-01-01

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

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

    DOEpatents

    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.

  12. Ultra High-Resolution Electrospray Ionization/Ion Mobility Spectrometer System for In-Situ Detection of Organic Compounds

    NASA Technical Reports Server (NTRS)

    Kanik, I.; Beegle, L. W.; Hill, H. H.

    2001-01-01

    The potential of the high-resolution Electrospray Ionization/Ion Mobility Spectrometry (ESI/IMS) technique as analytical separation tool in analyzing bio-molecular mixtures in the search for the chemical signatures of life is demonstrated. Additional information is contained in the original extended abstract.

  13. Compact ExB mass separator for heavy ion beams

    SciTech Connect

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

    2008-02-15

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

  14. Quantitative determination of residual active pharmaceutical ingredients and intermediates on equipment surfaces by ion mobility spectrometry.

    PubMed

    Qin, C; Granger, A; Papov, V; McCaffrey, J; Norwood, D L

    2010-01-01

    Ion mobility spectrometry (IMS) is an analytical technique that separates ions based on their gas phase mobility at atmospheric pressure. Since gas phase ion mobility is a function of the shape and structure of the ion, this technique has the potential to provide unique specificity and selectivity. Furthermore, IMS is very sensitive (subnanogram detection limits for many small molecules), and a single analysis is typically completed within 1 min. In principle, these features of IMS should make it an ideal choice for use in cleaning verification analysis of pharmaceutical manufacturing equipment. This report describes the successful development and validation of three different equipment cleaning verification methods using IMS. The methods were developed for a specific intermediate (Compound A) in the synthetic route for a drug substance as well as for final drug substances (active pharmaceutical ingredients Compounds B and C). The cleaning verification methods were validated with respect to specificity, linearity, precision, accuracy, stability, and limit-of-quantitation. In all cases, the limits-of-quantitation were determined to be at the nanogram or sub-nanogram level. Both swab and rinse samples collected from the equipment surfaces were successfully analyzed and manufacturing equipment down-time was significantly minimized due to the reduction in cleaning verification analysis time (for example, the total analysis time for more than 30 samples using IMS was reduced to less than 2h). PMID:19758781

  15. Direct Liquid Sampling for Corona Discharge Ion Mobility Spectrometry.

    PubMed

    Sabo, Martin; Malásková, Michaela; Harmathová, Olga; Hradski, Jasna; Masár, Marián; Radjenovic, Branislav; Matejčík, Štefan

    2015-07-21

    We present a new technique suitable for direct liquid sampling and analysis by ion mobility spectrometry (IMS). The technique is based on introduction of a droplet stream to the IMS reaction region. The technique was successfully used to detect explosives dissolved in methanol and oil as well as to analyze amino acids and dipeptides. One of the main advantages of this technique is its ability to analyze liquid samples without the requirement of any special solution. PMID:26154532

  16. Ion mobility and transport barriers in the tokamak plasmas

    SciTech Connect

    Xiao, H.; Hazeltine, R.D.; Valanju, P.M.; Zhang, Y.Z.

    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.

  17. Control of Ion Distortion in Field Asymmetric Waveform Ion Mobility Spectrometry via Variation of Dispersion Field and Gas Temperature

    PubMed Central

    Robinson, Errol W.; Shvartsburg, Alexandre A.; Tang, Keqi; Smith, Richard D.

    2009-01-01

    Field asymmetric waveform ion mobility spectrometry (FAIMS) has emerged as an analytical tool of broad utility, especially in conjunction with mass spectrometry. Of particular promise is the use of FAIMS and 2-D ion mobility methods that combine FAIMS with conventional IMS to resolve and characterize protein and other macromolecular conformers. However, FAIMS operation requires a strong electric field and ions are inevitably heated by energetic collisions with buffer gas molecules. This may induce ion isomerization or dissociation that distort the separation properties of FAIMS (and subsequent stages) and/or reduce instrumental sensitivity. As FAIMS employs a periodic waveform, whether those processes are controlled by ion temperature at maximum or average field intensity has been debated. Here we address this issue by measuring the unfolding of compact ubiquitin ion geometries as a function of waveform amplitude (dispersion field, ED) and gas temperature, T. The field heating is quantified by matching the dependences of structural transitions on ED and T: increasing ED from 12 to 16 or from 16 to 20 kV/cm is equivalent to heating the (N2) gas by ∼15 – 25 °C. The magnitude of field heating for any ED can be estimated using the two-temperature theory, and raising ED by 4 kV/cm augments heating by ∼15 – 30 °C for maximum and ∼4 – 8 °C for average field in the FAIMS cycle. Hence, isomerization of ions in FAIMS appears to be determined by the excitation at waveform peaks. PMID:18729473

  18. Profiling of phospholipids and related lipid structures using multidimensional ion mobility spectrometry-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah; Tan, Bo; Bohrer, Brian C.; O'Dell, David K.; Merenbloom, Samuel I.; Pazos, Mauricio X.; Clemmer, David E.; Walker, J. Michael

    2009-10-01

    Increasingly comprehensive questions related to the biosynthesis of lipids relevant to understanding new signaling pathways have created daunting tasks for their chemical analysis. Here, ion mobility spectrometry (IMS) and mass spectrometry (MS) techniques combined with electrospray ionization have been used to examine mixtures of closely related lipid structures. The drift time distributions of sphingomyelins show baseline separations for ethylene chain length differences ([Delta] ~ 1.2 ms) and partial separations in single unsaturation differences ([Delta] ~ 0.3 ms) revealing that the most compact structures are observed with shorter chains and increasing unsaturation. Drift time distributions of different ionizations frequently fall into families with the same drift times (isodrifts) indicating that the ion attached to the lipid has little structural influence. The present data show that phospholipids, especially phosphatidylinositol, aggregate to form inverted micelles. Phospholipids (phosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, sphingomyelin, and phosphatidylinositol) are effectively separated according to their polar head groups. This method also provides information about the mixture composition of the chemically different lipids N-palmitoyl glycine, N-arachidonoyl ethanolamide, and phosphatidylcholine existing over an array of charge states and sizes (inverted micelles) depending on mixture concentration. Multidimensional IMS3-MS introduces an additional dimension to fragmentation analysis by separating the fragmented ions into groups related to size, shape and charge and allows determination of sn-1 and sn-2 substitution as is shown for phosphatidylglycerols. This contribution provides evidence for extending the targeted approach to global lipidomics analysis using the high-efficiency gas-phase separation afforded by multidimensional IMS-MS.

  19. Development of a New Ion Mobility (Quadrupole) Time-of-Flight Mass Spectrometer

    PubMed Central

    Ibrahim, Yehia M.; Baker, Erin S.; Danielson, William F.; Norheim, Randolph V.; Prior, David C.; Anderson, Gordon A.; Belov, Mikhail E.; Smith, Richard D.

    2014-01-01

    A new ion mobility spectrometer (IMS) platform was developed to improve upon the sensitivity and reproducibility of our previous platforms, and further enhance IMS-MS utility for broad ‘pan-omics’ measurements. The new platform incorporated an improved electrospray ionization source and interface for enhanced sensitivity, and providing the basis for further benefits based upon implementation of multiplexed IMS. The ion optics included electrodynamic ion funnels at both the entrance and exit of the IMS, an ion funnel trap for ion injection, and a design in which nearly all ion optics (e.g. drift rings, ion funnels) were fabricated using printed circuit board technology. The IMS resolving power achieved was ~73 for singly-charged ions, very close to the predicted diffusion-limited resolving power (~75). The platform’s performance evaluation (e.g. for proteomics measurements) include LC-IMS-TOF MS datasets for 30 technical replicates for a trypsin digested human serum, and included platform performance in each dimension (LC, IMS and MS) separately. PMID:26185483

  20. New high-efficiency ion-trap mobility detection system for narcotics

    NASA Astrophysics Data System (ADS)

    McGann, William J.

    1997-02-01

    A new patented Ion Trap Mobility Spectrometer design is presented. Conventional IMS designs typically operate below 0.1 percent efficiency. This is due primarily to electric field driven, sample ion discharge on a shutter grid. Since 99.9 percent of the sample ions generated in the reaction region are lost int his discharge process, the sensitivity of conventional systems is limited. The new design provides greater detection efficiency than conventional designs through the use of an 'ion trap' concept. The paper describes the plasma and sample ion dynamics in the reaction region of the new detector and discusses the advantages of utilizing a 'field-free' space to generate sample ions with high efficiency. Fast electronic switching is described which is used to perturb the field-free space and pulse the sample ions into the drift region for separation and subsequent detection using pseudo real-time software for analysis and display of the data. One application for this new detector is now being developed, a portable, hand-held system with switching capability for the detection of drugs and explosives. Preliminary ion spectra and sensitivity data are presented for cocaine and heroin using a hand sniffer configuration.

  1. Combined ICR heating antenna for ion separation systems

    SciTech Connect

    Timofeev, A. V.

    2011-01-15

    A combination of one- and two-wave antennas (one and two turns of conductors around a plasma cylinder, respectively) is proposed. This combined antenna localizes an RF field within itself. It is shown that spent nuclear fuel processing systems based on ICR heating of nuclear ash by such a combined antenna have high productivity. A theory of the RF field excitation in ICR ion separation systems is presented in a simple and compact form.

  2. Ion optics system incorporating radio frequency mass separation

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  3. The quantitative ion exchange separation of uranium from impurities

    SciTech Connect

    Narayanan, U.I.; Mason, P.B.; Zebrowski, J.P.; Rocca, M.; Frank, I.W.; Smith, M.M.; Johnson, K.D.; Orlowicz, G.J.; Dallmann, E.

    1995-03-01

    Two methods were tested for the quantitative separation of uranium from elemental impurities using commercially available resins. The sorption and elution behavior of uranium and the separation of it from a variety of other elements was studied. The first method utilized an anion exchange resin while the second method employed an extraction resin. The first method, the anion exchange of uranium (VI) in an acid chloride medium, was optimized and statistically tested for quantitative recovery of uranium. This procedure involved adsorption of uranium onto Blo-Rad AG 1-X8 or MP-1 ion exchange resins in 8 M HCl, separation of uncompleted or weakly complexed matrix ions with an 8 M HCI wash, and subsequent elution of uranium with 1 M HCl. Matrix ions more strongly adsorbed than uranium were left on the resin. Uranium recoveries with this procedure averaged greater than 99.9% with a standard deviation of 0.1%. In the second method, recovery of uranium on the extraction resin did not meet the criteria of this study and further examination was terminated.

  4. High-Performance Ion Mobility Spectrometry Using Hourglass Electrodynamic Funnel And Internal Ion Funnel

    DOEpatents

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

    2004-11-16

    A method and apparatus enabling increased sensitivity in ion mobility spectrometry/mass spectrometry instruments which substantially reduces or eliminates the loss of ions in ion mobility spectrometer drift tubes utilizing an hourglass electrodynamic ion funnel at the entrance to the drift tube and/or an internal ion funnel at the exit of the drift tube. An hourglass electrodynamic funnel is formed of at least an entry element, a center element, and an exit element, wherein the aperture of the center element is smaller than the aperture of the entry element and the aperture of the exit elements. Ions generated in a relatively high pressure region by an ion source at the exterior of the hourglass electrodynamic funnel are transmitted to a relatively low pressure region at the entrance of the hourglass funnel through a conductance limiting orifice. Alternating and direct electrical potentials are applied to the elements of the hourglass electrodynamic funnel thereby drawing ions into and through the hourglass electrodynamic funnel thereby introducing relatively large quantities of ions into the drift tube while maintaining the gas pressure and composition at the interior of the drift tube as distinct from those at the entrance of the electrodynamic funnel and allowing a positive gas pressure to be maintained within the drift tube, if desired. An internal ion funnel is provided within the drift tube and is positioned at the exit of said drift tube. The advantage of the internal ion funnel is that ions that are dispersed away from the exit aperture within the drift tube, such as those that are typically lost in conventional drift tubes to any subsequent analysis or measurement, are instead directed through the exit of the drift tube, vastly increasing the amount of ions exiting the drift tube.

  5. MINOR ACTINIDE SEPARATIONS USING ION EXCHANGERS OR IONIC LIQUIDS

    SciTech Connect

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-09-20

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  6. Dynamic multiplexed analysis method using ion mobility spectrometer

    SciTech Connect

    Belov, Mikhail E

    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.

  7. Electron Attachment Studies for CHCl3 Using Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Han, Hai-yan; Feng, Hong-tao; Li, Hu; Wang, Hong-mei; Jiang, Hai-he; Chu, Yan-nan

    2011-04-01

    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/cm 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 ion-molecule reaction rate constants for the further reaction between Cl- and CHCl3 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 Cl- and CHCl3 are the first time detected using CD-IMS.

  8. Determination of ammonia in ethylene using ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Cross, J. H.; Limero, T. F.; Lane, J. L.; Wang, F.

    1997-01-01

    A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated.

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

    PubMed

    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. PMID:14961740

  10. Mobile ion distribution and anharmonic thermal motion in fast ion conducting Cu/sub 2/S

    SciTech Connect

    Cava, R.J.; Reidinger, F.; Wuensch, B.J.

    1981-01-01

    A unique model was determined for the mobile copper ion disorder in hexagonal Cu/sub 2/S between 120/sup 0/ and 325/sup 0/C via single crystal neutron diffraction. The copper ions partially occupy two sets of three-coordinated sites within the HCP sulfur array and display anharmonic thermal motion. The results suggest that the conductivity is two dimensional in nature.

  11. Implementation of Dipolar Resonant Excitation Collision Induced Dissociation with Ion Mobility/Time-of-Flight MS

    SciTech Connect

    Webb, Ian K.; Chen, Tsung-Chi; Danielson, William F.; Ibrahim, Yehia M.; Tang, Keqi; Anderson, Gordon A.; Smith, Richard D.

    2014-01-28

    Under and overfragmentation are significant hurdles to the data independent “bottom-up” approach to proteomics. Another challenge to the data independent approach is the convolution of fragments from different peptides that coelute in reverse-phase liquid chromatography/mass spectrometry (RPLC/MS). The ion mobility/collision induced dissociation/time-of flight mass spectrometry (IMS/CID/TOF MS) approach gives drift-time aligned fragment ions that have the same arrival time distributions as precursor ions, greatly aiding in fragment and peptide ion identification. We have modified an IMS/TOF MS platform to allow for resonant excitation CID experiments. Resonant excitation CID leads to highly efficient, mass-resolved fragmentation without additional excitation of product ions, alleviating the overfragmentation problem. The ability to apply resonant waveforms in mobility-resolved windows has been demonstrated with a peptide mixture yielding fragmentation over a range of mass-to-charge (m/z) ratios within a single IMS separation experiment.

  12. Continuous ion exchange separation of zirconium and hafnium

    SciTech Connect

    Begovich, J.M.; Sisson, W.G.

    1981-01-01

    A pressurized continuous annular chromatograph (CAC) has been developed for truly continuous ion exchange preparative separations. This device utilizes a slowly rotating annular bed of sorbent material, fixed multiple feed points, and fixed withdrawal locations. Most of our investigations have been performed with a 28-cm-diam by 60-cm-long CAC, but a larger model has recently been designed and constructed. A detailed study has been made of the separation of copper, nickel, and cobalt components from a simulated carbonate leach liquor of the Caron process for recovering nickel and cobalt from laterite ores. Recent studies have investigated the ion exchange separation of zirconium and hafnium from a sulfate feed solution. Nuclear reactor-grade zirconium, containing < 0.01 wt % hafnium, and hafnium, containing < 1% zirconium, have been continuously prepared using cation exchange resin in the pressurized CAC. This device, because of its continuous feed and product withdrawal, its adaptability to largescale operations, and its ability to separate many components, is expected to make chromatography a more competitive process in the industrial sector.

  13. Improving Ion Mobility Measurement Sensitivity by Utilizing Helium in an Ion Funnel-Trap

    SciTech Connect

    Ibrahim, Yehia M.; Garimella, Venkata BS; Tolmachev, Aleksey V.; Baker, Erin Shammel; Smith, Richard D.

    2014-05-01

    Ion mobility instruments that utilize nitrogen as buffer gas are often preceded by an ion trap and accumulation region that also uses nitrogen, and for different inert gases no significant effects upon performance are expected for IMS of larger ions. However, we have observed significantly improved performance for an ion funnel trap upon adding helium; the signal intensities for higher m/z species were improved by more than an order of magnitude compared to using pure nitrogen. The effect of helium upon IMS resolving power was also studied by introducing a He/N2 gas mixture into the drift cell, and in some cases a slight improvement was observed compared to pure N2. The improvement in signal can be largely attributed to faster and more efficient ion ejection into the drift tube from the ion funnel trap.

  14. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    DOE PAGESBeta

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-05-06

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts andmore » noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.« less

  15. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    NASA Astrophysics Data System (ADS)

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin S.; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-12-01

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm employs an analytical approach to identify and remove artifacts from the data, decreasing the likelihood of false identifications in subsequent data processing. Following application of the algorithm, IMS-MS measurement sensitivity is greatly increased and artifacts that previously limited the utility of applying the Hadamard transform to IMS are avoided. [Figure not available: see fulltext.

  16. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    SciTech Connect

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-12-01

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts and noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.

  17. Detecting and Removing Data Artifacts in Hadamard Transform Ion Mobility-Mass Spectrometry Measurements

    SciTech Connect

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; Ibrahim, Yehia M.; Clowers, Brian H.; Monroe, Matthew E.; Anderson, Gordon A.; Smith, Richard D.; Payne, Samuel H.

    2014-05-06

    Applying Hadamard transform multiplexing to ion mobility separations (IMS) can significantly improve the signal-to-noise ratio and throughput for IMS coupled mass spectrometry (MS) measurements by increasing the ion utilization efficiency. However, it has been determined that both fluctuations in ion intensity as well as spatial shifts in the multiplexed data lower the signal-to-noise ratios and appear as noise in downstream processing of the data. To address this problem, we have developed a novel algorithm that discovers and eliminates data artifacts. The algorithm uses knowledge of the true signal peaks derived from the encoded data and allows for both artifacts and noise to be removed with high confidence, decreasing the likelihood of false identifications in subsequent data processing. The result is that IMS-MS can be applied to increase measurement sensitivity while avoiding artifacts that have previously limited its utility.

  18. Ion Mobility-Derived Collision Cross Section As an Additional Measure for Lipid Fingerprinting and Identification

    PubMed Central

    2014-01-01

    Despite recent advances in analytical and computational chemistry, lipid identification remains a significant challenge in lipidomics. Ion-mobility spectrometry provides an accurate measure of the molecules’ rotationally averaged collision cross-section (CCS) in the gas phase and is thus related to ionic shape. Here, we investigate the use of CCS as a highly specific molecular descriptor for identifying lipids in biological samples. Using traveling wave ion mobility mass spectrometry (MS), we measured the CCS values of over 200 lipids within multiple chemical classes. CCS values derived from ion mobility were not affected by instrument settings or chromatographic conditions, and they were highly reproducible on instruments located in independent laboratories (interlaboratory RSD < 3% for 98% of molecules). CCS values were used as additional molecular descriptors to identify brain lipids using a variety of traditional lipidomic approaches. The addition of CCS improved the reproducibility of analysis in a liquid chromatography-MS workflow and maximized the separation of isobaric species and the signal-to-noise ratio in direct-MS analyses (e.g., “shotgun” lipidomics and MS imaging). These results indicate that adding CCS to databases and lipidomics workflows increases the specificity and selectivity of analysis, thus improving the confidence in lipid identification compared to traditional analytical approaches. The CCS/accurate-mass database described here is made publicly available. PMID:25495617

  19. Label-free quantification in ion mobility-enhanced data-independent acquisition proteomics.

    PubMed

    Distler, Ute; Kuharev, Jörg; Navarro, Pedro; Tenzer, Stefan

    2016-04-01

    Unbiased data-independent acquisition (DIA) strategies have gained increased popularity in the field of quantitative proteomics. The integration of ion mobility separation (IMS) into DIA workflows provides an additional dimension of separation to liquid chromatography-mass spectrometry (LC-MS), and it increases the achievable analytical depth of DIA approaches. Here we provide a detailed protocol for a label-free quantitative proteomics workflow based on ion mobility-enhanced DIA, which synchronizes precursor ion drift times with collision energies to improve precursor fragmentation efficiency. The protocol comprises a detailed description of all major steps including instrument setup, filter-aided sample preparation, LC-IMS-MS analysis and data processing. Our protocol can handle proteome samples of any complexity, and it enables a highly reproducible and accurate precursor intensity-based label-free quantification of up to 5,600 proteins across multiple runs in complete cellular lysates. Depending on the number of samples to be analyzed, the protocol takes a minimum of 3 d to complete from proteolytic digestion to data evaluation. PMID:27010757

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

    SciTech Connect

    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.

  1. Separation of ions using polyelectrolyte-modified nanoporous track-etched membranes.

    PubMed

    Armstrong, Jason A; Bernal, Edxon Eduardo Licón; Yaroshchuk, Andriy; Bruening, Merlin L

    2013-08-13

    Selective ion exclusion from charged nanopores in track-etched membranes allows separation of ions with different charges or mobilities. This study examines pressure-driven transport of dissolved ions through track-etched membranes modified by adsorption of poly(styrene sulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For nominal 30 nm pores modified with a single layer of PSS, Br(-)/SO4(2-) selectivities are ∼3.4 with SO4(2-) rejections around 85% due to selective electrostatic exclusion of the divalent anion from the negatively charged pore. Corresponding membranes containing an adsorbed PSS/PAH bilayer are positively charged and exhibit average K(+)/Mg(2+) selectivities >10 at 8 mM ionic strength, and Mg(2+) rejections are >97.5% at ionic strengths <5 mM. The high rejection of Mg(2+) compared to SO4(2-) likely results from both a smaller pore size after deposition of the PAH layer and higher surface charge because of Mg(2+) adsorption. Simultaneous modeling of K(+) and Mg(2+) rejections using the nonlinearized Poisson-Boltzmann equation gives an average modified pore diameter of 8.4 ± 2.1 nm, which does not vary significantly with ionic strength. This diameter is smaller than that calculated from hydraulic permeabilities and estimated pore densities, suggesting that narrow regions near the pore entrance control ion transport. In addition to simple electrostatic exclusion, streaming potentials lead to differing rejections of Br(-) and acetate in PSS/PAH-modified pores, and of Li(+) and Cs(+) in PSS-modified pores. For these cases, electrical migration of ions toward the feed solution results in higher rejection of the more mobile ion. PMID:23902372

  2. Identification of ion series using ion mobility mass spectrometry: the example of alkyl-benzothiophene and alkyl-dibenzothiophene ions in diesel fuels.

    PubMed

    Maire, Florian; Neeson, Kieran; Denny, Richard; McCullagh, Michael; Lange, Catherine; Afonso, Carlos; Giusti, Pierre

    2013-06-01

    Ion mobility-mass spectrometry (IMMS) has been presented as a promising method for analysis of highly complex mixtures. This coupling adds an additional postionization separation dimension to MS. The IM separation of ions is obtained in the millisecond time scale and can be particularly helpful when chromatographic separation is not possible. For obtaining relevant information about the samples, data processing is usually the bottleneck because of the high amount of data generated with IMMS. In the current work, we present a new workflow using specific comparison software dedicated to IMMS data, which allows one to compare m/z-drift time plots to highlight differences between samples. Two diesel fuels have been compared, i.e., the feed and the product of hydrodesulfurization (HDS) process, and this approach allowed us to clearly highlight the variation of intensity of several ions distributed along the plots of both samples. Accurate mass measurements and post IM collision induced dissociation experiments allowed us to identify two series of polycyclic aromatic sulfur-containing heterocycle (PASH) compounds among the matrix ions. PMID:23638962

  3. Demonstrated Potential of Ion Mobility Spectrometry for Detection of Adulterated Perfumes and Plant Speciation

    SciTech Connect

    Clark, Jared Matthew; Daum, Keith Alvin; Kalival, J. H.

    2003-01-01

    This initial study evaluates the use of ion mobility spectrometry (IMS) as a rapid test procedure for potential detection of adulterated perfumes and speciation of plant life. Sample types measured consist of five genuine perfumes, two species of sagebrush, and four species of flowers. Each sample type is treated as a separate classification problem. It is shown that discrimination using principal component analysis with K-nearest neighbors can distinguish one class from another. Discriminatory models generated using principal component regressions are not as effective. Results from this examination are encouraging and represent an initial phase demonstrating that perfumes and plants possess characteristic chemical signatures that can be used for reliable identification.

  4. Capillary electrophoresis separation of vinpocetine and related compounds: prediction of electrophoretic mobilities in partly aqueous media.

    PubMed

    Mazák, K; Szakács, Z; Nemes, A; Noszál, B

    2000-07-01

    Offord's equation, a relationship between electrophoretic mobility and charge, size and shape of peptides, has been extended to quantitate the electrophoretic mobility of vinca alkaloids. Partly aqueous protonation constants and the derived theoretical mobilities have been proven to be able to predict experimental electrophoretic mobilities. In practice, seven vincamine derivatives of very low water-solubility were separated by capillary electrophoresis. Buffer total concentration, apparent pH and methanol content, the three most important parameters of the running buffer, were used in triangular resolution mapping to characterize separation. Even though electrophoresis is well known to slow down in partly aqueous media, under our optimized circumstances a baseline separation was achieved within 8 min in each case. PMID:10939454

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

    SciTech Connect

    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.

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

    PubMed

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

    2016-07-19

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

  7. Automation of Extraction Chromatograhic and Ion Exchange Separations for Radiochemical Analysis and Monitoring

    SciTech Connect

    Grate, Jay W.; O'Hara, Matthew J.; Egorov, Oleg

    2009-08-19

    Radiochemical analysis, complete with the separation of radionuclides of interest from the sample matrix and from other interfering radionuclides, is often an essential step in the determination of the radiochemical composition of a nuclear sample or process stream. Although some radionuclides can be determined nondestructively by gamma spectroscopy, where the gamma rays penetrate significant distances in condensed media and the gamma ray energies are diagnostic for specific radionuclides, other radionuclides that may be of interest emit only alpha or beta particles. For these, samples must be taken for destructive analysis and radiochemical separations are required. For process monitoring purposes, the radiochemical separation and detection methods must be rapid so that the results will be timely. These results could be obtained by laboratory analysis or by radiochemical process analyzers operating on-line or at-site. In either case, there is a need for automated radiochemical analysis methods to provide speed, throughput, safety, and consistent analytical protocols. Classical methods of separation used during the development of nuclear technologies, namely manual precipitations, solvent extractions, and ion exchange, are slow and labor intensive. Fortunately, the convergence of digital instrumentation for preprogrammed fluid manipulation and the development of new separation materials for column-based isolation of radionuclides has enabled the development of automated radiochemical analysis methodology. The primary means for separating radionuclides in solution are liquid-liquid extraction and ion exchange. These processes are well known and have been reviewed in the past.1 Ion exchange is readily employed in column formats. Liquid-liquid extraction can also be implemented on column formats using solvent-impregnated resins as extraction chromatographic materials. The organic liquid extractant is immobilized in the pores of a microporous polymer material. Under

  8. Separation of basic oligopeptides by ion-pairing reversed-phase chromatography

    NASA Astrophysics Data System (ADS)

    Xie, Wenchun

    The present thesis consist of five chapters. Chapter I introduces background information on the ion-pairing reversed-phase chromatography and liquid chromatography in the critical condition. Chapter II decribes our study on the isocratic separation of oligolysine (dp = 2 to 8) using a fixed content of acetonitrile (ACN) (23%) and different concentrations of HFBA in the mobile phase (0.6-30.6 mM) on a Waters XBridge Shield RP18® column. We found that the retention time of oligolysine increases as the dp increases, because of an increased number of HFBA bound to the peptides. Furthermore, when [HFBA] increased, the retention time increased at different rates. The greater the dp, the faster the rate. Based on a closed pairing model that presumes an equilibrium between an unpaired state and the paired state with a fixed number of HFBA molecules, an equation was derived for the retention factor of oligolysine. In Chapter III, we compare retention behaviors of oligolysine (dp = 2 to 8) and oligoarginine (dp = 2 to 8) when they are separated on the Waters XBridge Shield RP18® using fixed a ACN content (23%) and difference concentrations of HFBA (0.4-30.6 mM) in the mobile phase. The retention time of oligoarginine also increased at different rates as [HFBA] increased. The greater the dp, the faster the rate. The retention time of oligolysine is shorter than that of oligarginine having the dame dp. We applied Eq.1 to analyze the plot of ln k as a function of [HFBA] for each oligopeptide component to obtain the values for n, Kip,m, and βKd,ip. For oligolysine, n increases linearly as dp increase and oligoarginine exhibits an accelerated increase in n as dp rises. The plot of ln βKd,ip against dp followed a linear relationship for both peptides. In Chapter IV, we study the effect of mobile phase composition on the retention of oligolysine (dp = 2 to 8) on the Waters XBridge Shield RP18 ®. The ACN content was changed from 20% to 33% and the HFBA concentration from 0.7 to

  9. Gas chromatography with tandem differential mobility spectrometry of fatty acid alkyl esters and the selective detection of methyl linolenate in biodiesels by dual-stage ion filtering.

    PubMed

    Pasupuleti, D; Pierce, K; Eiceman, G A

    2015-11-20

    Alkyl esters of fatty acids (FAAEs) with carbon numbers from 8 to 20 formed protonated monomers and proton bound dimers through atmospheric pressure chemical ionization reactions and these gas ions were characterized for their field dependent mobility coefficients using differential mobility spectrometry (DMS). Separation of ion peaks with a vapor modifier was achieved for ions with masses of 317-1033 Da though the differences in these coefficients and the resolution of ion peaks decreased proportionally with increased ion mass. Differences in dispersion curves were sufficient to isolate ions from specific FAAEs in the effluent of a gas chromatograph by dual stage ion filtering using a tandem DMS detector. Methyl linolenate was isolated from nearby eluting methyl oleate, methyl stearate and methyl linoleate within analysis times of 10s without measureable complications from charge suppression in the ion source or leakage in filtering of ions with close proximity of dispersion behavior. PMID:26427321

  10. Separation of glyceride positional isomers by silver ion chromatography.

    PubMed

    Févrie, P; Bine, A; Dufossé, L; Grée, R; Yvergnaux, F

    2001-07-20

    Separation of triglyceride and diglyceride positional isomers by silver ion high-performance liquid chromatography coupled with an evaporative light-scattering detector is described. The triglyceride isomers had a fatty acid composition of CLC and CCL, where C and L were caprylic acid and linoleic acid, respectively. Diglyceride isomers, 1,2(2,3)-diglyceride and 1,3-diglyceride, which contained caprylic acid were separated too. A solvent system based on n-hexane, 2-propanol, ethyl acetate, and acetonitrile with a flow-rate of 0.8 ml/min was developed. Calibration curves of CLC and CCL were achieved with triolein as internal standard. Using this method, the incorporation of linoleic acid onto specific a position of glycerol backbone can be monitored. PMID:11510559

  11. Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

    NASA Astrophysics Data System (ADS)

    Tudryn, Gregory J.

    aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used

  12. MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis of N-Linked Glycans

    NASA Astrophysics Data System (ADS)

    Harvey, David J.; Scarff, Charlotte A.; Crispin, Max; Scanlan, Christopher N.; Bonomelli, Camille; Scrivens, James H.

    2012-11-01

    The preference for singly charged ion formation by MALDI makes it a better choice than electrospray ionization for profiling mixtures of N-glycans. For structural analysis, fragmentation of negative ions often yields more informative spectra than fragmentation of positive ones but such ions are more difficult to produce from neutral glycans under MALDI conditions. This work investigates conditions for the formation of both positive and negative ions by MALDI from N-linked glycans released from glycoproteins and their subsequent MS/MS and ion mobility behaviour. 2,4,6-Trihydroxyacetophenone (THAP) doped with ammonium nitrate was found to give optimal ion yields in negative ion mode. Ammonium chloride or phosphate also yielded prominent adducts but anionic carbohydrates such as sulfated N-glycans tended to ionize preferentially. Carbohydrates adducted with all three adducts (phosphate, chloride, and nitrate) produced good negative ion CID spectra but those adducted with iodide and sulfate did not yield fragment ions although they gave stronger signals. Fragmentation paralleled that seen following electrospray ionization providing superior spectra than could be obtained by PSD on MALDI-TOF instruments or with ion traps. In addition, ion mobility drift times of the adducted glycans and the ability of this technique to separate isomers also mirrored those obtained following ESI sample introduction. Ion mobility also allowed profiles to be obtained from samples whose MALDI spectra showed no evidence of such ions allowing the technique to be used in conditions where sample amounts were limiting. The method was applied to N-glycans released from the recombinant human immunodeficiency virus glycoprotein, gp120.

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

    PubMed

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

    2016-02-01

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

  14. Using Measurements of Mobility, Diffusion, and Dispersion to Predict Separation Resolution in DNA Electrophoresis

    NASA Astrophysics Data System (ADS)

    Lo, Roger

    2005-03-01

    Electrophoresis of DNA continues to be a key component in a wide variety of genomic analysis assays. In order to customize and optimize these assay systems, much effort has been directed to improve and predict separation resolution using various sieving matrices and experimental platforms. Predicting separation resolution requires a much more detailed understanding of mobility, diffusion, and dispersion phenomena of DNA fragments migrating in the sieving matrix than is currently available in literature. In this study, we address this issue by obtaining a series of systematic measurements of mobility, diffusion, and dispersion using an automated DNA sequencer. Using this data, we are able to isolate key factors governing separation performance, and make comparisons with biased reptation theory to extract information on gel structure and predict achievable resolution under each set of operating conditions. We are also able to predict the separation resolution under specific run conditions, thereby giving researchers and engineers the ability to easily tailor DNA separation systems for required separation performance.

  15. Wakefield accelerators in the blowout regime with mobile ions

    SciTech Connect

    Lee, S.; Katsouleas, T.

    1999-07-12

    In the Plasma Wakefield Accelerator a high current drive-beam excites a large wake that can accelerate trailing particles. The wake is created when the space charge of the drive beam displaces plasma electrons. The plasma ions provide the restoring force on the displaced electrons. For symmetric bunches, the peak accelerating gradient is proportional to the current over a pulse length. For example, for a Gaussian bunch with 6nC of charge and bunch length {sigma}{sub z}{approx_equal}0.6 mm, a gradient of 1GeV/m can be obtained. For the case of dense (beam density greater than plasma density), narrow (beam spot size {sigma}{sub r} smaller than c/{omega}{sub p}) beams the plasma response is non-linear and is dominated by the radial blow out of all the plasma electrons. However, such dense beams are strongly focused by the plasma lens effect. As a result they become so dense that ion motion should become important even on the electron plasma frequency time-scale. We will present analytic and 2-D particle-in-cell (PIC) models of wake excitation including mobile ions. The effect of the ion motion on the accelerating and focusing wake and the dynamics of the drive beam are discussed.

  16. Wakefield accelerators in the blowout regime with mobile ions

    SciTech Connect

    Lee, S.; Katsouleas, T.

    1999-07-01

    In the Plasma Wakefield Accelerator a high current drive-beam excites a large wake that can accelerate trailing particles. The wake is created when the space charge of the drive beam displaces plasma electrons. The plasma ions provide the restoring force on the displaced electrons. For symmetric bunches, the peak accelerating gradient is proportional to the current over a pulse length. For example, for a Gaussian bunch with 6nC of charge and bunch length {sigma}{sub z}{approx}0.6&hthinsp;mm, a gradient of 1GeV/m can be obtained. For the case of dense (beam density greater than plasma density), narrow (beam spot size {sigma}{sub r} smaller than c/{omega}{sub p}) beams the plasma response is non-linear and is dominated by the radial blow out of all the plasma electrons. However, such dense beams are strongly focused by the plasma lens effect. As a result they become so dense that ion motion should become important even on the electron plasma frequency time-scale. We will present analytic and 2-D particle-in-cell (PIC) models of wake excitation including mobile ions. The effect of the ion motion on the accelerating and focusing wake and the dynamics of the drive beam are discussed. {copyright} {ital 1999 American Institute of Physics.}

  17. Wakefield accelerators in the blowout regime with mobile ions

    NASA Astrophysics Data System (ADS)

    Lee, S.; Katsouleas, T.

    1999-07-01

    In the Plasma Wakefield Accelerator a high current drive-beam excites a large wake that can accelerate trailing particles. The wake is created when the space charge of the drive beam displaces plasma electrons. The plasma ions provide the restoring force on the displaced electrons. For symmetric bunches, the peak accelerating gradient is proportional to the current over a pulse length. For example, for a Gaussian bunch with 6nC of charge and bunch length σz≈0.6 mm, a gradient of 1GeV/m can be obtained. For the case of dense (beam density greater than plasma density), narrow (beam spot size σr smaller than c/ωp) beams the plasma response is non-linear and is dominated by the radial blow out of all the plasma electrons. However, such dense beams are strongly focused by the plasma lens effect. As a result they become so dense that ion motion should become important even on the electron plasma frequency time-scale. We will present analytic and 2-D particle-in-cell (PIC) models of wake excitation including mobile ions. The effect of the ion motion on the accelerating and focusing wake and the dynamics of the drive beam are discussed.

  18. Unbalance magnetron plasma source for ion mass-separator

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    PubMed

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

    2010-01-01

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

  20. A critical overview of non-aqueous capillary electrophoresis. Part I: mobility and separation selectivity.

    PubMed

    Kenndler, Ernst

    2014-03-28

    This two-part review critically gives an overview on the theoretical and practical advances in non-aqueous capillary electrophoresis (NACE) achieved over the recent five years. Part I starts out by reviewing the aspects relevant to electromigration in organic solvents and evaluates potential advantages of the latter in comparison to aqueous solvent systems. The crucial role of solubility for the species involved in CE - analytes and back ground electrolyte constituents - is discussed both for ionic and neutral compounds. The impact of organic solvents on the electrophoretic and electroosmotic mobility and on the ionization (pKa values) of weak acids and bases is highlighted. Special emphasis is placed on methanol, acetonitrile and mixtures of these solvents, being the most frequent employed media for NACE applications. In addition, also solvents less commonly used in NACE will be covered, including other alcohols, amides (formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide), propylene carbonate, dimethylsulphoxide, and nitromethane. The discussions address the consequences of dramatic pKa shifts frequently seen for weak acids and bases, and the important contributions of medium-specific electroosmotic flow (EOF) to electromigration in nonaqueous media. Important for NACE, the role of the water content on pKa and mobility is analyzed. Finally, association phenomena rather specific to nonaqueous solvents (ion pairing, homo- and heteroconjugation) will be addressed, along with their potential advantages for the development of NACE separation protocols. It is pointed out that this review is not intended as a listing of all papers that have been published on NACE in the period mentioned above. It rather deals with general aspects of migration and selectivity in organic solvent systems, and discusses - critically - examples from the literature with particular interest to the topic. An analog discussion about the role of the solvent on efficiency

  1. Analysis of heterogeneous uptake by nanoparticles via differential mobility analysis-drift tube ion mobility spectrometry.

    PubMed

    Oberreit, Derek R; McMurry, Peter H; Hogan, Christopher J

    2014-04-21

    Improved methods are needed to study sorption of vapor molecules by particles in the gas phase (heterogeneous uptake), which is an important process in both natural and engineered environments. Here, a new measurement system, composed of a differential mobility analyzer (DMA) and drift tube ion mobility spectrometer (DTIMS) in series, is used to examine the heterogeneous uptake of water vapor by 2.85-7.6 nm particles composed of lithium and sodium iodide. The extent of heterogeneous uptake is determined by controlling the relative humidity of the drift region in the DTIMS in the 0-30% range (in air at atmospheric pressure and room temperature), and is quantified via the dimensionless growth factor (GF), i.e. the ratio of the mobility diameter of particles at a prescribed relative humidity relative to their mobility diameter under dry conditions. The precision in GF estimation of the DMA-DTIMS system is shown to be below 0.2%. An analytical equation to calculate the growth factor, based upon predictions of the equilibrium constants for the successive uptake of vapor molecules by particles, is also presented. While the equation is sufficiently general to enable comparison between measured GFs and predictions from any theoretical expression for equilibrium constants, we specifically compare measurements to GF predictions based on the classical Kelvin-Thomson-Raoult (KTR) model for the vapor pressure of a small particle, with consideration of the influence of the ion-dipole potential on water vapor-nanoparticle collisions. It is shown that KTR calculations drastically underpredict the extent of heterogeneous uptake for the examined nanoparticles. PMID:24600691

  2. Resolving Interferences in Negative Mode Ion Mobility Spectrometry Using Selective Reactant Ion Chemistry

    SciTech Connect

    Daum, Keith Alvin; Atkinson, David Alan; Ewing, Robert Gordon; Knighton, W. B.; Grimsrud, E. P

    2001-04-01

    During the investigation of the degradation products of 2,4,6-trinitrotoluene (TNT) using ion mobility spectrometry (IMS), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (DCP) were found to have IMS responses which overlapped those of the TNT degradation products. It was observed that the Cl- reactant ion chemistry, often used for explosives analysis, was not always successful in resolving peak overlap of analytes and interferents. It is shown here that resolution of the analytes and interferences can sometimes be achieved using only air for the formation of reactant ions, at other times through the use of Br- as an alternative to Cl- for producing reactant ions, and also through the promotion of adduct stability by lowering the IMS temperature.

  3. Control of the reactant ion chemistry for the analysis of explosives by ion mobility spectroscopy

    SciTech Connect

    Rodacy, P.J.; Ingersoll, D.

    1995-07-01

    Changes in the reactant ion composition in the ion mobility spectrometer (IMS) can result in a change in the ionization processes occurring in the ionization region, ultimately leading to an altered instrumental response for the analyte, and exacerbating the problem of qualitative and quantitative analysis. Some species are very susceptible to changes in reactant ions, while other species are relatively unaffected. These types of behavior are observed for two common explosives, namely, hexahydro-1,3,5-trinitrol,3,5-triazine (RDX) and 1,3,5-trinitrotoluene (TNT), respectively. To control the reactant ion composition, and hence the gas phase chemistry, it is necessary to control the composition of gases present in the ionization region of the IMS. A series of modifications are described for the PCP Phemto-Chem 100 IMS that afford the requisite control. The effectiveness of these modifications for analysis of RDX and TNT are described and contrasted with that observed for the unmodified system.

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

    PubMed

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; 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 Å(2) and 808 ± 2 Å(2). [M - 4H](4-) ions were comprised of more compact (Ω = 676 ± 3 Å(2)) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å(2)) 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. PMID:26620531

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Separator-Integrated, Reversely Connectable Symmetric Lithium-Ion Battery.

    PubMed

    Wang, Yuhang; Zeng, Jiren; Cui, Xiaoqi; Zhang, Lijuan; Zheng, Gengfeng

    2016-02-24

    A separator-integrated, reversely connectable, symmetric lithium-ion battery is developed based on carbon-coated Li3V2(PO4)3 nanoparticles and polyvinylidene fluoride-treated separators. The Li3V2(PO4)3 nanoparticles are synthesized via a facile solution route followed by calcination in Ar/H2 atmosphere. Sucrose solution is used as the carbon source for uniform carbon coating on the Li3V2(PO4)3 nanoparticles. Both the carbon and the polyvinylidene fluoride treatments substantially improve the cycling life of the symmetric battery by preventing the dissolution and shuttle of the electroactive Li3V2(PO4)3. The obtained symmetric full cell exhibits a reversible capacity of ≈ 87 mA h g(-1), good cycling stability, and capacity retention of ≈ 70% after 70 cycles. In addition, this type of symmetric full cell can be operated in both forward and reverse connection modes, without any influence on the cycling of the battery. Furthermore, a new separator integration approach is demonstrated, which enables the direct deposition of electroactive materials for the battery assembly and does not affect the electrochemical performance. A 10-tandem-cell battery assembled without differentiating the electrode polarity exhibits a low thickness of ≈ 4.8 mm and a high output voltage of 20.8 V. PMID:26725040

  7. Bayesian Deconvolution of Mass and Ion Mobility Spectra: From Binary Interactions to Polydisperse Ensembles

    PubMed Central

    Marty, Michael T.; Baldwin, Andrew J.; Marklund, Erik G.; Hochberg, Georg K. A.; Benesch, Justin L. P.; Robinson, Carol V.

    2015-01-01

    Interpretation of mass spectra is challenging because they report a ratio of two physical quantities, mass and charge, which may each have multiple components that overlap in m/z. Previous approaches to disentangling the two have focused on peak assignment or fitting. However, the former struggle with complex spectra, and the latter are generally computationally intensive and may require substantial manual intervention. We propose a new data analysis approach that employs a Bayesian framework to separate the mass and charge dimensions. Based on this approach, we developed UniDec (Universal Deconvolution), software that provides a rapid, robust, and flexible deconvolution of mass spectra and ion mobility-mass spectra with minimal user intervention. Incorporation of the charge-state distribution in the Bayesian prior probabilities provides separation of the m/z spectrum into its physical mass and charge components. We have evaluated our approach using systems of increasing complexity, enabling us to deduce lipid binding to membrane proteins, to probe the dynamics of subunit exchange reactions, and to characterize polydispersity in both protein assemblies and lipoprotein Nanodiscs. The general utility of our approach will greatly facilitate analysis of ion mobility and mass spectra. PMID:25799115

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. PMID:27056565

  11. Noncontact measurement of electrostatic fields: Verification of modeled potentials within ion mobility spectrometer drift tube designs

    SciTech Connect

    Scott, Jill R.; Tremblay, Paul L.

    2007-03-15

    The heart of an ion mobility spectrometer is the drift region where ion separation occurs. While the electrostatic potentials within a drift tube design can be modeled, no method for independently validating the electrostatic field has previously been reported. Two basic drift tube designs were modeled using SIMION 7.0 to reveal the expected electrostatic fields: (1) A traditional alternating set of electrodes and insulators and (2) a truly linear drift tube. One version of the alternating electrode/insulator drift tube and two versions of linear drift tubes were then fabricated. The stacked alternating electrodes/insulators were connected through a resistor network to generate the electrostatic gradient in the drift tube. The two linear drift tube designs consisted of two types of resistive drift tubes with one tube consisting of a resistive coating within an insulating tube and the other tube composed of resistive ferrites. The electrostatic fields within each type of drift tube were then evaluated by a noncontact method using a Kelvin-Zisman type electrostatic voltmeter and probe (results for alternative measurement methods provided in supplementary material). The experimental results were then compared with the electrostatic fields predicted by SIMION. Both the modeling and experimental measurements reveal that the electrostatic fields within a stacked ion mobility spectrometer drift tube are only pseudo-linear, while the electrostatic fields within a resistive drift tube approach perfect linearity.

  12. Indoor and outdoor atmospheric ion mobility spectra, diurnal variation, and relationship with meteorological parameters

    NASA Astrophysics Data System (ADS)

    Wright, Matthew D.; Holden, Nicola K.; Shallcross, Dudley E.; Henshaw, Denis L.

    2014-03-01

    We report measurements of small ion mobility spectra and concentrations made over a 5 month period using a Gerdien-type ion mobility spectrometer at one indoor site in central Bristol, UK, and one indoor and one outdoor site in a semirural area. We assess the diurnal variation in ion concentration and mobility, variability with meteorological parameters, and features within the ion mobility spectra. Ion concentration (typically in the range 100-1000 cm-3) was highest overnight and lowest in late morning and afternoon. Total conductivity also followed this trend suggesting that small ions contribute more to conductivity than larger charged particles, although at the semirural site, indoor activity produced charged aerosol intermittently, while infiltration of outdoor aerosol contributed at the urban site. Negative ion mobility (typically 1.6-1.9 cm2 V-1 s-1) was higher overnight than at other times, while positive ion mobility (typically 1.2-1.4 cm2 V-1 s-1) showed no diurnal variability. In general, temperature, pressure, wind speed, and water vapor pressure were inversely related to both concentration and mobility, except outdoors when (negative) mobility increased with increasing temperature and pressure, while increased relative humidity was associated with higher ion mobilities and concentrations. Analysis of high-resolution mobility spectra revealed several mobilities for each polarity at which peaks were identified across all sites, suggesting similarity in composition but with varying importance at each site. Intermediate ions (mobilities 0.2-0.3 cm2 V-1 s-1) were observed at the outdoor site, but individual nucleation events which may be associated with them were not identifiable.

  13. Large-Scale Collision Cross-Section Profiling on a Traveling Wave Ion Mobility Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Lietz, Christopher B.; Yu, Qing; Li, Lingjun

    2014-12-01

    Ion mobility (IM) is a gas-phase electrophoretic method that separates ions according to charge and ion-neutral collision cross-section (CCS). Herein, we attempt to apply a traveling wave (TW) IM polyalanine calibration method to shotgun proteomics and create a large peptide CCS database. Mass spectrometry methods that utilize IM, such as HDMSE, often use high transmission voltages for sensitive analysis. However, polyalanine calibration has only been demonstrated with low voltage transmission used to prevent gas-phase activation. If polyalanine ions change conformation under higher transmission voltages used for HDMSE, the calibration may no longer be valid. Thus, we aimed to characterize the accuracy of calibration and CCS measurement under high transmission voltages on a TW IM instrument using the polyalanine calibration method and found that the additional error was not significant. We also evaluated the potential error introduced by liquid chromatography ( LC)-HDMSE analysis, and found it to be insignificant as well, validating the calibration method. Finally, we demonstrated the utility of building a large-population peptide CCS database by investigating the effects of terminal lysine position, via LysC or LysN digestion, on the formation of two structural sub-families formed by triply charged ions.

  14. Large-scale collision cross-section profiling on a travelling wave ion mobility mass spectrometer

    PubMed Central

    Lietz, Christopher B.; Yu, Qing; Li, Lingjun

    2014-01-01

    Ion mobility (IM) is a gas-phase electrophoretic method that separates ions according to charge and ion-neutral collision cross-section (CCS). Herein, we attempt to apply a travelling wave (TW) IM polyalanine calibration method to shotgun proteomics and create a large peptide CCS database. Mass spectrometry methods that utilize IM, such as HDMSE, often use high transmission voltages for sensitive analysis. However, polyalanine calibration has only been demonstrated with low voltage transmission used to prevent gas-phase activation. If polyalanine ions change conformation under higher transmission voltages used for HDMSE, the calibration may no longer be valid. Thus, we aimed to characterize the accuracy of calibration and CCS measurement under high transmission voltages on a TW IM instrument using the polyalanine calibration method and found that the additional error was not significant. We also evaluated the potential error introduced by liquid chromatography (LC)-HDMSE analysis, and found it to be insignificant as well, validating the calibration method. Finally, we demonstrated the utility of building a large-population peptide CCS database by investigating the effects of terminal lysine position, via LysC or LysN digestion, on the formation of two structural sub-families formed by triply charged ions. PMID:24845359

  15. Enhancement of mass spectrometry performance for proteomic analyses using high-field asymmetric waveform ion mobility spectrometry (FAIMS).

    PubMed

    Bonneil, Eric; Pfammatter, Sibylle; Thibault, Pierre

    2015-11-01

    Remarkable advances in mass spectrometry sensitivity and resolution have been accomplished over the past two decades to enhance the depth and coverage of proteome analyses. As these technological developments expanded the detection capability of mass spectrometers, they also revealed an increasing complexity of low abundance peptides, solvent clusters and sample contaminants that can confound protein identification. Separation techniques that are complementary and can be used in combination with liquid chromatography are often sought to improve mass spectrometry sensitivity for proteomics applications. In this context, high-field asymmetric waveform ion mobility spectrometry (FAIMS), a form of ion mobility that exploits ion separation at low and high electric fields, has shown significant advantages by focusing and separating multiply charged peptide ions from singly charged interferences. This paper examines the analytical benefits of FAIMS in proteomics to separate co-eluting peptide isomers and to enhance peptide detection and quantitative measurements of protein digests via native peptides (label-free) or isotopically labeled peptides from metabolic labeling or chemical tagging experiments. PMID:26505763

  16. Application of Ion Mobility Mass Spectrometry for Detection and Identification of Oxidized Organic Species during SOAS 2013

    NASA Astrophysics Data System (ADS)

    Canagaratna, M. R.; Krechmer, J.; Kimmel, J.; Junninen, H.; Knochenmuss, R.; Cubison, M.; Massoli, P.; Stark, H.; Jayne, J. T.; Jimenez, J. L.; Worsnop, D. R.

    2013-12-01

    We present results obtained with a chemical ionization ion mobility time-of-flight mass spectrometer (CI-IMS-TOF) that was deployed during the Southern Oxidant and Aerosol Study (SOAS) at the Supersite in Centreville, AL. This two dimensional technique, which separates ions on the basis of their interactions with buffer gases before analysis by high-resolution time-of-flight mass spectrometry, allows for detailed separation and identification of isomeric and isobaric species. During SOAS the IMS-TOF was coupled to a chemical ionization source that utilized NO3- as the reagent ion. The NO3- reagent ion clusters with highly oxidized species and allows for a unique means of directly detecting particle phase precursors in the gas phase. Gas phase molecules corresponding to oxidized products of isoprene and terpenes were detected throughout the campaign with a time resolution of 5 minutes. Ion mobility separation and trends observed for several of these key species are discussed. In addition to ambient sampling, the CI-IMS-TOF was also operated behind a potential aerosol mass (PAM) flow reactor which exposed ambient air to high levels of OH radical. Ambient CI-IMS-TOF spectra obtained with and without the flow reactor are presented and compared with laboratory flow reactor spectra generated from isoprene and terpene precursors.

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

    PubMed

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

    2016-05-17

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

  18. The role of ion optics modeling in the design and development of ion mobility spectrometers

    NASA Astrophysics Data System (ADS)

    Griffin, Matthew T.

    2005-05-01

    Detection of trace gases by ion mobility spectroscopy (IMS) has become common in recent years. In fact, IMS devices are the most commonly deployed military devices for the detection of classical chemical warfare agents (CWA). IMS devices are protecting the homeland by aiding first responders in the identification of toxic industrial chemicals (TICs) and providing explosive and narcotic screening systems. Spurred by the asymmetric threat posed by new threat agents and the ever expanding list of toxic chemicals, research in the development, improvement, and optimization of IMS systems has increased. Much of the research is focused on increasing the sensitivity and selectivity of IMS systems. Ion optics is a large area of study in the field of mass spectrometry, but has been mostly overlooked in the design and development of IMS systems. Ion optics provides insight into particle trajectories, duty cycle, and efficiency of these systems. This paper will outline the role that ion optics can have in the development of IMS systems and introduce the trade space for traditional IMS as well as differential mobility spectroscopy.

  19. Ion mobility spectrometry for pharmacokinetic studies – exemplary application

    PubMed Central

    Ruzsanyi, V.

    2013-01-01

    Breath analysis is an attractive non-invasive method for diagnosis and therapeutic monitoring. It uses endogenously produced compounds and metabolites of isotopically labelled precursors. In order to make such tests clinically useful, it is important to have relatively small portable instruments detecting volatile compounds within short time. A particularly promising analytical technique is ion mobility spectrometry (IMS) coupled to a multicapillary column (MCC). The present paper focuses on demonstrating the suitability of breath analysis for pharmacokinetic applications using MCC-IMS with respect to practicability and reproducibility testing the model substrate eucalyptol. Validation of the MCC-IMS measurements were performed using proton transfer reaction mass spectrometry (PTR-MS) and resulted in an excellent correspondence of the time-dependent concentrations presented by the two different analytical techniques. Moreover, the good accordance in variance of kinetic parameters with repeated measures, and the determined inter-subject differences indicate the eligibility of the analysis method. PMID:24287589

  20. Development of Ion Mobility Spectrometry for Exobiology Flight Experiments

    NASA Technical Reports Server (NTRS)

    Kojiro, Daniel R.; Carle, Glenn C.; Humphry, Donald E.; Shao, Maxine; Takeuchi, Nori; Chang, Sherwood (Technical Monitor)

    1996-01-01

    Ion Mobility Spectrometry (IMS) can provide gas chromatography with sample identification independent of sample retention time, with minimal interface. Initial commercial methods of IMS however, did not possess sufficient analytical capabilities and presented operational parameters which were unsuitable for exobiology missions. Subsequent development of IMS technology, with the focus on exobiology analytical requirements and mission imposed operational limitations, has produced an IMS interfaced with a GC capable of fulfilling the analytical requirements of several exobiology missions. Future exobiology missions will require further development of the IMS, particularly in the areas of overall instrument miniaturization and complex sample identification. The evolution of the exobiology focused IMS will be presented up to the current prototype design, which is a component of several proposed exobiology instruments. Areas of future development will also be discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  2. Recent developments in ion mobility spectrometry detection technology

    NASA Astrophysics Data System (ADS)

    Ritchie, Robert K.; Kuja, Frank J.; Jackson, Ronald A.; Loveless, Arthur J.; Danylewich-May, Lucy L.

    1994-03-01

    Barringer's new IONSCANTM model 350 provides improved operational flexibility, reliability, and effectiveness in the rapid on-site detection and identification of narcotics and explosives. The model 350 is a modular integrated design, with DC-power capabilities, and wheels or vehicle mounts to facilitate transportation to and operation in a variety of operational locations. Recent developments in IONSCAN ion mobility spectrometer (IMS) technology in the model 350 include a long-life air dryer/purification system and new software for improved substance detection and false alarm rate performance. New multiple peak detection capabilities for more reliable substance identification are described. Studies on IMS temperature and pressure effects are reported and their possible future use to further improve peak detection performance are discussed. Some recent applications in narcotics interdiction are described.

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

    PubMed

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

    2016-06-01

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

  4. Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation.

    PubMed

    Kamcev, Jovan; Galizia, Michele; Benedetti, Francesco M; Jang, Eui-Soung; Paul, Donald R; Freeman, Benny D; Manning, Gerald S

    2016-02-17

    Equilibrium partitioning of ions between a membrane and a contiguous external solution strongly influences transport properties of polymeric membranes used for water purification and energy generation applications. This study presents a theoretical framework to quantitatively predict ion sorption from aqueous electrolytes (e.g., NaCl, MgCl2) into charged (i.e., ion exchange) polymers. The model was compared with experimental NaCl, MgCl2, and CaCl2 sorption data in commercial cation and anion exchange membranes. Ion sorption in charged polymers was modeled using a thermodynamic approach based on Donnan theory coupled with Manning's counter-ion condensation theory to describe non-ideal behavior of ions in the membrane. Ion activity coefficients in solution were calculated using the Pitzer model. The resulting model, with no adjustable parameters, provides remarkably good agreement with experimental values of membrane mobile salt concentration. The generality of the model was further demonstrated using literature data for ion sorption of various electrolytes in charged polymers, including HCl sorption in Nafion. PMID:26840776

  5. Gas phase studies on terpenes by ion mobility spectrometry using different atmospheric pressure chemical ionization techniques

    NASA Astrophysics Data System (ADS)

    Borsdorf, H.; Stone, J. A.; Eiceman, G. A.

    2005-11-01

    The ionization pathways and drift behavior were determined for sets of constitutional isomeric and stereoisomeric non-polar hydrocarbons (unsaturated monocyclic terpenes, unsaturated and saturated bicyclic terpenes) using ion mobility spectrometry (IMS) with different techniques of atmospheric pressure chemical ionization (APCI) to assess how structural and stereochemical differences influence ion formation. Depending on the structural features, different ions were observed for constitutional isomers using ion mobility spectrometry with photoionization (PI) and corona discharge (CD) ionization. Photoionization provides ion mobility spectra containing one major peak for saturated compounds while at two peaks were observed for unsaturated compounds, which can be assigned to product ions related to monomer and dimer ions. However, differences in relative abundance of product ions were found depending on the position of the double bond. Although IMS using corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra are complex and differ from those obtained using photoionization. Additional cluster ions and fragment ions were detected. Only small differences in ion mobility spectra were observed for the diastereomers while the enantiomers provide identical spectra. The structure of the product ions formed was checked by investigations using the coupling of ion mobility spectrometry with mass spectrometry (IMS-MS).

  6. Oversampling Selective Accumulation Trapped Ion Mobility Spectrometry Coupled to FT-ICR MS: Fundamentals and Applications.

    PubMed

    Benigni, Paolo; Fernandez-Lima, Francisco

    2016-07-19

    In the present paper, we describe the fundamentals and analytical advantages of Oversampling Selective Accumulation Trapped Ion Mobility Spectrometry (OSA-TIMS) when coupled to ultrahigh resolution mass analyzers (e.g., FT-ICR MS). During TIMS analysis, ion packages are spatially resolved based on their mobilities along the TIMS analyzer axis and multiple strategies can be utilized during the trapping and elution of the ion population of interest. In the case of OSA-TIMS-FT-ICR MS, the TIMS operation sequence, trapping conditions, and operations are optimized to increase the signal-to-noise and the number of points across the mobility domain, which leads to more accurate mobility and mass measurements. Experimental results show that accurate ion-neutral collision cross sections (<1%) can be measured using OSA-TIMS-FT-ICR MS with high mobility resolving powers (RIMS up to 250), high mass accuracy (<1 ppm), and ultrahigh mass resolution (RMS up to 600-1200k at m/z 400) in a single analysis. The analytical advantages of OSA-TIMS over SA-TIMS were illustrated for the analysis of structural peptide isomers (SDGRG and GRGDS [M + H](+)), conformational isomers (AT-hook peptide 3 KRGRGRPRK [M + 2H](+2)), and a complex mixture of polyaromatic hydrocarbons (PAH) from coal tar. Baseline separation of the structural peptide isomers SDGRG and GRGDS, [M + H](+), was observed, and three conformations were identified for the AT-hook peptide 3 KRGRGRPRK [M + 2H](+2) during OSA-TIMS-FT-ICR MS. A 2-fold increase in the number of molecular features and a 2-6-fold signal-to-noise increase was observed for OSA-TIMS when compared with SA-TIMS during the PAH analysis. This work provides the proof-of-principle for further application of OSA-TIMS-FT-ICR MS for the unsupervised analysis of complex mixtures based on the characterization of the conformational space and the assignment of chemical formulas in a single analysis. PMID:27340830

  7. The Role of Oxygen in the Formation of TNT Product Ions in Ion Mobility Spectrometry

    SciTech Connect

    Daum, Keith Alvin; Atkinson, David Alan; Ewing, Robert Gordon

    2002-03-01

    The atmospheric pressure ionization of 2,4,6-trinitrotoluene (TNT) in air yields the (TNT-H)- product ion. It is generally accepted that this product ion is formed by the direct proton abstraction of neutral TNT by O2- reactant ions. Data presented here demonstrate the reaction involves the formation of an intermediate (TNT·O2)-, from the association of either TNT+O2- or TNT-+O2. This intermediate has two subsequent reaction branches. One of these branches involves simple dissociation of the intermediate to TNT-; the other branch is a terminal reaction that forms the typically observed (TNT-H)- ion via proton abstraction. The dissociation reaction involving electron transfer to TNT- appeared to be kinetically favored and prevailed at low concentrations of oxygen (less than 2%). The presence of significant amounts of oxygen, however, resulted in the predominant formation of the (TNT-H)- ion by the terminal reaction branch. With TNT- in the system, either from direct electron attachment or by simple dissociation of the intermediate, increasing levels of oxygen in the system will continue to reform the intermediate, allowing the cycle to continue until proton abstraction occurs. Key to understanding this complex reaction pathway is that O2- was observed to transfer an electron directly to neutral TNT to form the TNT-. At oxygen levels of less than 2%, the TNT- ion intensity increased with increasing levels of oxygen (and O2-) and was larger than the (TNT-H)- ion intensity. As the oxygen level increased from 2 to 10%, the (TNT-H)- product ion became predominant. The potential reaction mechanisms were investigated with an ion mobility spectrometer, which was configured to independently evaluate the ionization pathways.

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

    PubMed

    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

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

    PubMed Central

    Li, Lingjun

    2014-01-01

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

  10. Materials for Electroactive Ion-Exchange (EaIX) Separations of Pertechnetate Ion

    SciTech Connect

    Stender, Matthias; Hubler, Timothy L.; Alhoshan, Mansour; Smyrl, William H.

    2004-03-29

    Many contaminants of interest to the U.S. Department of Energy (DOE) exist as anions (e.g. chromate, pertechnetate and nitrate). The objective of this study is to develop Electroactive Ion-Exchange (EaIX) materials. Such materials can be used to separate pertechnetate ion from radioactive wastes located at DOE sites while limiting the amount of secondary wastes generated. We have developed a synthetic strategy to prepare vinyl-bipyridyl and -terpyridyl ligands which allow incorporation of ion-selective architectures with a polymerizable handle. Fe complexes formed with these ligands provide the working core of the electroactive polymers. The polymers can be directly used as materials for EaIX or they can be incorporated into porous composite materials that are then used for EaIX.

  11. Direct analysis of pharmaceutical drug formulations using ion mobility spectrometry/quadrupole-time-of-flight mass spectrometry combined with desorption electrospray ionization.

    PubMed

    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. PMID:16316164

  12. Total residue analysis of swabs by ion mobility spectrometry.

    PubMed

    Strege, Mark A

    2009-06-01

    Ion mobility spectrometry (IMS) is a technique attractive for use within the pharmaceutical industry for at-line determination of residues on swabs taken from the surfaces of manufacturing equipment for the purposes of cleaning validation or verification. In this study, the development of a novel IMS method to provide a measurement of total residue present on a swab is described. The technique is based upon quantitation of charged atmospheric gas reactant ion consumption (RIC) within the instrument as a direct measure of the mass of total ionizable residue. Coupled with the conventional analysis of the active pharmaceutical ingredient within a single 2 min analysis, RIC determination provided the benefit of a single measure representative of the presence of multiple residue components or unknown components. To account for differences in response between components of a model drug product (Cymbalta) and its associated cleaning agents, a strategy was proposed to determine a "worst case" total residue test result based on RIC. A limitation of the IMS method was its incompatibility with cleaners containing a high concentration of inorganic components. The methodology provided a range from 5-50 microg per 25 cm(2) surface area and acceptable analyte recovery (50-100%). PMID:19476393

  13. Low-temperature plasma ionization differential ion mobility spectrometry.

    PubMed

    Kuklya, Andriy; Engelhard, Carsten; Uteschil, Florian; Kerpen, Klaus; Marks, Robert; Telgheder, Ursula

    2015-09-01

    A low-temperature plasma (LTP) was used as an ionization source for differential ion mobility spectrometry (DMS) for the first time. This ionization source enhances the potential of DMS as a miniaturized system for on-site rapid monitoring. The effects of experimental parameters (e.g., discharge/carrier gas composition and flow rate, applied voltage) on the analysis of model aromatic compounds were investigated and discussed. It was found that the nature of reactant ion positive (RIP) is dependent on the discharge/carrier gas composition. The best response to the analyte was achieved when pure nitrogen was used as the discharge/carrier gas. The ability to perform analysis with zero helium consumption is especially attractive in view of the potential application of LTP-DMS for online (and on-site) monitoring. Analytical performance was determined with six environmentally relevant model compounds (benzene, toluene, ethylbenzene, p-xylene, 1,2,4-trimethylbenzene, and naphthalene) using LTP and directly compared to APPI and APCI ((63)Ni) ionization sources. When LTP was coupled to DMS, calculated LOD values were found to be in the range of 35-257 ng L(-1) (concentration in the carrier gas). These values are competitive with those calculated for two DMS equipped with traditional ionization sources (APPI, (63)Ni). The obtained results are promising enough to ensure the potential of LTP as ionization source for DMS. PMID:26266836

  14. Site-Specific Characterization of d-Amino Acid Containing Peptide Epimers by Ion Mobility Spectrometry

    PubMed Central

    2013-01-01

    Traditionally, the d-amino acid containing peptide (DAACP) candidate can be discovered by observing the differences of biological activity and chromatographic retention time between the synthetic peptides and naturally occurring peptides. However, it is difficult to determine the exact position of d-amino acid in the DAACP candidates. Herein, we developed a novel site-specific strategy to rapidly and precisely localize d-amino acids in peptides by ion mobility spectrometry (IMS) analysis of mass spectrometry (MS)-generated epimeric fragment ions. Briefly, the d/l-peptide epimers were separated by online reversed-phase liquid chromatography and fragmented by collision-induced dissociation (CID), followed by IMS analysis. The epimeric fragment ions resulting from d/l-peptide epimers exhibit conformational differences, thus showing different mobilities in IMS. The arrival time shift between the epimeric fragment ions was used as criteria to localize the d-amino acid substitution. The utility of this strategy was demonstrated by analysis of peptide epimers with different molecular sizes, [d-Trp]-melanocyte-stimulating hormone, [d-Ala]-deltorphin, [d-Phe]-achatin-I, and their counterparts that contain all-l amino acids. Furthermore, the crustacean hyperglycemia hormones (CHHs, 8.5 kDa) were isolated from the American lobster Homarus americanus and identified by integration of MS-based bottom-up and top-down sequencing approaches. The IMS data acquired using our novel site-specific strategy localized the site of isomerization of l- to d-Phe at the third residue of the CHHs from the N-terminus. Collectively, this study demonstrates a new method for discovery of DAACPs using IMS technique with the ability to localize d-amino acid residues. PMID:24328107

  15. Modular calibrant sets for the structural analysis of nucleic acids by ion mobility spectrometry mass spectrometry.

    PubMed

    Lippens, Jennifer L; Ranganathan, Srivathsan V; D'Esposito, Rebecca J; Fabris, Daniele

    2016-06-20

    This study explored the use of modular nucleic acid (NA) standards to generate calibration curves capable of translating primary ion mobility readouts into corresponding collision cross section (CCS) data. Putative calibrants consisted of single- (ss) and double-stranded (ds) oligo-deoxynucleotides reaching up to ∼40 kDa in size (i.e., 64 bp) and ∼5700 Å(2) in CCS. To ensure self-consistency among reference CCS values, computational data obtained in house were preferred to any experimental or computational data from disparate sources. Such values were obtained by molecular dynamics (MD) simulations and either the exact hard sphere scattering (EHSS) or the projection superposition approximation (PSA) methods, and then plotted against the corresponding experimental values to generate separate calibration curves. Their performance was evaluated on the basis of their correlation coefficients and ability to provide values that matched the CCS of selected test samples mimicking typical unknowns. The results indicated that the predictive power benefited from the exclusion of higher charged species that were more susceptible to the destabilizing effects of Coulombic repulsion. The results revealed discrepancies between EHSS and PSA data that were ascribable to the different approximations used to describe the ion mobility process. Within the boundaries defined by these approximations and the challenges of modeling NA structure in a solvent-free environment, the calibrant sets enabled the experimental determination of CCS with excellent reproducibility (precision) and error (accuracy), which will support the analysis of progressively larger NA samples of biological significance. PMID:27152369

  16. Machine learning based prediction for peptide drift times in ion mobility spectrometry

    PubMed Central

    Shah, Anuj R.; Agarwal, Khushbu; Baker, Erin S.; Singhal, Mudita; Mayampurath, Anoop M.; Ibrahim, Yehia M.; Kangas, Lars J.; Monroe, Matthew E.; Zhao, Rui; Belov, Mikhail E.; Anderson, Gordon A.; Smith, Richard D.

    2010-01-01

    Motivation: Ion mobility spectrometry (IMS) has gained significant traction over the past few years for rapid, high-resolution separations of analytes based upon gas-phase ion structure, with significant potential impacts in the field of proteomic analysis. IMS coupled with mass spectrometry (MS) affords multiple improvements over traditional proteomics techniques, such as in the elucidation of secondary structure information, identification of post-translational modifications, as well as higher identification rates with reduced experiment times. The high throughput nature of this technique benefits from accurate calculation of cross sections, mobilities and associated drift times of peptides, thereby enhancing downstream data analysis. Here, we present a model that uses physicochemical properties of peptides to accurately predict a peptide's drift time directly from its amino acid sequence. This model is used in conjunction with two mathematical techniques, a partial least squares regression and a support vector regression setting. Results: When tested on an experimentally created high confidence database of 8675 peptide sequences with measured drift times, both techniques statistically significantly outperform the intrinsic size parameters-based calculations, the currently held practice in the field, on all charge states (+2, +3 and +4). Availability: The software executable, imPredict, is available for download from http:/omics.pnl.gov/software/imPredict.php Contact: rds@pnl.gov Supplementary information: Supplementary data are available at Bioinformatics online. PMID:20495001

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

    PubMed Central

    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

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

    DOE PAGESBeta

    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; et al

    2016-07-25

    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) ambientmore » 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

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

    NASA Astrophysics Data System (ADS)

    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

  20. Separation of traces of metal ions from sodium matrices

    NASA Technical Reports Server (NTRS)

    Korkisch, J.; Orlandini, K. A.

    1969-01-01

    Method for isolating metal ion traces from sodium matrices consists of two extractions and an ion exchange step. Extraction is accomplished by using 2-thenoyltrifluoracetone and dithizone followed by cation exchange.

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

    SciTech Connect

    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].

  2. Advances in ion mobility spectrometry–mass spectrometry reveal key insights into amyloid assembly☆

    PubMed Central

    Woods, L.A.; Radford, S.E.; Ashcroft, A.E.

    2013-01-01

    Interfacing ion mobility spectrometry to mass spectrometry (IMS–MS) has enabled mass spectrometric analyses to extend into an extra dimension, providing unrivalled separation and structural characterization of lowly populated species in heterogeneous mixtures. One biological system that has benefitted significantly from such advances is that of amyloid formation. Using IMS–MS, progress has been made into identifying transiently populated monomeric and oligomeric species for a number of different amyloid systems and has led to an enhanced understanding of the mechanism by which small molecules modulate amyloid formation. This review highlights recent advances in this field, which have been accelerated by the commercial availability of IMS–MS instruments. This article is part of a Special Issue entitled: Mass spectrometry in structural biology. PMID:23063533

  3. Detection and characterization of smokeless powders with ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Hernandez, Neiza M.; Rosario, Santa V.; Hernandez, Samuel P.; Mina, Nairmen

    2005-05-01

    Smokeless Powders are a class of propellants that were developed in the late 19th century to replace black powder; it has been used as an explosive in shotguns, rifles, firearms and many other larger caliber weapons. These propellants can be placed into one of three different classes according to the chemical composition of their primary energetic ingredients. Advance equipment have been designed and used for the detection of explosives devices and compounds potentially energetic. In this research we are developing an analytical methodology to detect different formulation of smokeless powders: Alliant-American Select, Alliant-Bullseye, and Alliant-Red Dot using the ion mobility spectrometry (IMS) technique. We used different surfaces like computer diskettes, CD"s, book covers and plastics to study their adsorption/desorption process. Using micropipettes, we delivered solutions with different amounts of Smokeless Powders from a 1000 ppm solution and deposit it on various types of filters to make a calibration curve. Several amounts of Smokeless Powder were deposited to the different surfaces and collected with filter paper. The samples were desorbed directly from the filter to the instrument inlet port. Subsequently, the percentage of explosive recovered was calculated.

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

    PubMed

    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. PMID:26851088

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed Central

    2015-01-01

    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 Vp-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 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 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. PMID:25152066

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

    PubMed Central

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

    2016-01-01

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

  8. Optimization of a Differential Ion Mobility Spectrometry-Tandem Mass Spectrometry Method for High-Throughput Analysis of Nicotine and Related Compounds: Application to Electronic Cigarette Refill Liquids.

    PubMed

    Regueiro, Jorge; Giri, Anupam; Wenzl, Thomas

    2016-06-21

    Fast market penetration of electronic cigarettes is leading to an exponentially growing number of electronic refill liquids with different nicotine contents and an endless list of flavors. Therefore, rapid and simple methods allowing a fast screening of these products are necessary to detect harmful substances which can negatively impact the health of consumers. In this regard, the present work explores the capabilities of differential ion mobility spectrometry coupled to tandem mass spectrometry for high-throughput analysis of nicotine and 11 related compounds in commercial refill liquids for electronic cigarettes. The influence of main factors affecting the ion mobility separation, such as modifier types and concentration, separation voltage, and temperature, was systematically investigated. Despite small molecular weight differences among the studied compounds, a good separation was achieved in the ion mobility cell under the optimized conditions, which involved the use of ethanol as a polar gas-phase chemical modifier. Indeed, differential ion mobility was able to resolve (resolution >4) nicotine from its structural isomer anabasine without the use of any chromatographic separation. The quantitative performance of the proposed method was then evaluated, showing satisfactory precision (RSD ≤ 16%) and recoveries ranging from 85 to 100% for nicotine, and from 84 to 126% for the rest of the target analytes. Several commercial electronic cigarette refill liquids were analyzed to demonstrate the applicability of the method. In some cases, significant differences were found between labeled and measured levels of nicotine. Anatabine, cotinine, myosmine, and nornicotine were also found in some of the analyzed samples. PMID:27173877

  9. Decreased Gap Width in a Cylindrical High-Field Asymmetric Waveform Ion Mobility Spectrometry Device Improves Protein Discovery.

    PubMed

    Swearingen, Kristian E; Winget, Jason M; Hoopmann, Michael R; Kusebauch, Ulrike; Moritz, Robert L

    2015-12-15

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas phase ions according to their characteristic dependence of ion mobility on electric field strength. FAIMS can be implemented as a means of automated gas-phase fractionation in liquid chromatography-tandem mass spectrometry (LC-MS/MS) experiments. We modified a commercially available cylindrical FAIMS device by enlarging the inner electrode, thereby narrowing the gap and increasing the effective field strength. This modification provided a nearly 4-fold increase in FAIMS peak capacity over the optimally configured unmodified device. We employed the modified FAIMS device for on-line fractionation in a proteomic analysis of a complex sample and observed major increases in protein discovery. NanoLC-FAIMS-MS/MS of an unfractionated yeast tryptic digest using the modified FAIMS device identified 53% more proteins than were identified using an unmodified FAIMS device and 98% more proteins than were identified with unaided nanoLC-MS/MS. We describe here the development of a nanoLC-FAIMS-MS/MS protocol that provides automated gas-phase fractionation for proteomic analysis of complex protein digests. We compare this protocol against prefractionation of peptides with isoelectric focusing and demonstrate that FAIMS fractionation yields comparable protein recovery while significantly reducing the amount of sample required and eliminating the need for additional sample handling. PMID:26560994

  10. Broadscale resolving power performance of a high precision uniform field ion mobility-mass spectrometer.

    PubMed

    May, Jody C; Dodds, James N; Kurulugama, Ruwan T; Stafford, George C; Fjeldsted, John C; McLean, John A

    2015-10-21

    An extensive study of two current ion mobility resolving power theories ("conditional" and "semi-empirical") was undertaken using a recently developed drift tube ion mobility-mass spectrometer. The current study investigates the quantitative agreement between experiment and theory at reduced pressure (4 Torr) for a wide range of initial ion gate widths (100 to 500 μs), and ion mobility values (K0 from 0.50 to 3.0 cm(2) V(-1) s(-1)) representing measurements obtained in helium, nitrogen, and carbon dioxide drift gas. Results suggest that the conditional resolving power theory deviates from experimental results for low mobility ions (e.g., high mass analytes) and for initial ion gate widths beyond 200 μs. A semi-empirical resolving power theory provided close-correlation of predicted resolving powers to experimental results across the full range of mobilities and gate widths investigated. Interpreting the results from the semi-empirical theory, the performance of the current instrumentation was found to be highly linear for a wide range of analytes, with optimal resolving powers being accessible for a narrow range of drift fields between 14 and 17 V cm(-1). While developed using singly-charged ion mobility data, preliminary results suggest that the semi-empirical theory has broader applicability to higher-charge state systems. PMID:26191544

  11. Optimization of ion-exchange protein separations using a vector quantizing neural network.

    PubMed

    Klein, E J; Rivera, S L; Porter, J E

    2000-01-01

    In this work, a previously proposed methodology for the optimization of analytical scale protein separations using ion-exchange chromatography is subjected to two challenging case studies. The optimization methodology uses a Doehlert shell design for design of experiments and a novel criteria function to rank chromatograms in order of desirability. This chromatographic optimization function (COF) accounts for the separation between neighboring peaks, the total number of peaks eluted, and total analysis time. The COF is penalized when undesirable peak geometries (i.e., skewed and/or shouldered peaks) are present as determined by a vector quantizing neural network. Results of the COF analysis are fit to a quadratic response model, which is optimized with respect to the optimization variables using an advanced Nelder and Mead simplex algorithm. The optimization methodology is tested on two case study sample mixtures, the first of which is composed of equal parts of lysozyme, conalbumin, bovine serum albumin, and transferrin, and the second of which contains equal parts of conalbumin, bovine serum albumin, tranferrin, beta-lactoglobulin, insulin, and alpha -chymotrypsinogen A. Mobile-phase pH and gradient length are optimized to achieve baseline resolution of all solutes for both case studies in acceptably short analysis times, thus demonstrating the usefulness of the empirical optimization methodology. PMID:10835256

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

    PubMed

    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. PMID:25619987

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

    NASA Astrophysics Data System (ADS)

    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

  14. Correlation of ion-ion interaction with electrical conductivity in solid state polymeric separator for energy storage applications

    NASA Astrophysics Data System (ADS)

    Sharma, Parul Kumar; Sadiq, M.; Bhatt, Chandni; Sharma, A. L.

    2016-05-01

    In the present study, we report innovative study on the prepared high quality solid state free standing thin polymeric separator. In prepared free standing polymeric separator, polymer (PEO) has been used as host matrix; appropriate bulky anion salt (LiPF6) as conducting species and Nano ceramic filler (BaTiO3) is used to enrich the mechanical and thermal stability of separator used for the device applications. The Fourier Transform Infra-Red (FTIR) result has been analysed properly of the prepared materials to look the microscopic interaction among polymer-ion, ion-ion and polymer-ion-clay interaction. Electrical conductivity results has been recorded using the impedance spectroscopy results which gives the estimated value of the order of ˜10-3 Scm-1 of the nano ceramic doped polymeric separator which is desirable for energy storage application. A fine correlation has been established between the obtained results by this two analysis.

  15. Detection and classification of explosive compounds utilizing laser ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Langmeier, A.; Heep, W.; Oberhuettinger, C.; Oberpriller, H.; Kessler, M.; Goebel, J.; Mueller, G.

    2009-05-01

    Detection of explosives by ion mobility spectroscopy has become common in recent years. We demonstrate explosive detection with a novel Laser Ion Mobility Spectrometer (LIMS) developed at EADS Innovation Works. A Laser operating at 266nm was used for the two-photon ionisation of dopant and calibrant substances. Quantitative measurements of trace residues of explosives have been performed to quantify the sensitivity of the LIMS system. Findings demonstrate the suitability of this technique as a screening tool for explosive compounds.

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

    SciTech Connect

    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.

  17. Theoretical evaluation of peak capacity improvements by use of liquid chromatography combined with drift tube ion mobility-mass spectrometry.

    PubMed

    Causon, Tim J; Hann, Stephan

    2015-10-16

    In the domain of liquid phase separations, the quality of separation obtainable is most readily gauged by consideration of classical chromatographic peak capacity theory. Column-based multidimensional strategies for liquid chromatography remain the most attractive and practical route for increasing the number of spatially resolved components in order to reduce stress on necessary mass spectrometric detection. However, the stress placed on a chromatographic separation step as a second dimension in a comprehensive online methodology (i.e. online LC×LC) is rather high. As an alternative to online LC×LC combinations, coupling of HPLC with ion mobility spectrometry hyphenated to mass spectrometry (IMS-MS) has emerged as an attractive approach to permit comprehensive sampling of first dimension chromatographic peaks and subsequent introduction to an orthogonal IMS separation prior to measurement of ions by a mass spectrometer. In the present work, utilization of classical peak capacity and ion mobility theory allows theoretical assessment of the potential of two- (LC×IMS-MS) or even three-dimensional (LC×LC×IMS-MS) experimental setups to enhance peak capacity and, therefore, the number of correctly annotated features within the framework of complex, non-targeted analysis problems frequently addressed using HPLC-MS strategies. Theoretical calculations indicate that newly-available drift tube IMS-MS instrumentation can yield peak capacities of between 10 and 40 using nitrogen drift gas for typical non-targeted metabolomic, lipidomic and proteomic applications according to the expected reduced mobilities of components in the respective samples. Theoretically, this approach can significantly improve the overall peak capacity of conventional HPLC-(MS) methodologies to in excess of 10(4) depending upon the column length and gradient time employed. A more elaborate combination of LC×LC×IMS-MS would improve the ion suppression limitation and possibly allow access to

  18. Gas molecule scattering & ion mobility measurements for organic macro-ions in He versus N2 environments.

    PubMed

    Larriba-Andaluz, Carlos; Fernández-García, Juan; Ewing, Michael A; Hogan, Christopher J; Clemmer, David E

    2015-06-14

    A pending issue in linking ion mobility measurements to ion structures is that the collisional cross section (CCS, the measured structural parameter in ion mobility spectrometry) of an ion is strongly dependent upon the manner in which gas molecules effectively impinge on and are reemitted from ion surfaces (when modeling ions as fixed structures). To directly examine the gas molecule impingement and reemission processes and their influence, we measured the CCSs of positively charged ions of room temperature ionic liquids 1-ethyl-3-methylimidazolium dicyanamide (EMIM-N(CN)2) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) in N2 using a differential mobility analyzer-mass spectrometer (DMA-MS) and in He using a drift tube mobility spectrometer-mass spectrometer (DT-MS). Cluster ions, generated via electrosprays, took the form (AB)N(A)z, spanning up to z = 20 and with masses greater than 100 kDa. As confirmed by molecular dynamics simulations, at the measurement temperature (∼300 K), such cluster ions took on globular conformations in the gas phase. Based upon their attained charge levels, in neither He nor N2 did the ion-induced dipole potential significantly influence gas molecule-ion collisions. Therefore, differences in the CCSs measured for ions in the two different gases could be primarily attributed to differences in gas molecule behavior upon collision with ions. Overwhelmingly, by comparison of predicted CCSs with selected input impingement-reemission laws to measurements, we find that in N2, gas molecules collide with ions diffusely--they are reemitted at random angles relative to the gas molecule incoming angle--and inelastically. Meanwhile, in He, gas molecules collide specularly and elastically and are emitted from ion surfaces at determined angles. The results can be rationalized on the basis of the momentum transferred per collision; in the case of He, individual gas molecule collisions minimally perturb the atoms within a cluster ion

  19. Evaluation of drift gas selection in complex sample analyses using a high performance drift tube ion mobility-QTOF mass spectrometer.

    PubMed

    Kurulugama, Ruwan T; Darland, Ed; Kuhlmann, Frank; Stafford, George; Fjeldsted, John

    2015-10-21

    A recently developed uniform-field high resolution ion mobility (IM) quadrupole time of flight (Q-TOF) mass spectrometer is used for evaluating the utility of alternate drift gases for complex sample analyses. This study provides collision cross section comparison for 275 total pesticides including structural isomers in nitrogen, helium, carbon dioxide, nitrous oxide and sulfur hexafluoride drift gases. Furthermore, a set of small molecules and Agilent tune mix compounds were used to study the trends in experimentally derived collision cross section values in argon and the alternate drift gases. Two isomeric trisaccharides, melezitose and raffinose, were used to evaluate the effect of the drift gasses for mobility separation. The hybrid ion mobility Q-TOF mass analyzer used in this study consists of a low pressure uniform field drift tube apparatus coupled to a high resolution Q-TOF mass spectrometer. Conventionally, low pressure ion mobility instruments are operated using helium drift gas to obtain optimal structural information and collision cross-section (CCS) values that compare to theoretical CCS values. The instrument employed in this study uses nitrogen as the standard drift gas but also allows the utility of alternate drift gases for improved structural analysis and selectivity under certain conditions. The use of alternate drift gases with a wide range of polarizabilities allows the evaluation of mobility separation power in terms of induced dipole interactions between the drift gas and the analyte ions. PMID:26178817

  20. Novel Nanofiber-based Membrane Separators for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Yanilmaz, Meltem

    Lithium-ion batteries have been widely used in electronic devices including mobile phones, laptop computers, and cameras due to their high specific energy, high energy density, long cycling lifetime, and low self-discharge rate. Nowadays, lithium-ion batteries are finding new applications in electric/hybrid vehicles and energy storage for smart grids. To be used in these new applications, novel battery components are needed so that lithiumion batteries with higher cell performance, better safety, and lower cost can be developed. A separator is an important component to obtain safe batteries and its primary function is to prevent electronic contact between electrodes while regulating cell kinetics and ionic flow. Currently, microporous membranes are the most commonly used separator type and they have good mechanical properties and chemical stability. However, their wettability and thermal stabilities are not sufficient for applications that require high operating temperature and high performance. Due to the superior properties such as large specific surface area, small pore size and high porosity, electrospun nanofiber membranes can be good separator candidate for highperformance lithium-ion batteries. In this work, we focus our research on fabricating nanofiber-based membranes to design new high-performance separators with good thermal stability, as well as superior electrochemical performance compared to microporous polyolefin membranes. To combine the good mechanical strength of PP nonwovens with the excellent electrochemical properties of SiO2/polyvinylidene fluoride (PVDF) composite nanofibers, SiO 2/PVDF composite nanofiber-coated PP nonwoven membranes were prepared. It was found that the addition of SiO2 nanoparticles played an important role in improving the overall performance of these nanofiber-coated nonwoven membranes. Although ceramic/polymer composites can be prepared by encapsulating ceramic particles directly into polymer nanofibers, the performance

  1. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    SciTech Connect

    Bartsch, Richard A.

    2012-06-04

    The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

  2. Properties of nickel-cadmium separators. [ion exchange membrances

    NASA Technical Reports Server (NTRS)

    Lee, J.

    1977-01-01

    The thickness, moisture content, exchange capacity, tensile strength, diffusion characteristics, stability, and electrical properties are discussed for the 2291 radiation-grafted separator used in military vented nickel cadmium aircraft batteries. A regression analysis of separator resistance as a function of temperature and KOH concentration is included.

  3. Design for gas chromatography-corona discharge-ion mobility spectrometry.

    PubMed

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

    2012-11-20

    A corona discharge ionization-ion mobility spectrometry (CD-IMS) with a novel sample inlet system was designed and constructed as a detector for capillary gas chromatography. In this design, a hollow needle was used instead of a solid needle which is commonly used for corona discharge creation, helping us to have direct axial interfacing for GC-IMS. The capillary column was passed through the needle, resulting in a reaction of effluents with reactant ions on the upstream side of the corona discharge ionization source. Using this sample introduction design, higher ionization efficiency was achieved relative to the entrance direction through the side of the drift tube. In addition, the volume of the ionization region was reduced to minimize the resistance time of compounds in the ionization source, increasing chromatographic resolution of the instrument. The effects of various parameters such as drift gas flow, makeup gas flow, and column tip position inside the needle were investigated. The designed instrument was exhaustively validated in terms of sensitivity, resolution, and reproducibility by analyzing the standard solutions of methyl isobutyl ketone, heptanone, nonanone, and acetophenone as the test compounds. The results obtained by CD-IMS detector were compared with those of the flame ionization detector, which revealed the capability of the proposed GC-IMS for two-dimensional separation (based on the retention time and drift time information) and identification of an analyte in complex matrixes. PMID:23083064

  4. Data for Users of Handheld Ion Mobility Spectrometers

    SciTech Connect

    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

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

    PubMed

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

    2015-08-01

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

  6. Electrophoretic mobility as a tool to separate immune adjuvant saponins from Quillaja saponaria Molina.

    PubMed

    Gilabert-Oriol, Roger; Weng, Alexander; von Mallinckrodt, Benedicta; Stöshel, Anja; Nissi, Linda; Melzig, Matthias F; Fuchs, Hendrik; Thakur, Mayank

    2015-06-20

    Quillaja saponins are used as adjuvants in animal vaccines but their application in human vaccination is still under investigation. Isolation and characterization of adjuvant saponins is very tedious. Furthermore, standardization of Quillaja saponins is critical pertaining to its application in humans. In this study, a convenient method based on agarose gel electrophoresis was developed for the separation of Quillaja saponins. Six different commercial Quillaja saponins were segregated by size/charge into numerous fractions. Each of the fractions was characterized by ESI-TOF-MS spectroscopy and thin layer chromatography. Real-time impedance-based monitoring and red blood cell lysis assay were used to evaluate cytotoxicity and hemolytic activities respectively. Two specific regions in the agarose gel (delimited by specific relative electrophoretic mobility values) were identified and characterized by exclusive migration of acylated saponins known to possess immune adjuvant properties (0.18-0.58), and cytotoxic and hemolytic saponins (0.18-0.94). In vivo experiments in mice with the isolated fractions for evaluation of adjuvant activity also correlated with the relative electrophoretic mobility. In addition to the separation of specific Quillaja saponins with adjuvant effects as a pre-purification step to HPLC, agarose gel electrophoresis stands out as a new method for rapid screening, separation and quality control of saponins. PMID:25839418

  7. Pulsed discharge ionization source for miniature ion mobility spectrometers

    DOEpatents

    Xu, Jun; Ramsey, J. Michael; Whitten, William B.

    2004-11-23

    A method and apparatus is disclosed for flowing a sample gas and a reactant gas (38, 43) past a corona discharge electrode (26) situated at a first location in an ion drift chamber (24), applying a pulsed voltage waveform comprising a varying pulse component and a dc bias component to the corona discharge electrode (26) to cause a corona which in turn produces ions from the sample gas and the reactant gas, applying a dc bias to the ion drift chamber (24) to cause the ions to drift to a second location (25) in the ion drift chamber (24), detecting the ions at the second location (25) in the drift chamber (24), and timing the period for the ions to drift from the corona discharge electrode to the selected location in the drift chamber.

  8. A Highly Thermostable Ceramic-Grafted Microporous Polyethylene Separator for Safer Lithium-Ion Batteries.

    PubMed

    Zhu, Xiaoming; Jiang, Xiaoyu; Ai, Xinping; Yang, Hanxi; Cao, Yuliang

    2015-11-01

    The safety concern is a critical obstacle to large-scale energy storage applications of lithium-ion batteries. A thermostable separator is one of the most effective means to construct the safe lithium-ion batteries. Herein, we demonstrate a novel ceramic (SiO2)-grafted PE separator prepared by electron beam irradiation. The separator shows similar thickness and pore structure to the bare separator, while displaying strong dimensional thermostability, as the shrinkage ratio is only 20% even at an elevated temperature of 180 °C. Besides, the separator is highly electrochemically inert, showing no adverse effect on the energy and power output of the batteries. Considering the excellent electrochemical and thermal stability, the SiO2-grafted PE separator developed in this work is greatly beneficial for constructing safer lithium-ion batteries. PMID:26457445

  9. Lorentz effect imaging of ionic currents in solution using correct values for ion mobility

    NASA Astrophysics Data System (ADS)

    Wijesinghe, Ranjith S.; Roth, Bradley J.

    2010-06-01

    Truong and his colleagues have recently published a paper introducing a new method called Lorentz effect imaging (LEI) to detect ionic currents in a solution. Their main goal was to prove that the Lorentz force acting on ions in the presence of a static magnetic field could be used as a contrast mechanism to measure neural currents with magnetic resonance imaging. However, they failed to use the correct values for the ion mobilities. In this investigation, we have used correct ion mobility values and show that LEI cannot be used as a contrast mechanism to directly image neural currents.

  10. Waste separation and pretreatment using crystalline silicotitanate ion exchangers

    SciTech Connect

    Tadros, M.E.; Miller, J.E.; Anthony, R.G.

    1997-10-01

    A new class of inorganic ion exchangers called crystalline silicotitanates (CSTs) has been developed jointly by Sandia National Laboratories and Texas A&M University to selectively remove Cs and other radionuclides from a wide spectrum of radioactive defense wastes. The CST exhibits high selectivity and affinity for Cs and Sr under a wide range of conditions. Tests show it can remove part-per-million concentrations of Cs{sup +} from highly alkaline, high-sodium simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. The materials exhibit ion exchange properties based on ionic size selectivity. Specifically, crystalline lattice spacing is controlled to be highly selective for Cs ions even in waste streams containing very high (5 to 10 M) concentrations of sodium. The CST technology is being demonstrated with actual waste at several DOE facilities. The use of inorganic ion exchangers. The inorganics are more resistant to chemical, thermal, and radiation degradation. Their high selectivities result in more efficient operations offering the possibility of a simple single-pass operation. In contrast, regenerable organic ion exchangers require additional processing equipment to handle the regeneration liquids and the eluant with the dissolved Cs.

  11. Liquid extraction surface analysis field asymmetric waveform ion mobility spectrometry mass spectrometry for the analysis of dried blood spots.

    PubMed

    Griffiths, Rian L; Dexter, Alex; Creese, Andrew J; Cooper, Helen J

    2015-10-21

    Liquid extraction surface analysis (LESA) is a surface sampling technique that allows electrospray mass spectrometry analysis of a wide range of analytes directly from biological substrates. Here, we present LESA mass spectrometry coupled with high field asymmetric waveform ion mobility spectrometry (FAIMS) for the analysis of dried blood spots on filter paper. Incorporation of FAIMS in the workflow enables gas-phase separation of lipid and protein molecular classes, enabling analysis of both haemoglobin and a range of lipids (phosphatidylcholine or phosphatidylethanolamine, and sphingomyelin species) from a single extraction sample. The work has implications for multiplexed clinical assays of multiple analytes. PMID:26198596

  12. SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

    DOEpatents

    Schubert, J.

    1958-06-01

    A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

  13. Comparison of Experimental and Calculated Ion Mobilities of Small Molecules in Air.

    PubMed

    Gunzer, Frank

    2016-01-01

    Ion mobility spectrometry is a well-known technique for analyzing gases. Examples are military applications, but also safety related applications, for example, for protection of employees in industries working with hazardous gases. In the last 15 years, this technique has been further developed as a tool for structural analysis, for example, in pharmaceutical applications. In particular, the collision cross section, which is related to the mobility, is of interest here. With help of theoretic principles, it is possible to develop molecular models that can be verified by the comparison of their calculated cross sections with experimental data. In this paper, it is analyzed how well the ion trajectory method is suitable to reproduce the measured ion mobility of small organic molecules such as the water clusters forming the positively charged reactant ions, simple aromatic substances, and n-alkanes. PMID:27298751

  14. Comparison of Experimental and Calculated Ion Mobilities of Small Molecules in Air

    PubMed Central

    2016-01-01

    Ion mobility spectrometry is a well-known technique for analyzing gases. Examples are military applications, but also safety related applications, for example, for protection of employees in industries working with hazardous gases. In the last 15 years, this technique has been further developed as a tool for structural analysis, for example, in pharmaceutical applications. In particular, the collision cross section, which is related to the mobility, is of interest here. With help of theoretic principles, it is possible to develop molecular models that can be verified by the comparison of their calculated cross sections with experimental data. In this paper, it is analyzed how well the ion trajectory method is suitable to reproduce the measured ion mobility of small organic molecules such as the water clusters forming the positively charged reactant ions, simple aromatic substances, and n-alkanes. PMID:27298751

  15. Electric Double-Layer Effects Induce Separation of Aqueous Metal Ions.

    PubMed

    Ji, Qinghua; An, Xiaoqiang; Liu, Huijuan; Guo, Lin; Qu, Jiuhui

    2015-11-24

    Metal ion separation is crucial to environmental decontamination, chromatography, and metal recovery and recycling. Theoretical studies have suggested that the ion distributions in the electric double-layer (EDL) region depend on the nature of the ions and the characteristics of the charged electrode surface. We believe that rational design of the electrode material and device structure will enable EDL-based devices to be utilized in the separation of aqueous metal ions. On the basis of this concept, we fabricate an EDL separation (EDLS) device based on sandwich-structured N-functionalized graphene sheets (CN-GS) for selective separation of aqueous toxic heavy metal ions. We demonstrate that the EDLS enables randomly distributed soluble ions to form a coordination-driven layer and electrostatic-driven layer in the interfacial region of the CN-GS/solution. Through tuning the surface potential of the CN-GS, the effective separation of heavy metal ions (coordination-driven layer) from alkali or alkaline earth metal ions (electrostatic-driven layer) can be achieved. PMID:26481603

  16. Characterization of an Ion Mobility-Multiplexed Collision Induced Dissociation-Tandem Time-of-Flight Mass Spectrometry Approach

    PubMed Central

    Ibrahim, Yehia M.; Prior, David C.; Baker, Erin S.; Smith, Richard D.; Belov, Mikhail E.

    2010-01-01

    The confidence in peptide (and protein) identifications with ion mobility spectrometry time-of-flight mass spectrometry (IMS-TOFMS) is expected to drastically improve with the addition of information from an efficient ion dissociation step prior to MS detection. High throughput IMS-TOFMS analysis imposes a strong need for multiplexed ion dissociation approaches where multiple precursor ions yield complex sets of fragment ions that are often intermingled with each other in both the drift time and m/z domains. We have developed and evaluated an approach for collision-induced dissociation (CID) using IMS-TOFMS instrument. It has been shown that precursor ions activated inside an rf-device with an axial dc-electric field produce abundant fragment ions which are radially confined with the rf-field and collisionally cooled at an elevated pressure, resulting in high CID efficiencies comparable or higher than those measured in triple-quadrupole instruments. We have also developed an algorithm for deconvoluting these complex multiplexed tandem MS spectra by clustering both the precursor and fragment ions into matching drift time profiles and by utilizing the high mass measurement accuracy achievable with TOFMS. In a single IMS separation from direct infusion of tryptic digest of bovine serum albumin (BSA), we have reliably identified 20 unique peptides using a multiplexed CID approach downstream of the IMS separation. Peptides were identified based upon the correlation between the precursor and fragment drift time profiles and by matching the profile representative masses to those of in silico BSA tryptic peptides and their fragments. The false discovery rate (FDR) of peptide identifications from multiplexed MS/MS spectra was less than 1%. PMID:20596241

  17. Analysis of psychoactive cathinones and tryptamines by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry.

    PubMed

    Kanu, A Bakarr; Brandt, Simon D; Williams, Mike D; Zhang, Nancy; Hill, Herbert H

    2013-09-17

    The ability to use positive ion monitoring mode with an atmospheric pressure ion mobility time-of-flight mass spectrometer (APIM(tof)MS) to detect psychoactive cathinones and tryptamines from aqueous phase samples was evaluated. The study used a traditional electrospray ionization (ESI) source for sample introduction and ionization. A total of four cathinones (mephedrone, butylone, 4-Me-PPP, and 4-MEC) and five tryptamines (5-EtO-DPT, 5-EtO-DALT, 5-EtO-MIPT, 5-EtO-ALCHT, and 5-EtO-2MALET) were investigated, and we report on parent ions, collision induced dissociation (CID) fragment ions, reduced mobility (Ko), mass flight times, and detection limits obtained from a single instrument run for the psychoactive substances. Detection limits reported ranged from 3 to 11 μM concentration for the compounds studied. This detection limit range corresponded to 1-5 ng of material needed for improved detection on the instrument. This article demonstrates that it was possible to use a single instrument platform for the separation, detection, and identification of cathinones and tryptamines in less than 1 min. The application holds great promise for detecting and identifying a new class of drugs often referred to as "bath salts" or "legal highs" distributed over the Internet. PMID:23875808

  18. Ion-exchange membranes for bulk separation of acid gases

    SciTech Connect

    Giarratano, P.; Pellegrino, J.J.

    1992-12-01

    The field test has continued with PFSA composite membranes. The substrates have been a microporous polypropylene supplied by 3M Co. The membranes have been imbibed with either aqueous solutions of methyldiethanolamine (MDEA) or n-methylpyrrolidone (NMP). Data from five composite membranes have thusfar been obtained and are presented in the following Figure 6. The composite 1 membrane gave erratic performance before it mechanically failed, but most of the observed separation factors were high enough (>35) to be consistent with the initial results from the gel-NE 111 membrane. The separation factor for the other four composites have been consistently low (between 13 and 3). The main difference is that between composite l and the rest we installed an inertial separator to remove excess moisture from the feed stream. This separator may be too efficient and the membranes may be drying out. Another possibility is that the membranes may just not be made well enough and sufficient uncoated pores may exist to subvert the separation efficiency. We tested a membrane which had been removed from the field test rig in our laboratory permeation equipment. Those results are presented in Figures 7 and 8. Again good agreement between the field test and our lab experiments.

  19. Ion-exchange membranes for bulk separation of acid gases

    SciTech Connect

    Giarratano, P.; Pellegrino, J.J.

    1992-01-01

    The field test has continued with PFSA composite membranes. The substrates have been a microporous polypropylene supplied by 3M Co. The membranes have been imbibed with either aqueous solutions of methyldiethanolamine (MDEA) or n-methylpyrrolidone (NMP). Data from five composite membranes have thusfar been obtained and are presented in the following Figure 6. The composite 1 membrane gave erratic performance before it mechanically failed, but most of the observed separation factors were high enough (>35) to be consistent with the initial results from the gel-NE 111 membrane. The separation factor for the other four composites have been consistently low (between 13 and 3). The main difference is that between composite l and the rest we installed an inertial separator to remove excess moisture from the feed stream. This separator may be too efficient and the membranes may be drying out. Another possibility is that the membranes may just not be made well enough and sufficient uncoated pores may exist to subvert the separation efficiency. We tested a membrane which had been removed from the field test rig in our laboratory permeation equipment. Those results are presented in Figures 7 and 8. Again good agreement between the field test and our lab experiments.

  20. Separate Detection of Sodium and Potassium Ions with Sub-micropipette Probe

    NASA Astrophysics Data System (ADS)

    Takami, Tomohide; Son, Jong Wan; Lee, Joo-Kyung; Park, Bae Ho; Kawai, Tomoji

    2011-08-01

    A novel method of detecting sodium and potassium ions separately with a sub-micropipette probe of approximately 100 nm inner diameter has been demonstrated. A poly(vinyl chloride) film containing crown ether ligands in sub-micropipettes filtered the ions. Sodium ions were trapped with bis(12-crown-4), whereas potassium ions were trapped with bis(benzo-15-crown-5). Alternate and direct bias voltages were applied to the counter electrode in the sub-micropipette so that the local ion concentrations could be observed as current signals after conversion to milivolt output signals with our low-current detection system prepared for this study.

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

    PubMed

    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. PMID:26919030

  2. Modeling of ion transport through a porous separator in vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

    2016-09-01

    In this work, we develop a two-dimensional, transient model to investigate the mechanisms of ion-transport through a porous separator in VRFBs and their effects on battery performance. Commercial-available separators with pore sizes of around 45 nm are particularly investigated and effects of key separator design parameters and operation modes are explored. We reveal that: i) the transport mechanism of vanadium-ion crossover through available separators is predominated by convection; ii) reducing the pore size below 15 nm effectively minimizes the convection-driven vanadium-ion crossover, while further reduction in migration- and diffusion-driven vanadium-ion crossover can be achieved only when the pore size is reduced to the level close to the sizes of vanadium ions; and iii) operation modes that can affect the pressure at the separator/electrode interface, such as the electrolyte flow rate, exert a significant influence on the vanadium-ion crossover rate through the available separators, indicating that it is critically important to equalize the pressure on each half-cell of a power pack in practical applications.

  3. Radio-frequency ion deflector for mass separation

    SciTech Connect

    Schlösser, Magnus Rudnev, Vitaly; Ureña, Ángel González

    2015-10-15

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

  4. Radio-frequency ion deflector for mass separation.

    PubMed

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

    2015-10-01

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

  5. Separation of ammonia from wastewater using clinoptilolite as ion exchanger

    SciTech Connect

    Czaran, E.; Meszaros-Kis, A.; Domokos, E.; Papp, J.

    1988-01-01

    The cation exchange properties of a Hungarian clinoptilolite rock from the Tokaj mountains have been studied. The aim of this work has been to prepare suitable cation containing forms for NH/sub 4//sup +/-removal and regeneration of the NH/sub 4//sup +/-form. The process has been followed from the start with static laboratory experiments through laboratory dynamic measurements up to pilot plant. The static CEC of the clinoptilolite containing rock proved to be 1.2 meq/q. However, under dynamic conditions this value is only 0.2 - 0.3 depending on the circumstances, thus this material is capable of the elimination of 3 - 5 mg NH/sub 3/ per g rock. The exhausted clinoptilolite can be regenerated more efficiently by potassium ions than by the usually applied sodium ions.

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

    PubMed

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

    2014-12-01

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

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

    PubMed Central

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

    2014-01-01

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

  8. Determination of perchlorate in drinking water by ion chromatography using macrocycle-based concentration and separation methods.

    PubMed

    Lamb, John D; Simpson, David; Jensen, Bryce D; Gardner, Joseph S; Peterson, Quinn P

    2006-06-16

    Macrocycle-based ion chromatography provides a convenient, reliable method for the determination of perchlorate ion, which is currently of great interest to the environmental community. This study shows that effective perchlorate determinations can be made using standard conductimetric detection by combining an 18-crown-6-based mobile phase with an underivatized reversed-phase mobile phase ion chromatography (MPIC) column. One unique feature of this method is the flexibility in column capacity that is achieved through simple variations in eluent concentrations of 18-crown-6 and KOH, facilitating the separation of target analyte anions such as perchlorate. Using a standard anion exchange column as concentrator makes possible the determination of perchlorate as low as 0.2 ug/L in low ionic strength matrices. Determination of perchlorate at the sub-ug/L level in pure water and in spiked local city hard water samples with high background ion concentrations can be achieved this way. However, like other IC techniques, this method is challenged to achieve analyses at the ug/L level in the demanding high ionic strength matrix described by the United States Environmental Protection Agency (EPA) (1,000 mg/L chloride, sulfate and carbonate). We approached this challenge by use of the Cryptand C1 concentrator column, provided by Dionex Corporation, to effectively preconcentrate perchlorate while reducing background ion concentrations in the high ionic strength matrix. The retention characteristics of the concentrator column were studied in order to maximize its effectiveness for perchlorate determinations. The method makes possible the determination of perchlorate at the 5 ug/L level in the highest ionic strength matrix described by the EPA. PMID:16516902

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

    PubMed

    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. PMID:22841099

  10. Determination of Benzene, Toluene, and Xylene by means of an ion mobility spectrometer device using photoionization

    NASA Technical Reports Server (NTRS)

    Leonhardt, J. W.; Bensch, H.; Berger, D.; Nolting, M.; Baumbach, J. I.

    1995-01-01

    The continuous monitoring of changes on the quality of ambient air is a field of advantage of ion mobility spectrometry. Benzene, Toluene, and Xylene are substances of special interest because of their toxicity. We present an optimized drift tube for ion mobility spectrometers, which uses photo-ionization tubes to produce the ions to be analyzed. The actual version of this drift tube has a length of 45 mm, an electric field strength established within the drift tube of about 180 V/cm and a shutter-opening-time of 400 mus. With the hydrogen tube used for ionisation a mean flux of 10(exp 12) photons/sq cm s was established for the experiments described. We discuss the results of investigations on Benzene, Toluene, and Xylene in normal used gasoline SUPER. The detection limits obtained with the ion mobility spectrometer developed in co-operation are in the range of 10 ppbv in this case. Normally, charge transfer from Benzene ions to Toluene takes place. Nevertheless the simultaneous determination in mixtures is possible by a data evaluation procedure developed for this case. The interferences found between Xylene and others are rather weak. The ion mobility spectra of different concentrations of gasoline SUPER are attached as an example for the resolution and the detection limit of the instrument developed. Resolution and sensitivity of the system are well demonstrated. A hand-held portable device produced just now is to be tested for special environmental analytical problems in some industrial and scientific laboratories in Germany.

  11. High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

    NASA Astrophysics Data System (ADS)

    Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

    2013-11-01

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4-10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

  12. Calcium Activities During Different Ion Exchange Separation Procedures

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Zhu, H.; Liu, Y.; Liu, F.; Zhang, C.; Sun, W.

    2014-12-01

    Calcium is a major element and participates in many geological processes. Investigations on stable calcium isotopic compositions of natural geological samples provide a great powerful tool to understand all kinds of those geological processes from a view of the field of isotope geochemistry. With the development of modern instruments and chemical separation techniques, calcium isotopic compositions could be determined even more precisely if the column chemistry brings no deviation. Usually, Calcium is separated from matrix elements using cation resin columns and the related chemical separation techniques seem to be robust. However, more detailed work still need to be done on matrix effects and calcium isotopic fractionations on column chemistry or during elution processes. If calcium is run on TIMS instruments, the interference effect could be lower and easier controlled, thus, the requirement to the chemistry is relatively not critic, but calcium fractionation on filaments could be much difficult to monitor. If calcium is run on MC-ICP-MS instruments, the interference effect could be huge and is really difficult to be recognized and subtracted, the requirement to the chemistry is much more critical in order to get a real result of the sample, but the instrument fractionation could be easier to monitor. Here we investigate calcium activities on several kinds of cation resins under different column/acid conditions. We seek to find a good balance between recovery and interference effect on column chemistry and are intend to set up a better chemical separation procedure to satisfy the instrument requirements for calcium. In addition, Calcium isotopic fractionation on column will also be discussed further here based on our previous and ongoing results.

  13. Method for mobilization of hazardous metal ions in soils

    DOEpatents

    Dugan, Patrick R.; Pfister, Robert M.

    1995-01-01

    A microbial process for removing heavy metals such as bismuth, cadmium, lead, thorium, uranium and other transuranics from soils and sediments, utilizing indigenous, or isolates of indigenous, microorganisms and reducing agents, such as cysteine or sodium thioglycollate, or complexing agents such as the amino acid glycine, to effect the mobilization or release of the metals from the soil particles.

  14. Facilitated ion diffusion in multiscale porous particles: application in battery separators.

    PubMed

    Kim, Young Bum; Tran-Phu, Thanh; Kim, Min; Jung, Dae-Woong; Yi, Gi-Ra; Park, Jong Hyeok

    2015-03-01

    Polyethylene (PE) separators have been the most popular option for commercial Li-ion batteries because of their uniform pore size, high tensile strength, low cost, and electrochemical stability. Unfortunately, PE separators generally suffer from significant dimensional changes at high temperatures, which frequently results in serious safety problems. In this regard, the integration of inorganic nanoparticles with PE separators has been considered to be a promising approach. Here, inorganic nanoparticles with a hierarchical pore structure were coated on a conventional polymer separator. The resultant composite separator exhibited superior Li ion transportation compared with separators coated with mesopore-only nanoparticles or conventional nonporous nanoparticles. The mesopores and macropores act synergistically to improve the electrolyte uptake and ionic conductivity of the inorganic nanoparticles, while other positive aspects such as their thermal and mechanical properties are still maintained. PMID:25594365

  15. High Resolution Separations and Improved Ion Production and Transmission in Metabolomics

    SciTech Connect

    Metz, Thomas O.; Page, Jason S.; Baker, Erin Shammel; Tang, Keqi; Ding, Jie; Shen, Yufeng; Smith, Richard D.

    2008-03-31

    The goal of metabolomics experiments is the detection and quantitation of as many sample components as reasonably possible in order to identify “features” that can be used to characterize the samples under study. When utilizing electrospray ionization to produce ions for analysis by mass spectrometry (MS), it is imperative that metabolome sample constituents be efficiently separated prior to ion production, in order to minimize the phenomenon of ionization suppression. Similarly, optimization of the MS inlet can lead to increased measurement sensitivity. This review will focus on the role of high resolution liquid chromatography (LC) separations in conjunction with improved ion production and transmission for LC-MS-based metabolomics.

  16. Wet-laid non-woven fabric for separator of lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Yi, Wang; Huaiyu, Zhan; Jian, Hu; Yun, Liang; Shushu, Zeng

    In this paper, a wet-laid non-woven material consisted of fibrillated fibers is presented, which is potential to be separator for lithium-ion battery. Average pore size of the separators calendered at different line pressures is 0.180 μm and 0.372 μm, respectively. The results show that the pore size of non-woven separator could be controlled efficiently by fibrillated fiber and pressure of calender which could help to reduce the internal short circuit. The permeability and the rate of absorption of non-woven separator are higher than those of the conventional polyolefin separator.

  17. Bacterial cellulose nanofibrous membrane as thermal stable separator for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Jiang, Fengjing; Yin, Lei; Yu, Qingchun; Zhong, Chunyan; Zhang, Junliang

    2015-04-01

    Thermal shrinkage is a severe problem for the conventional polyolefin separators. In this work, we report the excellent performance of bacterial cellulose (BC) nanofibrous membranes as separators for lithium (Li) ion batteries. Properties of BC separator including morphology, ionic conductivity, electrochemical stability, thermal stability, mechanical strength and battery charge-discharge performance are characterized and compared to a commercial separator membrane (Celgard® 2325). Because of the unique fibrous and cross-linked three-dimensional network structure, BC separator shows excellent dimensional stability up to 180 °C, good ionic conductivity and competitive battery performance.

  18. Separation study of cadmium through an emulsion liquid membrane using triisooctylamine as mobile carrier.

    PubMed

    Li, Q M; Liu, Q; Zhang, Q F; Wei, X J; Guo, J Z

    1998-08-01

    A study of the transport of Cd(2+) ions through a triisooctylamine (TIOA)-sorbitan monooleate (Span 80)-dimethylbenzene liquid membrane has been performed with varying concentrations of HCl, KI, TIOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed with 0.025 M HCl, 0.01 M KI, 0.02 M TIOA, 3% (w/v) Span 80 and 0.05 M NaOH. With this system cadmium could be completely separated with Cu(2+), Zn(2+), Fe(2+), Co(2+), Ni(2+), Mn(2+), Cr(3+) and Al(3+). The transport mechanism of this metal ions through the membrane has been discussed. PMID:18967215

  19. Method and system for producing hydrogen using sodium ion separation membranes

    DOEpatents

    Bingham, Dennis N; Klingler, Kerry M; Turner, Terry D; Wilding, Bruce M; Frost, Lyman

    2013-05-21

    A method of producing hydrogen from sodium hydroxide and water is disclosed. The method comprises separating sodium from a first aqueous sodium hydroxide stream in a sodium ion separator, feeding the sodium produced in the sodium ion separator to a sodium reactor, reacting the sodium in the sodium reactor with water, and producing a second aqueous sodium hydroxide stream and hydrogen. The method may also comprise reusing the second aqueous sodium hydroxide stream by combining the second aqueous sodium hydroxide stream with the first aqueous sodium hydroxide stream. A system of producing hydrogen is also disclosed.

  20. Magnetic separation of Dy(III) ions from homogeneous aqueous solutions

    SciTech Connect

    Pulko, B. Yang, X.; Lei, Z.; Odenbach, S.; Eckert, K.

    2014-12-08

    The possibility to enrich paramagnetic dysprosium(III) ions in a magnetic field gradient is proved by means of interferometry, which may open the route for a magnetic separation of rare earth ions from aqueous solutions. The separation dynamics are studied for three different concentrations of DyCl{sub 3} and compared with those found recently in a sulphate solution of the 3d ion Mn(II). In view of the similar-sized hydration spheres for Dy(III) and Mn(II), the slower separation dynamics in DyCl{sub 3} is attributed to both a higher densification coefficient and the strong impact of Brownian motion due to the absence of ion-pair clusters.

  1. High resolution ion mobility measurements of peptides, proteins, and atomic clusters

    NASA Astrophysics Data System (ADS)

    Hudgins, Robert Ransone

    1999-12-01

    A novel high resolution ion mobility apparatus has been constructed and applied to the study of atomic clusters and biological molecules in the gas phase. The resolving power of the high resolution apparatus is over an order of magnitude higher than has been achieved using conventional injected-ion drift tube techniques. A number of advantages of the experimental configuration, in addition to the higher resolution, are described. High resolution ion mobility measurements have been performed on atomic clusters of various composition. Several isomers for carbon cluster anions have been resolved for the first time. By comparison to computationally derived structures, detailed structural information can be extracted from the measurements. For small carbon cluster anions, ``tadpole'' isomers, where a short carbon chain is attached to a carbon ring, have been identified. Mobility measurements for (NaCl)nCl- clusters have revealed multiple isomers with the same fcc packing but different j x k x l dimensions. Metastable (NaCl)nCl- geometries isomerize on the timescale of the mobility measurements (hundreds of milliseconds). Rate constants and activation energies for the isomerization processes are extracted directly from the mobility measurements; the activation energies are found to be remarkably low. Indium and silicon cluster mobilities are found to be sensitive to the degree of electron spillout from the surface of the cluster, as revealed in differences in the anionic and cationic cluster mobilities. Mobility measurements of solvent-free biological molecules reveal important information about their intramolecular forces. Due to the gentle ion sampling in the high resolution ion mobility apparatus electrospray interface, high resolution mobilities of gas-phase proteins are found to be sensitive to the nature of the electrosprayed solution. Although calculations have shown that neutral polyalanine in vacuo is mostly helical, gas- phase polyalanine ions, AnH+, are found

  2. Electrode-supported thin α-alumina separators for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mi, Wanliang; Sharma, Gaurav; Dong, Xueliang; Jin, Yi; Lin, Y. S.

    2016-02-01

    Lithium ion batteries with an inorganic separator offer improved safety and enhanced reliability. The free-standing inorganic separators recently studied for lithium ion batteries are brittle and expensive. To address these issues, this paper reports the synthesis of a new and stable electrode-supported separator using a low-cost ceramic powder. Thin and porous α-Al2O3 separator films of thicknesses down to 40 μm were coated on Li4Ti5O12 (LTO) electrode by blade-coating a slurry of α-Al2O3, water and a small amount of polyvinyl alcohol (PVA). The performance of the LTO/Li cells with coated α-Al2O3 separator improves with decreasing PVA content. Cells with coated α-Al2O3 separator containing 0.4wt% PVA exhibit similar discharge capacity but better rate capability than those with commercial polypropylene (PP) or thick sintered α-Al2O3 separator. The coated α-Al2O3 separator does not react with LTO even after many charge/discharge cycles. Fabrication of the electrode-supported α-Al2O3 separator is scalable and cost-effective, offering high potential for practical application in industrial lithium ion battery manufacturing.

  3. Method and apparatus for compressing ions

    DOEpatents

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

    2015-06-23

    A method and apparatus for compressing ions inside an ion mobility device is disclosed. Ions are introduced into the mobility device. The ions are subjected to a non-constant electric field to form a potential gradient along a portion of the device so that ions with similar mobilities bunch together into sharper peaks while maintaining separation between other ions. The potential gradient progressively increases or decreases along the length of the device.

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

    PubMed

    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. PMID:27278825

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Electrodialysis-ion exchange for the separation of dissolved salts

    SciTech Connect

    Baroch, C.J.; Grant, P.J.

    1995-12-31

    The Department of Energy generates and stores a significant quantity of low level, high level, and mixed wastes. As some of the DOE facilities are decontaminated and decommissioned, additional and possibly different forms of wastes will be generated. A significant portion of these wastes are aqueous streams containing acids, bases, and salts, or are wet solids containing inorganic salts. Some of these wastes are quite dilute solutions, whereas others contain large quantities of nitrates either in the form of dissolved salts or acids. Many of the wastes are also contaminated with heavy metals, radioactive products, or organics. Some of these wastes are in storage because a satisfactory treatment and disposal processes have not been developed. This report describes the process of electrodialysis-ion exchange (EDIX) for treating aqueous wastes streams consisting of nitrates, sodium, organics, heavy metals, and radioactive species.

  8. Electrodialysis-ion exchange for the separation of dissolved salts

    SciTech Connect

    Baroch, C.J.; Grant, P.J.

    1995-10-01

    The Department of Energy generates and stores a significant quantity of low level, high level, and mixed wastes. As some of the DOE facilities are decontaminated and decommissioned, additional and possibly different forms of wastes will be generated. A significant portion of these wastes are aqueous streams containing acids, bases, and salts, or are wet solids containing inorganic salts. Some of these wastes are quite dilute solutions, whereas others contain large quantities of nitrates either in the form of dissolved salts or acids. Many of the wastes are also contaminated with heavy metals, radioactive products, or organics. Some of these wastes are in storage because a satisfactory treatment and disposal processes have not been developed. There is considerable interest in developing processes that remove or destroy the nitrate wastes. Electrodialysis-Ion Exchange (EDIX) is a possible process that should be more cost effective in treating aqueous waste steams. This report describes the EDIX process.

  9. Effect of mobile ions on the electric field needed to orient charged diblock copolymer thin films

    SciTech Connect

    Dehghan, Ashkan; Shi, An-Chang; Schick, M.

    2015-10-07

    We examine the behavior of lamellar phases of charged/neutral diblock copolymer thin films containing mobile ions in the presence of an external electric field. We employ self-consistent field theory and focus on the aligning effect of the electric field on the lamellae. Of particular interest are the effects of the mobile ions on the critical field, the value required to reorient the lamellae from the parallel configuration favored by the surface interaction to the perpendicular orientation favored by the field. We find that the critical field depends strongly on whether the neutral or charged species is favored by the substrates. In the case in which the neutral species is favored, the addition of charges decreases the critical electric field significantly. The effect is greater when the mobile ions are confined to the charged lamellae. In contrast, when the charged species is favored by the substrate, the addition of mobile ions stabilizes the parallel configuration and thus results in an increase in the critical electric field. The presence of ions in the system introduces a new mixed phase in addition to those reported previously.

  10. Method for mobilization of hazardous metal ions in soils

    DOEpatents

    Dugan, P.R.; Pfister, R.M.

    1995-06-27

    A microbial process is revealed for removing heavy metals such as bismuth, cadmium, lead, thorium, uranium and other transuranics from soils and sediments. The method utilizes indigenous, or isolates of indigenous, microorganisms and reducing agents, such as cysteine or sodium thioglycollate, or complexing agents such as the amino acid glycine, to effect the mobilization or release of the metals from the soil particles. 5 figs.

  11. The detection of energetic materials with a laser ionization ion mobility spectrometer

    NASA Astrophysics Data System (ADS)

    Clark, Alistair; Deas, Robert M.; Kosmidis, Constantinos; Ledingham, Kenneth W. D.; Marshall, Archibald; Singhal, Ravi P.

    1995-04-01

    Laser induced multiphoton ionization (MPI) has been used to produce positive and negative ions at atmospheric pressure in an ion mobility spectrometer. This paper deals particularly with the application of this technique to the ultra-trace detection of a number of energetic materials such as RDX and PETN. In conventional ion mobility spectrometry (IMS), a radioactive 63Ni β-foil is used as the ionization source. The laser IMS spectra will be compared with the 63Ni spectra and it will be shown that the analyte ions produced by laser ionization have a wavelength dependent fingerprint which provides an additional degree of selectivity. It is felt that this new approach to IMS will develop considerably the scope and applicability of this powerful technique.

  12. Off-line coupling of multidimensional immunoaffinity chromatography and ion mobility spectrometry: A promising partnership.

    PubMed

    Armenta, Sergio; de la Guardia, Miguel; Abad-Fuentes, Antonio; Abad-Somovilla, Antonio; Esteve-Turrillas, Francesc A

    2015-12-24

    The extreme specificity of immunoaffinity chromatography (IAC) columns coupled to the high sensitivity of ion mobility spectrometry (IMS) measurements makes this combination really useful for rapid, selective, and sensitive determination of a high variety of analytes in different samples. The capabilities of the IAC-IMS coupling have been highlighted under three different scenarios: (i) multiclass residue analysis using a single IAC column, (ii) multiclass residue analysis using stacked IAC columns, and (iii) isomer analysis. In the first case, the determination of three strobilurin fungicides - azoxystrobin, picoxystrobin, and pyraclostrobin - in water and strawberry juice was considered, obtaining limits of quantification (LOQs) from 11 to 63μgL(-1). Recoveries from 96 to 106% for water, and from 67 to 104% for strawberry juice were obtained. In the second case, anilinopyrimidine compounds, including two analytes with similar drift time, were selectively retained in different IAC columns and analyzed after independent elution in commercial wine samples by IMS. LOQ values of 16, 14 and 12μgL(-1) were obtained for pyrimethanil, mepanipyrim, and cyprodinil, respectively. The obtained recoveries for wine samples spiked with 25 and 100μgL(-1) were from 82 to 123%. Additionally, the stacked IAC columns concept was applied to the separation of Z and E isomers of azoxystrobin that were selectively retained in specific IAC columns and quantified by IMS. Recoveries between 91 and 94% were obtained for both isomers in water samples. PMID:26654255

  13. Simultaneous determination of three azo dyes in food product by ion mobility spectrometry.

    PubMed

    Jiao, Jiandong; Wang, Jinfeng; Li, Mingfeng; Li, Junqing; Li, Qihong; Quan, Qinbo; Chen, Jinquan

    2016-07-01

    Color is an important property for food evaluation. Synthetic azo dyes are usually used in food product to obtain better appearance because of their stability and low cost. However, such dyes should be strictly controlled because of their potential threat to human health. A simple, rapid and sensitive method has been developed to determine orange II, allura red, and para red simultaneously by ion mobility spectrometry. The three dyes could be separated at the same time and the migration time of orange II, allura red, and para red are 12.070±0.010, 8.180±0.015, and 11.037±0.016ms, respectively. The effects of different parameters, such as pH, solvent, percentage of water, were investigated to establish the optimal condition. The detection limits were 0.1, 0.05, and 0.2μg/mL for orange II, allura red, and para red, respectively. The recoveries of the three azo dyes from jellies were all higher than 81%. The developed method is fast and accurate for the detection of the three synthetic dyes. PMID:27235999

  14. Lipid Analysis and Lipidomics by Structurally Selective Ion Mobility-Mass Spectrometry

    PubMed Central

    Kliman, Michal; May, Jody C.

    2012-01-01

    Recent advances in mass spectrometry approaches to the analysis of lipids include the ability to incorporate both lipid class identification with lipid structural information for increased characterization capabilities. The detailed examination of lipids and their biosynthetic and biochemical pathways made possible by novel instrumental and bioinformatics approaches is advancing research in fundamental cellular and medical studies. Recently, high-throughput structural analysis has been demonstrated through the use of rapid gas-phase separation on the basis of the ion mobility (IM) analytical technique combined with mass spectrometry (IM-MS). While IM-MS has been extensively utilized in biochemical research for peptide, protein and small molecule analysis, the role of IM-MS in lipid research is still an active area of development. In this review of lipid-based IM-MS research, we begin with an overview of three contemporary IM techniques which show great promise in being applied towards the analysis of lipids. Fundamental concepts regarding the integration of IM-MS are reviewed with emphasis on the applications of IM-MS towards simplifying and enhancing complex biological sample analysis. Finally, several recent IM-MS lipid studies are highlighted and the future prospects of IM-MS for integrated omics studies and enhanced spatial profiling through imaging IM-MS are briefly described. PMID:21708282

  15. METHOD OF SEPARATING RARE EARTHS BY ION EXCHANGE

    DOEpatents

    Spedding, F.H.; Powell, J.E.

    1960-10-18

    A process is given for separating yttrium and rare earth values having atomic numbers of from 57 through 60 and 68 through 71 from an aqueous solution whose pH value can range from 1 to 9. All rare earths and yttrium are first adsorbed on a cation exchange resin, and they are then eluted with a solution of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) in the order of decreasing atomic number, yttrium behaving like element 61; the effluents are collected in fractions. The HEDTA is recovered by elution with ammonia solution and the resin is regenerated with sulfuric acid. Rare earths are precipitated from the various effluents with oxalic acid, and each supernatant is passed over cation exchange resin for adsorption of HEDTA and nonprecipitated rare earths: the oxalic acid is not retained by the resin.

  16. Tannic-Acid-Coated Polypropylene Membrane as a Separator for Lithium-Ion Batteries.

    PubMed

    Pan, Lei; Wang, Haibin; Wu, Chaolumen; Liao, Chenbo; Li, Lei

    2015-07-29

    To solve the wetting capability issue of commercial polypropylene (PP) separators in lithium-ion batteries (LIBs), we developed a simple dipping surface-coating process based on tannic acid (TA), a natural plant polyphenol. Fourier transform infrared and X-ray photoelectron measurements indicate that the TA is coated successfully on the PP separators. Scanning electron microscopy images show that the TA coating does not destroy the microporous structure of the separators. After being coated with TA, the PP separators become more hydrophilic, which not only enhances the liquid electrolyte retention ability but also increases the ionic conductivity. The battery performance, especially for power capability, is improved after being coated with TA. It indicates that this TA-coating method provides a promising process by which to develop an advanced polymer membrane separator for lithium-ion batteries. PMID:26177514

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

    SciTech Connect

    Waltman, Melanie J.

    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.

  18. Combining ion mobility spectrometry, mass spectrometry, and photoelectron spectroscopy in a high-transmission instrument.

    PubMed

    Vonderach, Matthias; Ehrler, Oli T; Weis, Patrick; Kappes, Manfred M

    2011-02-01

    We have developed a novel instrument that combines ion mobility spectrometry, mass spectro-metry, and photoelectron spectroscopy. The instrument couples an electrospray ion source, a high-transmission ion mobility cell based on ion funnels, a quadrupole mass filter, and a time-of-flight (magnetic bottle) photoelectron spectrometer operated with a pulsed detachment laser. We show that the instrument can resolve highly structured anion arrival time distributions and at the same time provide corresponding photoelectron spectra-using the DNA oligonucleotide ion [dC(6) - 5H](5-) as a test case. For this multianion we find at least four different, noninterconverting isomers (conformers) simultaneously present in the gas phase at room temperature. For each of these we record well-resolved and remarkably different photoelectron spectra at each of three different detachment laser wavelengths. Two-dimensional ion mobility/electron binding energy plots can be acquired with an automated data collection procedure. We expect that this kind of instrument will significantly improve the capabilities for structure determination of (bio)molecular anions in the gas phase. PMID:21214198

  19. Digitally-multiplexed nanoelectrospray ionization atmospheric pressure drift tube ion mobility spectrometry.

    PubMed

    Kwasnik, Mark; Caramore, Joe; Fernández, Facundo M

    2009-02-15

    One of the shortcomings of atmospheric pressure drift tube ion mobility spectrometry (DTIMS) is its intrinsically low duty cycle (approximately 0.04-1%) caused by the rapid pulsing of the ion gate (25-400 micros) followed by a comparatively long drift time (25-100 ms), which translates into a loss of sensitivity. Multiplexing approaches via Hadamard and Fourier-type gating techniques have been reported for increasing the sensitivity of DTIMS. Here, we report an extended multiplexing approach which encompasses arbitrary binary ion injection waveforms with variable duty cycles ranging from 0.5 to 50%. In this approach, ion mobility spectra can be collected using conventional signal averaging, arbitrary, standard Hadamard and/or "extended" Hadamard operation modes. Initial results indicate signal-to-noise gains ranging from 2-7-fold for both arbitrary and "extended" Hadamard sequences. Standard Hadamard transform IMS provided increased sensitivity, with gains ranging from 9-12-fold, however, mobility spectra suffered from defects that appeared as false peaks, which were reduced or eliminated when using arbitrary or "extended" Hadamard waveforms for multiplexing. Digital multiplexing enables variation of the duty cycle in a continuous manner, minimizing the contribution of imperfect modulation on spectral defects without the need for complex spectral correction methods. By reducing the frequency of gating events employed in the variable duty cycle sequences, the contributions of factors such as ion depletion prior to gating, interaction of successively injected ion packets, and the cumulative effect of imperfect gating events were mitigated. PMID:19133785

  20. Formation of Iron Complexes from Trifluoroacetic Acid Based Liquid Chromatography Mobile Phases as Interference Ions in LC-ESI-MS Analysis

    PubMed Central

    Shukla, Anil; Zhang, Rui; Orton, Daniel; Zhao, Rui; Clauss, Therese; Moore, Ronald; Smith, Richard

    2011-01-01

    Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid that severely interfered with sample analysis. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are composed of three components; clusters of trifluoroacetic acid, clusters of mass 159 and iron. Formation of these ions is inhibited by removing trifluoroacetic acid from the mobile phases and using formic acid in its place, replacing the stainless steel union with a titanium union or by adding a small blank fused silica capillary column between the chromatography column and the electrospray tip via a stainless steel union without any adverse effects to chromatographic separation, peak broadening or peptide identifications. PMID:21504012

  1. Deformation and failure characteristics of four types of lithium-ion battery separators

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaowei; Sahraei, Elham; Wang, Kai

    2016-09-01

    Mechanical properties and failure mechanisms of battery separators play a crucial role in integrity of Lithium-ion batteries during an electric vehicle crash event. In this study, four types of commonly used battery separators are characterized and their mechanical performance, strength, and failure are compared. This includes two dry-processed polyethylene (PE) and trilayer separators, a wet-processed ceramic-coated separator, and a nonwoven separator. In detail, uniaxial tensile tests were performed along machine direction (MD), transverse direction (TD) and diagonal direction (DD). Also, through-thickness compression tests and biaxial punch tests were conducted. Comprehensive mechanical tests revealed interesting deformation and failure patterns under extreme mechanical loads. Last, a finite element model of PE separator was developed in LSDYNA based on the uniaxial tensile and through-thickness compression test data. The model succeeded in predicting the response of PE separator under punch tests with different sizes of punch head.

  2. Shutdown-functionalized nonwoven separator with improved thermal and electrochemical properties for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Youngkwon; Lee, Won-Yeol; Kim, Ki Jae; Yu, Ji-Sang; Kim, Young-Jun

    2016-02-01

    A shutdown-functionalized nonwoven separator (SFNS) with improved thermal and electrochemical stabilities is prepared by a simple dip coating method for use in lithium-ion battery (LiB) applications. The SFNS shows thermal stability at 200 °C, while providing shutdown functionality at approximately 140 °C, similar to commercial porous polyethylene separators. The surface-coated polymer prevents leakage current problems and in addition, shows air permeability values similar to that of bare nonwoven separators, while maintaining a thickness of about 20 μm, which is a desired attribute of effective separators for LiBs. The SFNS also shows increased electrolyte uptake and higher conductivity, compared to a bare polyethylene separator. Therefore, a cell with the SFNS exhibits higher discharge capacity and better cycle property than that with a porous polyethylene separator. These results suggest that SFNS is an effective separator for high-performance LiBs.

  3. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  4. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  5. Enhanced capacity and stability for the separation of cesium in electrically switched ion exchange

    SciTech Connect

    Tawfic, A.F.; Dickson, S.E.; Kim, Y.; Mekky, W.

    2015-03-15

    Electrically switched ion exchange (ESIX) can be used to separate ionic contaminants from industrial wastewater, including that generated by the nuclear industry. The ESIX method involves sequential application of reduction and oxidation potentials to an ion exchange film to induce the respective loading and unloading of cesium. This technology is superior to conventional methods (e.g electrodialysis reversal or reverse osmosis) as it requires very little energy for ionic separation. In previous studies, ESIX films have demonstrated relatively low ion exchange capacities and limited film stabilities over repeated potential applications. In this study, the methodology for the deposition of electro-active films (nickel hexacyanoferrate) on nickel electrodes was modified to improve the ion exchange capacity for cesium removal using ESIX. Cyclic voltammetry was used to investigate the ion exchange capacity and stability. Scanning electron microscopy (SEM) was used to characterize the modified film surfaces. Additionally, the films were examined for the separation of cesium ions. This modified film preparation technique enhanced the ion exchange capacity and improves the film stability compared to previous methods for the deposition of ESIX films. (authors)

  6. Separation of Metal Ions from Liquid Waste Streams

    SciTech Connect

    Glasgow, D. G.; Kennel, E. B.

    2004-12-01

    A unique mechanism was verified for removing uranium from continuously flowing aqueous solutions on a carbon nanofiber electrode with a bias voltage of -0.9 volts (dc versus Ag/AgC1). Uranium concentration was reduced from 100 ppm in the inlet feed to below 1 ppm in a single pass. Cell sizes of 1 cm, 2 inch and 4 inch evaluated during this program were all found to electrosorb uranium from an aqueous stream. The 4 inch cell performed well at uranium concentrations of 1000 ppm. Normally, ordinary electrolysis is not an option for removing uranyl ions because the electrodeposition potential is higher than the dissociation voltage of water. Thus, the ability to electrosorb uranium with greater than 99% effectiveness is a surprising result. In addition, the process was found to be reversible, so that the uranium can be released in a highly concentrated form. In addition to verifying the effectiveness of the system on bench top scale, a regeneration protocol was developed, consisting of passing a 0.1 M KNO{sub3}, solution at a pH of 2.0 and an applied potential of +1.0 V (dc versus Ag/AgC1) which resulted in a measured regeneration of 70% of the electrosorbed uranium. Other experiments studied the effect of pH on electrosorption and desorption, establishing a range of pH for both processes. Finally, it was found that, for an inlet solution of 100 ppm, the carbon nanofiber electrodes were able to electrosorb an amount of uranium in excess of 60% of the electrode mass.

  7. High-Resolution Differential Ion Mobility Spectrometry of a Protein

    PubMed Central

    Shvartsburg, Alexandre A.; Smith, Richard D.

    2013-01-01

    Use of elevated electric fields and helium-rich gases has recently enabled differential IMS with resolving power up to R ~ 300. Here we applied that technique to a protein (namely, ubiquitin), achieving R up to ~80 and separating many previously unresolved conformers. While still limited by conformational multiplicity, this resolution is some four times greater than that previously reported using either conventional (drift-tube or traveling-wave) or differential IMS. The capability for fine resolution of protein conformers may open new avenues for proteoform separations in top-down and intact-protein proteomics. PMID:23244633

  8. Effects of separator breakdown on abuse response of 18650 Li-ion cells

    NASA Astrophysics Data System (ADS)

    Roth, E. P.; Doughty, D. H.; Pile, D. L.

    The thermal abuse tolerance of Li-ion cells depends not only on the stability of the active materials in the anode and cathode but also on the stability of the separator which prevents direct interaction between these electrodes. Separator response has been measured as a function of temperature and high voltage both for isolated materials and in full 18650 cells. Separators with different compositions and properties were measured to determine the effect of separator melt integrity on cell response under abusive conditions. These studies were performed as part of the U.S. Department of Energy (DOE) Advanced Technology Development (ATD) Program.

  9. In-depth correlation of separator pore structure and electrochemical performance in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Yunju; Park, Joonam; Jeon, Hyunkyu; Yeon, Daeyong; Kim, Byung-Hyun; Cho, Kuk Young; Ryou, Myung-Hyun; Lee, Yong Min

    2016-09-01

    To establish an accurate correlation between a separator's pore structure and the electrochemical performance of a lithium-ion battery (LIB), we fabricate well defined polyethylene (PE) separators on the same production line while maintaining most processing variables, except for composition. Four PE separators having different thicknesses and porosities (16 μm/37%, 16 μm/40%, 16 μm/47%, 22 μm/47%, respectively) are physically and electrochemically evaluated in detail. Although thickness and porosity remain good parameters by which to represent the separators' characteristics, both the normalized Gurley number and ionic conductance are found to have much stronger relationships with the rate capability.

  10. Preparation and characterization of a Lithium-ion battery separator from cellulose nanofibers.

    PubMed

    Zhang, Hongfeng; Wang, Xiwen; Liang, Yun

    2015-10-01

    Optimizing the desired properties for stretch monolayer separators used in Lithium-ion batteries has been a challenge. In the present study a cellulose nanofiber/PET nonwoven composite separator is successfully fabricated, using a wet-laid nonwoven (papermaking) process, which can attain optimal properties in wettability, mechanical strength, thermal resistance, and electrochemical performance simultaneously. The PET nonwoven material, which is fabricated from ultrafine PET fibers by a wet-laid process, is a mechanical support layer. The porous structure of the composite separator was created by cellulose nanofibers coating the PET in a papermaking process. Cellulose nanofibers (CNFs), which are an eco-friendly sustainable resource, have been drawing considerable attention due to their astounding properties, such as: incredible specific surface area, thermal and chemical stability, high mechanical strength and hydrophilicity. The results show that the CNF separator exhibits higher porosity (70%) than a PP (polypropylene) separator (40%). The CNF separator can also be wetted by electrolyte in a few seconds while a PP separator cannot be entirely wetted after 1 min. The CNF separator has an electrolyte uptake of 250%, while a PP separator has only 65%. Another notable finding is that the CNF separator has almost no shrinkage when exposed to 180 °C for 1 h, whereas a PP separator shrinks by more than 50%. Differential Scanning Calorimetry (DSC) shows that the CNF separator has a higher melting point than a PP separator. These findings all indicate that the CNF 29 separator will be more favorable than stretch film for use in Lithium-ion batteries. PMID:27441220

  11. Analysis of Supramolecular Complexes of 3-Methylxanthine with Field Asymmetric Waveform Ion Mobility Spectrometry Combined with Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Arthur, Kayleigh L.; Eiceman, Gary A.; Reynolds, James C.; Creaser, Colin S.

    2016-05-01

    Miniaturised field asymmetric waveform ion mobility spectrometry (FAIMS), combined with mass spectrometry (MS), has been applied to the study of self-assembling, noncovalent supramolecular complexes of 3-methylxanthine (3-MX) in the gas phase. 3-MX forms stable tetrameric complexes around an alkali metal (Na+, K+) or ammonium cation, to generate a diverse array of complexes with single and multiple charge states. Complexes of (3-MX)n observed include: singly charged complexes where n = 1-8 and 12 and doubly charged complexes where n = 12-24. The most intense ions are those associated with multiples of tetrameric units, where n = 4, 8, 12, 16, 20, 24. The effect of dispersion field on the ion intensities of the self-assembled complexes indicates some fragmentation of higher order complexes within the FAIMS electrodes (in-FAIMS dissociation), as well as in-source collision induced dissociation within the mass spectrometer. FAIMS-MS enables charge state separation of supramolecular complexes of 3-MX and is shown to be capable of separating species with overlapping mass-to-charge ratios. FAIMS selected transmission also results in an improvement in signal-to-noise ratio for low intensity complexes and enables the visualization of species undetectable without FAIMS.

  12. Analyzing slowly exchanging protein conformations by ion mobility mass spectrometry: study of the dynamic equilibrium of prolyl oligopeptidase.

    PubMed

    López, Abraham; Vilaseca, Marta; Madurga, Sergio; Varese, Monica; Tarragó, Teresa; Giralt, Ernest

    2016-07-01

    Ion mobility mass spectrometry (IMMS) is a biophysical technique that allows the separation of isobaric species on the basis of their size and shape. The high separation capacity, sensitivity and relatively fast time scale measurements confer IMMS great potential for the study of proteins in slow (µs-ms) conformational equilibrium in solution. However, the use of this technique for examining dynamic proteins is still not generalized. One of the major limitations is the instability of protein ions in the gas phase, which raises the question as to what extent the structures detected reflect those in solution. Here, we addressed this issue by analyzing the conformational landscape of prolyl oligopeptidase (POP) - a model of a large dynamic enzyme in the µs-ms range - by native IMMS and compared the results obtained in the gas phase with those obtained in solution. In order to interpret the experimental results, we used theoretical simulations. In addition, the stability of POP gaseous ions was explored by charge reduction and collision-induced unfolding experiments. Our experiments disclosed two species of POP in the gas phase, which correlated well with the open and closed conformations in equilibrium in solution; moreover, a gas-phase collapsed form of POP was also detected. Therefore, our findings not only support the potential of IMMS for the study of multiple co-existing conformations of large proteins in slow dynamic equilibrium in solution but also stress the need for careful data analysis to avoid artifacts. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27434808

  13. Analysis of Supramolecular Complexes of 3-Methylxanthine with Field Asymmetric Waveform Ion Mobility Spectrometry Combined with Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Arthur, Kayleigh L.; Eiceman, Gary A.; Reynolds, James C.; Creaser, Colin S.

    2016-02-01

    Miniaturised field asymmetric waveform ion mobility spectrometry (FAIMS), combined with mass spectrometry (MS), has been applied to the study of self-assembling, noncovalent supramolecular complexes of 3-methylxanthine (3-MX) in the gas phase. 3-MX forms stable tetrameric complexes around an alkali metal (Na+, K+) or ammonium cation, to generate a diverse array of complexes with single and multiple charge states. Complexes of (3-MX)n observed include: singly charged complexes where n = 1-8 and 12 and doubly charged complexes where n = 12-24. The most intense ions are those associated with multiples of tetrameric units, where n = 4, 8, 12, 16, 20, 24. The effect of dispersion field on the ion intensities of the self-assembled complexes indicates some fragmentation of higher order complexes within the FAIMS electrodes (in-FAIMS dissociation), as well as in-source collision induced dissociation within the mass spectrometer. FAIMS-MS enables charge state separation of supramolecular complexes of 3-MX and is shown to be capable of separating species with overlapping mass-to-charge ratios. FAIMS selected transmission also results in an improvement in signal-to-noise ratio for low intensity complexes and enables the visualization of species undetectable without FAIMS.

  14. Analysis of Supramolecular Complexes of 3-Methylxanthine with Field Asymmetric Waveform Ion Mobility Spectrometry Combined with Mass Spectrometry.

    PubMed

    Arthur, Kayleigh L; Eiceman, Gary A; Reynolds, James C; Creaser, Colin S

    2016-05-01

    Miniaturised field asymmetric waveform ion mobility spectrometry (FAIMS), combined with mass spectrometry (MS), has been applied to the study of self-assembling, noncovalent supramolecular complexes of 3-methylxanthine (3-MX) in the gas phase. 3-MX forms stable tetrameric complexes around an alkali metal (Na(+), K(+)) or ammonium cation, to generate a diverse array of complexes with single and multiple charge states. Complexes of (3-MX)n observed include: singly charged complexes where n = 1-8 and 12 and doubly charged complexes where n = 12-24. The most intense ions are those associated with multiples of tetrameric units, where n = 4, 8, 12, 16, 20, 24. The effect of dispersion field on the ion intensities of the self-assembled complexes indicates some fragmentation of higher order complexes within the FAIMS electrodes (in-FAIMS dissociation), as well as in-source collision induced dissociation within the mass spectrometer. FAIMS-MS enables charge state separation of supramolecular complexes of 3-MX and is shown to be capable of separating species with overlapping mass-to-charge ratios. FAIMS selected transmission also results in an improvement in signal-to-noise ratio for low intensity complexes and enables the visualization of species undetectable without FAIMS. Graphical Abstract ᅟ. PMID:26914231

  15. Estimating collision cross sections of negatively charged N-glycans using traveling wave ion mobility-mass spectrometry.

    PubMed

    Hofmann, Johanna; Struwe, Weston B; Scarff, Charlotte A; Scrivens, James H; Harvey, David J; Pagel, Kevin

    2014-11-01

    Glycosylation is one of the most common post-translational modifications occurring in proteins. A detailed structural characterization of the involved carbohydrates, however, is still one of the greatest challenges in modern glycoproteomics, since multiple regio- and stereoisomers with an identical monosaccharide composition may exist. Recently, ion mobility-mass spectrometry (IM-MS), a technique in which ions are separated according to their mass, charge, and shape, has evolved as a promising technique for the separation and structural analysis of complex carbohydrates. This growing interest is based on the fact that the measured drift times can be converted into collision cross sections (CCSs), which can be compared, implemented into databases, and used as additional search criteria for structural identification. However, most of the currently used commercial IM-MS instruments utilize a nonuniform traveling wave field to propel the ions through the IM cell. As a result, CCS measurements cannot be performed directly and require calibration. Here, we present a calibration data set consisting of over 500 reference CCSs for negatively charged N-glycans and their fragments. Moreover, we show that dextran, already widely used as a calibrant in high performance liquid chromatography, is also a suitable calibrant for CCS estimations. Our data also indicate that a considerably increased error has to be taken into account when reference CCSs acquired in a different drift gas are used for calibration. PMID:25268221

  16. Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

    PubMed Central

    Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

    2009-01-01

    A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

  17. Silver-Ion Solid Phase Extraction Separation of Classical, Aromatic, Oxidized, and Heteroatomic Naphthenic Acids from Oil Sands Process-Affected Water.

    PubMed

    Huang, Rongfu; Chen, Yuan; Gamal El-Din, Mohamed

    2016-06-21

    The separation of classical, aromatic, oxidized, and heteroatomic (sulfur-containing) naphthenic acid (NA) species from unprocessed and ozone-treated oil sands process-affected water (OSPW) was performed using silver-ion (Ag-ion) solid phase extraction (SPE) without the requirement of pre-methylation for NAs. OSPW samples before SPE and SPE fractions were characterized using ultra performance liquid chromatography ion mobility time-of-flight mass spectrometry (UPLC-IM-TOFMS) to corroborate the separation of distinct NA species. The mass spectrum identification applied a mass tolerance of ±1.5 mDa due to the mass errors of NAs were measured within this range, allowing the identification of O2S-NAs from O2-NAs. Moreover, separated NA species facilitated the tandem mass spectrometry (MS/MS) characterization of NA compounds due to the removal of matrix and a simplified composition. MS/MS results showed that classical, aromatic, oxidized, and sulfur-containing NA compounds were eluted into individual SPE fractions. Overall results indicated that the separation of NA species using Ag-ion SPE is a valuable method for extracting individual NA species that are of great interest for environmental toxicology and wastewater treatment research, to conduct species-specific studies. Furthermore, the separated NA species on the milligram level could be widely used as the standard materials for environmental monitoring of NAs from various contamination sites. PMID:27183033

  18. High Mobility SiGe/Si Transistor Structures on Sapphire Substrates Using Ion Implantation

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Mueller, C. H.; Croke, E. T.

    2003-01-01

    High mobility n-type SiGe/Si transistor structures have been fabricated on sapphire substrates by ion implanting phosphorus ions into strained 100 Angstrom thick silicon channels for the first time. The strained Si channels were sandwiched between Si(sub 0.7)Ge(sub 0.3) layers, which, in turn, were deposited on Si(sub 0.7)Ge(sub 0.3) virtual substrates and graded SiGe buffer layers. After the molecular beam epitaxy (MBE) film growth process was completed, ion thick silicon channels implantation and post-annealing were used to introduce donors. The phosphorous ions were preferentially located in the Si channel at a peak concentration of approximately 1x10(exp 18)/cu cm. Room temperature electron mobilities exceeding 750 sq cm/V-sec at carrier densities of 1x10(exp 12)/sq cm were measured. Electron concentration appears to be the key factor that determines mobility, with the highest mobility observed for electron densities in the 1 - 2x10(exp 12)/sq cm range.

  19. Structure of aldehyde cluster ions in the gas phase, according to data from ion mobility spectrometry and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Lantsuzskaya (Krisilova), E. V.; Krisilov, A. V.; Levina, A. M.

    2015-09-01

    Ion-mobility spectra of a set of aliphatic linear aldehydes with the number of carbon atoms from 3 to 7 are obtained. Values of the mobility corresponding to two most intense peaks, considered to be those of a monomer and dimer, are determined according the spectra. Based on mobility, collision cross sections are calculated using the Mason-Schamp equation. The linear increase in the collision cross sections upon an increase in molecular weight is determined. According to the experimental results, the contribution to the cross section that has no dependence on molecular weight diminishes with the formation of dimers. It is established using quantum chemical calculations that this is associated with a reduction in the dipole moment upon the formation of dimers.

  20. Identification of novel isomeric pectic oligosaccharides using hydrophilic interaction chromatography coupled to traveling-wave ion mobility mass spectrometry.

    PubMed

    Leijdekkers, Antonius G M; Huang, Jie-Hong; Bakx, Edwin J; Gruppen, Harry; Schols, Henk A

    2015-03-01

    Separation and characterization of complex mixtures of pectic oligosaccharides still remains challenging and often requires the use of multiple analytical techniques, especially when isomeric structures are present. In this work, it is demonstrated that the coupling of hydrophilic interaction chromatography (HILIC) to traveling-wave ion mobility mass spectrometry (TWIMMS) enabled the simultaneous separation and characterization of complex mixtures of various isomeric pectic oligosaccharides. Labeling of oligosaccharides with 3-aminoquinoline (3-AQ) improved MS-ionization efficiency of the oligosaccharides and reduced the complexity of the product ion mass spectra, without losing resolution of the HILIC separation. In addition, labeling enabled quantification of oligosaccharides on molar basis using in-line fluorescence detection. Isomeric structures were distinguished using TWIMMS. The 3-AQ-HILIC-TWIMMS method was used to characterize a series of isomeric sugar beet rhamnogalacturonan I derived oligosaccharides carrying a glucuronic acid substituent. Thereby, some novel structural features were identified for the first time: glucuronic acid was attached to O-3 or to O-2 of galacturonic acid residues and a single galacturonic acid residue within an oligomer could contain both an acetyl group and a glucuronic acid substituent. PMID:25647688

  1. Drift tube measurements of mobilities and longitudinal diffusion coefficients of ions in gases

    SciTech Connect

    Chelf, R.D.

    1982-01-01

    The zero-field mobilities of Br/sup -/ and NH/sub 4//sup +/ in O/sub 2/ were determined as a function of gas temperature in a high pressure drift tube mass spectrometer. The mobilities and longitudinal diffusion coefficients of the ion-gas combinations Br/sup -/ in Ne and Kr, Li/sup +/ in Xe, and Tl//sup +/ in Kr and Xe were determined as a function of E/N, where E is the electric field strength and N is the gas number density in a low pressure drift tube mass spectrometer. The measured longitudinal diffusion coefficients were used for a test and comparison of the generalized Einstein relations of Viehland-Mason and Waldman-Mason theories. The measured mobilities of Br/sup -/ in Kr and Tl//sup +/ in Kr were used in an iterative-inversion scheme from which the ion-neutral interaction potentials were determined.

  2. Cryogenic molecular separation system for radioactive {sup 11}C ion acceleration

    SciTech Connect

    Katagiri, K.; Noda, A.; Suzuki, K.; Nagatsu, K.; Nakao, M.; Hojo, S.; Wakui, T.; Noda, K.; Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.; Donets, E. E.; Ramzdorf, A. Yu.

    2015-12-15

    A {sup 11}C molecular production/separation system (CMPS) has been developed as part of an isotope separation on line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive {sup 11}C ion beams. In the ISOL system, {sup 11}CH{sub 4} molecules will be produced by proton irradiation and separated from residual air impurities and impurities produced during the irradiation. The CMPS includes two cryogenic traps to separate specific molecules selectively from impurities by using vapor pressure differences among the molecular species. To investigate the fundamental performance of the CMPS, we performed separation experiments with non-radioactive {sup 12}CH{sub 4} gases, which can simulate the chemical characteristics of {sup 11}CH{sub 4} gases. We investigated the separation of CH{sub 4} molecules from impurities, which will be present as residual gases and are expected to be difficult to separate because the vapor pressure of air molecules is close to that of CH{sub 4}. We determined the collection/separation efficiencies of the CMPS for various amounts of air impurities and found desirable operating conditions for the CMPS to be used as a molecular separation device in our ISOL system.

  3. Collision-Induced Dissociation Ion Mobility Mass Spectrometry for the Elucidation of Unknown Structures in Strained Polycyclic Aromatic Hydrocarbon Macrocycles.

    PubMed

    Zhang, Wen; Quernheim, Martin; Räder, Hans Joachim; Müllen, Klaus

    2016-01-01

    Structure determination of unexpected products obtained during synthesis of large carbon nanotube sidewall segments with more than 200 carbon atoms represents a challenging task for traditional analytical methods. Herein, we investigate a homologous series of four products having the same number of carbon atoms but slightly different hydrogen numbers ranging from 168 to 162. We demonstrate that the combination of mass spectrometry, ion mobility separation, and collision-induced dissociation (CID) can be used to finally elucidate the complete structures with high certainty. The postulated 1,2-phenyl shift as origin for the side reaction could be proven by changes in the minimum fragment sizes. A combination of CID and ion mobility spectrometry was applied for the first time to prove the cyclic nature of all molecules by the significant size increase upon ring opening. Thereby, also, more compact molecules were discovered in the gas phase with thus far unknown structures. Finally, the potential presence of numerous isomers could be ruled out by drift time measurements and molecular modeling together with theoretical collision cross-section (CCS) calculations. Surprisingly, only one defined structure could be assigned to each macrocycle in the homologous series, most likely as a result of natural selection rules driven by ring strain and steric hindrance. With a decreasing hydrogen content, the macrocycles undergo a stepwise transition from a cylindrical to conical shape. Overall, ion mobility mass spectrometry together with molecular modeling shows great potential to analyze unknown structures, especially in cases where structure determination by X-ray single-crystal analysis is not applicable. PMID:26613508

  4. Ion-exchange chromatography separation applied to mineral recycle in closed systems

    NASA Technical Reports Server (NTRS)

    Ballou, E.; Spitze, L. A.; Wong, F. W.; Wydeven, T.; Johnson, C. C.

    1981-01-01

    As part of the controlled ecological life support system (CELSS) program, a study is being made of mineral separation on ion-exchange columns. The purpose of the mineral separation step is to allow minerals to be recycled from the oxidized waste products of plants, man, and animals for hydroponic food production. In the CELSS application, relatively large quantities of minerals in a broad concentration range must be recovered by the desired system, rather than the trace quantities and very low concentrations treated in analytical applications of ion-exchange chromatography. Experiments have been carried out to assess the parameters pertinent to the scale-up of ion-exchange chromatography and to determine feasibility. Preliminary conclusions are that the column scale-up is in a reasonable size range for the CELSS application. The recycling of a suitable eluent, however, remains a major challenge to the suitability of using ion exchange chromatography in closed systems.

  5. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    NASA Astrophysics Data System (ADS)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A.; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV-VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag+) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg- 1 detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  6. Method and apparatus for ion mobility spectrometry with alignment of dipole direction (IMS-ADD)

    DOEpatents

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

    2007-01-30

    Techniques and instrumentation are described for analyses of substances, including complex samples/mixtures that require separation prior to characterization of individual components. A method is disclosed for separation of ion mixtures and identification of ions, including protein and other macromolecular ions and their different structural isomers. Analyte ions are not free to rotate during the separation, but are substantially oriented with respect to the drift direction. Alignment is achieved by applying, at a particular angle to the drift field, a much stronger alternating electric field that "locks" the ion dipoles with moments exceeding a certain value. That value depends on the buffer gas composition, pressure, and temperature, but may be as low as .about.3 Debye under certain conditions. The presently disclosed method measures the direction-specific cross-sections that provide the structural information complementing that obtained from known methods, and, when coupled to those methods, increases the total peak capacity and specificity of gas-phase separations. Simultaneous 2-D separations by direction-specific cross sections along and orthogonally to the ion dipole direction are also possible.

  7. Specific O₂⁻ generation in corona discharge for ion mobility spectrometry.

    PubMed

    Sabo, Martin; Matúška, Ján; Matejčík, Stefan

    2011-07-15

    This study deals with O(2)(-) generation in corona discharge (CD) in point to plane geometry for single flow ion mobility spectrometry (IMS) with gas outlet located behind the ionization source. We have designed CD of special geometry in order to achieve the high O(2)(-) yield. Using this ion source we have achieved in zero air conditions that up to 74% all negative ions were O(2)(-) or O(2)(-)(H(2)O). It has been demonstrated that the non-electronegative nitrogen positively influences the efficiency of O(2)(-) generation in O(2)/N(2) mixtures. The reduced ion mobility of 2.27 cm(2)V(-1)s(-1) has been measured for O(2)(-)/O(2)(-)(H(2)O) ions in zero air. Additional ions detected in zero air (less than 200 ppb CO(2)) using the mass spectrometric and IMS technique were, NO(2)(-), N(2)O(2)(-) (2.37 cm(2)V(-1)s(-1)), NO(3)(-), N(2)O(3)(-) and N(2)O(3)(-)(H(2)O). The CO(3)(-) and CO(4)(-) ions have been detected after the introduction of 5 ppm CO(2) into zero air. PMID:21645716

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

    NASA Astrophysics Data System (ADS)

    Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

    2015-04-01

    Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

  9. Non-monotonic mobility vs. length dependence observed in electrophoretic separation of 25 bp DNA ladder in Pluronic gels.

    NASA Astrophysics Data System (ADS)

    You, Seungyong; van Winkle, David

    2009-03-01

    We electrophoresed a double-stranded DNA ladder first in an agarose gel, then in gels of Pluronic F-127 at room temperature. The DNA ladder consisted of 19 discrete fragments ranging in length from 25 to 450 bp at 25 bp increments plus 500 bp. The DNA fragments were first separated in agarose gel and stacked normally with 25 bp having the highest mobility. A single lane of the separated DNA ladder in the agarose gel was inserted at the edge of a Pluronic gel slab. The DNA was electrophoresed from the agarose into the Pluronic gels perpendicular to the original separation axis. Mobilities of DNA fragments increased from 25 bp to 175 bp and then decreased from 175 bp to 500 bp. The 25 bp and 500 bp bands of the ladder had approximately the same mobility in several different Pluronic gel concentrations. Both were slower than most bands in between. The highest mobility fragments with length of 175 bp have 59.5 nm contour length which is about 3.5 times the diameter of a micelle (17 nm). This result suggests a crossover from chromatographic separation to electrophoretic separation for these short DNAs. This research is supported by the state of Florida (Martech) and Research Corporation.

  10. Effective Ion Mobility Calculations for Macromolecules by Scattering off Electron Clouds

    SciTech Connect

    Alexeev, Yuri; Fedorov, Dmitri; Shvartsburg, Alexandre A.

    2014-08-19

    Broad commercialization and increasing resolving power of ion mobility spectrometry/mass spectrometry (IMS/MS) platforms has engendered an explosion of IMS applications to structural characterization of gas-phase biomolecules. That has renewed interest in more accurate and rapid ion mobility calculations needed to elicit ion geometries from the measurements. An approach based on scattering off electron density isosurfaces (SEDI) that mirrors the physics of molecular collisions was proven superior to the common methods involving atomic coordinates a decade ago, but has remained impractical for large ions because of extreme computational demands. Here, we accelerate SEDI by up to ~500 times using the fragment molecular orbital (FMO) approach for surface generation and the multiplexed scattering algorithm in conjunction with the new grid extrapolation procedure for cross section evaluations. Parallelization of the code on a supercomputer has produced major further speed gains, allowing SEDI calculations for proteins (defined by over a million surface points) with the precision of <0.1% in one minute. Initial tests reveal the anticipated dependences of mobility on the ion charge state and lower cross sections in view of reduced surface roughness. Present developments are expected to lead to broad application of SEDI in IMS studies of macromolecules, enabling more accurate and reliable structural assignments.

  11. Direct analysis in real time coupled to multiplexed drift tube ion mobility spectrometry for detecting toxic chemicals.

    PubMed

    Harris, Glenn A; Kwasnik, Mark; Fernández, Facundo M

    2011-03-15

    Current and future chemical threats to homeland security motivate the need for new chemical detection systems to provide border, transportation, and workplace security. We present the first successful coupling of a commercial direct analysis in real time (DART) ion source to a resistive glass monolithic drift tube ion mobility spectrometer (DTIMS) as the basis for a low maintenance, versatile, and robust chemical monitoring system. in situ ionization within the electric field gradient of the instrument enhances sensitivity and provides a safe sampling strategy. The instrument uses nitrogen as both the DART discharge and DTIMS drift gases, allowing for a high electric field to be used for ion separation while keeping cost-of-use low. With the use of a traditional signal averaging acquisition mode, the 95% probability of detection (POD) for analytes sampled from melting point capillary tubes was 11.81% v/v for DMMP, 1.13% v/v for 2-CEES, and 10.61 mM for methamidophos. Sensitivity was improved via a prototype transmission-mode geometry interface, resulting in an almost 2 orders of magnitude decrease in the POD level for DMMP (0.28% v/v). As an alternative to transmission mode operation, digital multiplexing of the DTIMS ion injection step was also implemented, finding a 3-fold improvement in signal-to-noise ratios for 200 μs gate injections and a 4.5-fold for 400 μs gate injections. PMID:21319810

  12. Ion chromatographic separation of inorganic ions using a combination of hydrophilic interaction chromatographic column and cation-exchange resin column.

    PubMed

    Arai, Kaori; Mori, Masanobu; Hironaga, Takahiro; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2012-04-01

    A combination of hydrophilic interaction chromatographic (HILIC) column and a weakly acidic cation-exchange resin (WCX) column was used for simultaneous separation of inorganic anions and cations by ion chromatography (IC). Firstly, the capability of HILIC column for the separation of analyte ions was evaluated under acidic eluent conditions. The columns used were SeQuant ZIC-HILIC (ZIC-HILIC) with a sulfobetaine-zwitterion stationary phase (ZIC-HILIC) and Acclaim HILIC-10 with a diol stationary phase (HILIC-10). When using tartaric acid as the eluent, the HILIC columns indicated strong retentions for anions, based on ion-pair interaction. Especially, HILIC-10 could strongly retain anions compared with ZIC-HILIC. The selectivity for analyte anions of HILIC-10 with 5 mmol/L tartaric acid eluent was in the order of I(-) > NO3(-) > Br(-) > Cl(-) > H2PO4(-). However, since HILIC-10 could not separate analyte cations, a WCX column (TSKgel Super IC-A/C) was connected after the HILIC column in series. The combination column system of HILIC and WCX columns could successfully separate ten ions (Na+, NH4+, K+, Mg2+, Ca2+, H2PO4(-), Cl(-), Br(-), NO3(-) and I(-)) with elution of 4 mmol/L tartaric acid plus 8 mmol/L 18-crown-6. The relative standard deviations (RSDs) of analyte ions by the system were in the ranges of 0.02% - 0.05% in retention times and 0.18% - 5.3% in peak areas through three-time successive injections. The limits of detection at signal-to-noise ratio of 3 were 0.24 - 0.30 micromol/L for the cations and 0.31 - 1.2 micromol/L for the anions. This system was applied for the simultaneous determination of the cations and the anions in a vegetable juice sample with satisfactory results. PMID:22799200

  13. Characterization of tetramethylsilane for liquid-filled ionization dosimeters: Ion mobilities, free-ion yield and general recombination

    NASA Astrophysics Data System (ADS)

    Gago-Arias, A.; Argüeso, P.; Aguiar, P.; González-Castaño, D. M.; Gómez, F.; Pardo-Montero, J.

    2015-06-01

    Liquid-filled ionization chambers (LICs) are interesting detectors for the dosimetry of radiotherapy beams due to their water-equivalent response and high spatial resolution. Isooctane is the liquid most often used as an active medium, but other hydrocarbons, particularly tetramethylsilane (TMS), can be suitable for dosimetry. In this work we present a characterization of TMS (Merck, NMR calibration grade, purity > 99.7 %) for its use in LICs. The characterization consisted of measuring ion mobilities, using low dose 6 MV photon pulses from a medical linac, and free-ion yield, using a continuous cobalt-60 beam (the reference beam quality used in radiotherapy dosimetry). Those values were then used to model general recombination in a TMS-filled LIC. Measured ion mobilities, (2.6±0.3)×10-8 and (3.6±0.4)×10-8 m2 V-1 s-1, are similar to mobilities in isooctane, and two- to three-fold lower than some values reported for TMS. Such discrepancy can probably be attributed to the presence of different impurities. On the other hand, free-ion yield values obtained are approximately two-fold higher than for isooctane, in agreement with published data. Such high free-ion yield values result in a higher signal-to-noise ratio and may allow even better spatial resolution to be obtained with TMS-filled LICs. However, it comes at the cost of higher recombination effects that can compromise the operation of the chamber. Such high recombination and the low boiling point of TMS (≃ 28 ° C) make isooctane-filled LICs preferable to TMS-filled LICS for radiotherapy applications.

  14. Battery Separator Characterization and Evaluation Procedures for NASA's Advanced Lithium-Ion Batteries

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.; Bennet, William R.; Wong, Eunice K.; Lewton, MaryBeth R.; Harris, Megan K.

    2010-01-01

    To address the future performance and safety requirements for the electrical energy storage technologies that will enhance and enable future NASA manned aerospace missions, advanced rechargeable, lithium-ion battery technology development is being pursued within the scope of the NASA Exploration Technology Development Program s (ETDP's) Energy Storage Project. A critical cell-level component of a lithium-ion battery which significantly impacts both overall electrochemical performance and safety is the porous separator that is sandwiched between the two active cell electrodes. To support the selection of the optimal cell separator material(s) for the advanced battery technology and chemistries under development, laboratory characterization and screening procedures were established to assess and compare separator material-level attributes and associated separator performance characteristics.

  15. Polydopamine coated electrospun poly(vinyldiene fluoride) nanofibrous membrane as separator for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Cao, Chengying; Tan, Lei; Liu, Weiwei; Ma, Jiquan; Li, Lei

    2014-02-01

    In this study, polydopamine (PDA) coated electrospun poly(vinyldiene fluoride) (PVDF) nanofibrous membranes used as separator for lithium-ion batteries are successfully prepared. Their morphology, chemical and electrochemical characterization are investigated. The morphology and porosity measurements of the membranes show that the PDA coating does not harm to the structure of the electrospun PVDF nanofibrous membranes. Due to the PDA coating, it makes the PVDF surface hydrophilic and thus increases the electrolyte uptake and ionic conductivity, resulting in the enhanced performance of batteries. The battery using the PDA coated PVDF nanofibrous separator exhibits better cycling performance and higher power capability than that the battery using the bare PVDF nanofibrous separator. This study underlines that the PDA-coating treatment provides a promising process for the fabrication of advanced electrospun nanofibers separator in the lithium-ion battery applications.

  16. Facile and Nonradiation Pretreated Membrane as a High Conductive Separator for Li-Ion Batteries.

    PubMed

    Li, Bao; Li, Yongjun; Dai, Dongmei; Chang, Kun; Tang, Hongwei; Chang, Zhaorong; Wang, Chunru; Yuan, Xiao-Zi; Wang, Haijiang

    2015-09-16

    Polyolefin membranes are widely used as separators in commercialized Li-ion batteries. They have less polarized surfaces compared with polarized molecules of electrolyte, leading to a poor wetting state for separators. Radiation pretreatments are often adopted to solve such a problem. Unfortunately, they can only activate several nanometers deep from the surface, which limits the performance improvement. Here we report a facile and scalable method to polarize polyolefin membranes via a chemical oxidation route. On the surfaces of pretreated membrane, layers of poly(ethylene oxide) and poly(acrylic acid) can easily be coated, thus resulting in a high Li-ion conductivity of the membrane. Assembled with this decorated separator in button cells, both high-voltage (Li1.2Mn0.54Co0.13Ni0.13O2) and moderate-voltage (LiFePO4) cathode materials show better electrochemical performances than those assembled with pristine polyolefin separators. PMID:26320596

  17. Improved fluid simulations of radio-frequency plasmas using energy dependent ion mobilities

    SciTech Connect

    Greb, Arthur; Niemi, Kari; O'Connell, Deborah; Gans, Timo; Ennis, Gerard J.; MacGearailt, Niall

    2013-05-15

    Symmetric and asymmetric capacitively coupled radio-frequency plasmas in oxygen at 40 Pa, 300 V voltage amplitude and a discharge gap of 40 mm are investigated by means of one-dimensional numerical semi-kinetic fluid modeling on the basis of a simplified reaction scheme including the dominant positive and negative ions, background gas, and electrons. An improved treatment, by accounting for the dependence of ion mobilities on E/N, is compared to the standard approach, based on using zero-field mobility values only. The charged particle dynamics as a result of direct electron impact ionization of oxygen, secondary electron release from the electrodes, the spatial distribution of all involved particles as well as impact of geometry and model modification on ion energies is analyzed and compared to independent simulations and experiments.

  18. Electrospun Nanofiber-Coated Membrane Separators for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Lee, Hun

    Lithium-ion batteries are widely used as a power source for portable electronic devices and hybrid electric vehicles due to their excellent energy and power densities, long cycle life, and enhanced safety. A separator is considered to be the critical component in lithium-ion rechargeable batteries. The separator is placed between the positive and negative electrodes in order to prevent the physical contact of electrodes while allowing the transportation of ions. In most commercial lithium-ion batteries, polyolefin microporous membranes are commonly used as the separator due to their good chemical stability and high mechanical strength. However, some of their intrinsic natures, such as low electrolyte uptake, poor adhesion property to the electrodes, and low ionic conductivity, can still be improved to achieve higher performance of lithium-ion batteries. In order to improve these intrinsic properties, polyolefin microporous membranes can be coated with nanofibers by using electrospinning technique. Electrospinning is a simple and efficient method to prepare nanofibers which can absorb a significant amount of liquid electrolyte to achieve low internal resistance and battery performance. This research presents the preparation and investigation of composite membrane separators prepared by coating nanofibers onto polyolefin microporous membranes via electrospinning technique. Polyvinylidene fluoride polymers and copolymers were used for the preparation of electrospun nanofiber coatings because they have excellent electrochemical stability, good adhesion property, and high temperature resistance. The nanofiber coatings prepared by electrospinning form an interconnected and randomly orientated structure on the surface of the polyolefin microporous membranes. The size of the nanofibers is on a scale that does not interfere with the micropores in the membrane substrates. The resultant nanofiber-coated membranes have the potential to combine advantages of both the polyolefin

  19. Direct Separation of Molybdenum from Solid Uranium Matrices Employing Pyrohydrolysis, a Green Separation Method, and Its Determination by Ion Chromatography.

    PubMed

    Mishra, Vivekchandra G; Thakur, Uday K; Shah, Dipti J; Gupta, Neeraj K; Jeyakumar, Subbiah; Tomar, Bhupendra S; Ramakumar, Karanam L

    2015-11-01

    Pyrohydrolysis is a well-established separation method, and it is being used as a sample preparation method for several materials for further determination of non-metals such as halogens, boron, and sulfur. Analytes are retained in a diluted solution that is suitable for carrying out analysis by several determination techniques and minimizing the use of concentrated reagents. Pyrohydrolysis separation of metals has not been reported yet. The present study demonstrates the pyrohydrolysis separation of Mo as MoO4(2-) from uranium materials and its subsequent determination using ion chromatography coupled with suppressed conductivity detector. With use of TGA and XRD the volatilization behavior of Mo was studied. Important parameters for the pyrohydrolysis method required for the quantitative separation of Mo were evaluated. The precision of the method was better than 5% at 25 ppm of Mo. The accuracy was evaluated by analysis of a CRM (U3O8-ILCE-IV). The method was applied to determine Mo in ammonium diuranate samples, where the conventional methods suffer from the loss of Mo. PMID:26465172

  20. Mathematical modeling and remote monitoring of ion-exchange separation of transplutonium elements

    SciTech Connect

    Tselishchev, I.V.; Elesin, A.A.

    1988-07-01

    A mathematical model and calculational algorithms for the elution curves for ion-exchange separation of transplutonium elements (TPE) and the limits of optimal fractionation of the substances being separated, based on indicators of the process (yield, purification), are presented. The calculational programs are part of the programming provision of a small informational-calculational system based on the microcomputer Elektronika DZ-28, intended for remote monitoring of TPE separation. The elaborated programs can be implemented in the preliminary choice of necessary conditions of the TPE separation process, and also during and after the separation process for comparison of calculated results with the results of continuous, on-line remote monitoring and with the results of laboratory sample analysis. The possible application of the programs has been checked in the instance of the separation of curium and americium, and einsteinium and californium, the results of which are in satisfactory agreement with the results of remote and laboratory-analytical monitoring.

  1. INSTRUMENTS AND METHODS OF INVESTIGATION: Plasma isotope separation based on ion cyclotron resonance

    NASA Astrophysics Data System (ADS)

    Dolgolenko, Dmitrii A.; Muromkin, Yurii A.

    2009-04-01

    Experiments that have been conducted in the USA, France, and Russia to investigate isotopically selective ion cyclotron resonance (ICR) as a tool for plasma isotope separation are analyzed. Because this method runs into difficulties at low values of the relative isotope mass difference ΔM/M, for some elements (for gadolinium, as an example) isotope separation still remains a problem. There are ways to solve it, however, as experimental results and theoretical calculations suggest.

  2. Radical-Ion-Pair Spin Decoherence and the Quantum Efficiency of Photosynthetic Charge Separation

    NASA Astrophysics Data System (ADS)

    Kominis, Iannis; Dellis, A. T.

    2014-03-01

    We have pioneered the fundamental quantum dynamics of radical-ion-pair reactions, elucidating the basic spin-decoherence mechanism pertaining to these biochemical reactions. Radical-ion pair reactions appear in the avian magnetic compass, but more importantly, they participate in the cascade of electron-transfer reactions taking place in photosynthetic reaction centers. We will here present new insights on how the fundamental quantum dynamics of radical-ion pair reactions affect the quantum efficiency of charge separation in photosynthetic reaction centers.

  3. Ion exchange in the atomic energy industry with particular reference to actinide and fission product separation

    SciTech Connect

    Jenkins, I.L.

    1984-01-01

    Reviewed are some of the uses of ion exchange processes used by the nuclear industry for the period April, 1978 to April, 1983. The topics dealt with are: thorium, protactinium, uranium, neptunium, plutonium, americium, cesium and actinide-lanthanide separations; the higher actinides - Cm, Bk, Cf, Es and Fm; fission products; ion exchange in the geological disposal of radioactive waste. Consideration is given to safety in the use of ion exchangers and in safe methods of disposal of such materials. Full scale and pilot plant process descriptions are included as well as summaries of laboratory studies. 130 references.

  4. ION-EXCHANGE METHOD FOR SEPARATING RADIUM FROM RADIUM-BARIUM MIXTURES

    DOEpatents

    Fuentevilla, M.E.

    1959-06-30

    An improved process is presented for separating radium from an aqueous feed solution containing radium and barium values and a complexing agent for these metals. In this process a feed solutlon containing radium and barium ions and a complexing agent for said ions ls cycled through an exchange zone in resins. The radiumenriched resin is then stripped of radium values to form a regeneration liquid, a portion of which is collected as an enriched product, the remaining portion being recycled to the exchange zone to further enrich the ion exchange resin in radium.

  5. Ion imprinted polymeric nanoparticles for selective separation and sensitive determination of zinc ions in different matrices

    NASA Astrophysics Data System (ADS)

    Shamsipur, Mojtaba; Rajabi, Hamid Reza; Pourmortazavi, Seied Mahdi; Roushani, Mahmoud

    2014-01-01

    Preparation of Zn2+ ion-imprinted polymer (Zn-IIP) nanoparticles is presented in this report. The Zn-IIP nanoparticles are prepared by dissolving stoichiometric amounts of zinc nitrate and selected chelating ligand, 3,5,7,20,40-pentahydroxyflavone, in 15 mL ethanol-acetonitrile (2:1; v/v) mixture as a porogen solvent in the presence of ethylene glycol-dimethacrylate (EGDMA) as cross-linking, methacrylic acid (MAA) as functional monomer, and 2,2-azobisisobutyronitrile (AIBN) as initiator. After polymerization, Cavities in the polymer particles corresponding to the Zn2+ ions were created by leaching the polymer in HCl aqueous solution. The synthesized IIPs were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal analysis techniques. Also, the pH range for rebinding of Zn2+ ion on the IIP and equilibrium binding time were optimized, using flame atomic absorption spectrometry. In selectivity study, it was found that imprinting results increased affinity of the material toward Zn2+ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for six times without any significant decrease in polymer binding affinities. Finally, the prepared sorbent was successfully applied to the selective recognition and determination of zinc ion in different real samples.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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. Graphical Abstract ᅟ. PMID:27220844

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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. Ion Thermal Decoupling and Species Separation in Shock-Driven Implosions

    NASA Astrophysics Data System (ADS)

    Rinderknecht, Hans G.; Rosenberg, M. J.; Li, C. K.; Hoffman, N. M.; Kagan, G.; Zylstra, A. B.; Sio, H.; Frenje, J. A.; Gatu Johnson, M.; Séguin, F. H.; Petrasso, R. D.; Amendt, P.; Bellei, C.; Wilks, S.; Delettrez, J.; Glebov, V. Yu.; Stoeckl, C.; Sangster, T. C.; Meyerhofer, D. D.; Nikroo, A.

    2015-01-01

    Anomalous reduction of the fusion yields by 50% and anomalous scaling of the burn-averaged ion temperatures with the ion-species fraction has been observed for the first time in D 3He-filled shock-driven inertial confinement fusion implosions. Two ion kinetic mechanisms are used to explain the anomalous observations: thermal decoupling of the D and 3He populations and diffusive species separation. The observed insensitivity of ion temperature to a varying deuterium fraction is shown to be a signature of ion thermal decoupling in shock-heated plasmas. The burn-averaged deuterium fraction calculated from the experimental data demonstrates a reduction in the average core deuterium density, as predicted by simulations that use a diffusion model. Accounting for each of these effects in simulations reproduces the observed yield trends.

  10. Ion thermal decoupling and species separation in shock-driven implosions.

    PubMed

    Rinderknecht, Hans G; Rosenberg, M J; Li, C K; Hoffman, N M; Kagan, G; Zylstra, A B; Sio, H; Frenje, J A; Gatu Johnson, M; Séguin, F H; Petrasso, R D; Amendt, P; Bellei, C; Wilks, S; Delettrez, J; Glebov, V Yu; Stoeckl, C; Sangster, T C; Meyerhofer, D D; Nikroo, A

    2015-01-16

    Anomalous reduction of the fusion yields by 50% and anomalous scaling of the burn-averaged ion temperatures with the ion-species fraction has been observed for the first time in D^{3}He-filled shock-driven inertial confinement fusion implosions. Two ion kinetic mechanisms are used to explain the anomalous observations: thermal decoupling of the D and ^{3}He populations and diffusive species separation. The observed insensitivity of ion temperature to a varying deuterium fraction is shown to be a signature of ion thermal decoupling in shock-heated plasmas. The burn-averaged deuterium fraction calculated from the experimental data demonstrates a reduction in the average core deuterium density, as predicted by simulations that use a diffusion model. Accounting for each of these effects in simulations reproduces the observed yield trends. PMID:25635549

  11. Ion Thermal Decoupling and Species Separation in Shock-Driven Implosions

    DOE PAGESBeta

    Rinderknecht, Hans G.; Rosenberg, M. J.; Li, C. K.; Hoffman, N. M.; Kagan, G.; Zylstra, A. B.; Sio, H.; Johnson, M. Gatu; Seguin, F. H.; Petrasso, R. D.; et al

    2015-01-14

    Anomalous reduction of the fusion yields by 50% and anomalous scaling of the burn-averaged ion temperatures with the ion-species fraction has been observed for the first time in DHe3-filled shock-driven inertial confinement fusion implosions. Two ion kinetic mechanisms are used to explain the anomalous observations: thermal decoupling of the D and He3 populations and diffusive species separation. The observed insensitivity of ion temperature to a varying deuterium fraction is shown to be a signature of ion thermal decoupling in shock-heated plasmas. The burn-averaged deuterium fraction calculated from the experimental data demonstrates a reduction in the average core deuterium density, asmore » predicted by simulations that use a diffusion model. Accounting for each of these effects in simulations reproduces the observed yield trends.« less

  12. Ion Thermal Decoupling and Species Separation in Shock-Driven Implosions

    SciTech Connect

    Rinderknecht, Hans G.; Rosenberg, M. J.; Li, C. K.; Hoffman, N. M.; Kagan, G.; Zylstra, A. B.; Sio, H.; Johnson, M. Gatu; Seguin, F. H.; Petrasso, R. D.; Amendt, P.; Bellei, C.; Wilks, S.; Delettrez, J.; Glebov, V. Yu.; Stoeckl, C.; Sangster, T. C.; Meyerhofer, D. D.; Nikroo, A.

    2015-01-14

    Anomalous reduction of the fusion yields by 50% and anomalous scaling of the burn-averaged ion temperatures with the ion-species fraction has been observed for the first time in DHe3-filled shock-driven inertial confinement fusion implosions. Two ion kinetic mechanisms are used to explain the anomalous observations: thermal decoupling of the D and He3 populations and diffusive species separation. The observed insensitivity of ion temperature to a varying deuterium fraction is shown to be a signature of ion thermal decoupling in shock-heated plasmas. The burn-averaged deuterium fraction calculated from the experimental data demonstrates a reduction in the average core deuterium density, as predicted by simulations that use a diffusion model. Accounting for each of these effects in simulations reproduces the observed yield trends.

  13. Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

    PubMed

    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. PMID:24742534

  14. Probing the selective separation of potassium ion from sodium ion with cyclopentadienyl anion as receptor: a computational study.

    PubMed

    Desai, Mittal L; Si, Mrinal Kanti; Lo, Rabindranath; Ganguly, Bishwajit

    2015-08-01

    A systematic computational study has been carried out using post-Hartree-Fock and density functional theory methods on half sandwich (M-Cp), sandwich (Cp-M-Cp), inversed sandwich (M-Cp-M), and multi-decker chain complexes of alkali metal ions (Na(+), and K(+)). The binding affinity of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions has been studied in half sandwich, sandwich, inversed sandwich, and multi-decker chain complexes. These complexes have been examined in the aqueous phase. The calculated results show that Cp anion can preferentially bind with Na(+) ion over K(+) ion in aqueous phase. The results obtained from DFT calculations have been compared with the crystal structures of Cp-Na and Cp-K complexes. The Bader's atoms in molecule (AIM) analysis were performed to characterize the non-covalent cation-π interactions in the Cp-M complexes. The calculated electron density at cage critical point indicates the strength of the Cp-M complexes. Energy decomposition analysis (EDA) has also been performed to investigate the origins of these interactions. The electrostatic interaction contributes significantly to the total interaction energy in Cp-M complexes. The relative stability difference of cyclopentadienyl anion (Cp) with K(+) and Na(+) ions in aqueous phase can be exploited for the separations from mixture such as sea bittern. The lower stability of K-Cp complex can induce to precipitate the K(+) ions more easily than the corresponding Na(+) ions. Graphical Abstract Potassium ion from sodium ion with cyclopentadienyl anion as receptor. PMID:26232185

  15. Utilization of deep eutectic solvents as novel mobile phase additives for improving the separation of bioactive quaternary alkaloids.

    PubMed

    Tan, Ting; Zhang, Mingliang; Wan, Yiqun; Qiu, Hongdeng

    2016-03-01

    Deep eutectic solvents (DESs) were used as novel mobile phase additives to improve chromatographic separation of four quaternary alkaloids including coptisine chloride, sanguinarine, berberine chloride and chelerythrine on a C18 column. DESs as a new class of ionic liquids are renewably sourced, environmentally benign, low cost and easy to prepare. Seven DESs were obtained by mixing different hydrogen acceptors and hydrogen-bond donors. The effects of organic solvents, the concentration of DESs, the types of DESs and the pH values of the buffer solution on the separation of the analytes were investigated. The composition of acetonitrile and 1.0% deep eutectic solvents aqueous solution (pH 3.3, adjusted with hydrochloric acid) in a 32:68 (v/v) ratio was used as optimized mobile phase, with which four quaternary alkaloids were well separated. When a small amount of DESs was added in the mobile phase for the separation of alkaloids on the C18 column, noticeable improvements were distinctly observed such as decreasing peak tailing and improving resolution. The separation mechanism mediated by DESs as mobile phase additives can be attributed to combined effect of both hydrogen acceptors and hydrogen-bond donors. For example, choline chloride can effectively cover the residual silanols on silica surface and ethylene glycol can reduce the retention time of analytes. The proposed method has been applied to determine BerbC in Lanqin Chinese herbal oral solution and BerbC tablet. Utilization of DESs in mobile phase can efficiently improve separation and selectivity of analytes from complex samples. PMID:26717817

  16. Separation of Lanthanide Ions with Kläui Ligand Resin

    SciTech Connect

    Granger, Trinity D.; Henry, Victoria A.; Latesky, Stanley

    2007-07-01

    Separation and pre-concentration of the desired analyte is often a critical step in many radioanalytical methods. Current procedures for separating and concentrating analytes for detection are complex, and can be both expensive and time consuming. Therefore, the purpose of this research is to develop an alternative method of separating lanthanide ions through the use of an extraction chromatography resin containing a Klaui ligand salt. This research is a continuation of a concerted effort to develop new methods of detecting small concentrations of radionuclides and lanthanides using Klaui ligands. The Klaui ligands, C5Me5Co(OP(OR)2)3- (R=Me, Et, n-Pr) (LOR-), have unique affinity for lanthanide and actinide ions in the presence of competing metal ions. The use of 1 wt% NaLOR (R=Et or n-Pr) adsorbed onto resin support has been shown to extract lanthanide ions from aqueous nitric acid solutions of different concentrations. In order to further evaluate the utility of these materials in radiochemical separation, the selectivity of the resins for the different lanthanide ions was examined by measuring the distribution coefficients (Kd) for a series of lanthanides over a range of solution conditions. Based on prior research with actinide ions, it was hypothesized that the lanthanide ions would bond strongly with the Klaui ligands. The success of this research is important, because it will assist in expanding and improving current automated radiochemical methods, which will decrease the cost of developing and implementing radiochemical methods. To date, Kd values have been determined for Eu+3, Nd+3 and Pr+3 under varying nitric acid (HNO3) concentration, using a resin consisting of 1.0 wt% NaLOPr on Amberlite XAD-7HP. The dependence of the Kd values for Eu+3 has also been examined as a function of the ligand-to-europium ratio and the nitrate concentration. Decreasing Kd values were obtained upon increasing the nitric acid concentration, indicating protonation of the

  17. Pressure-dependent mobility of negative ions in mixtures of H2O with Ar

    NASA Astrophysics Data System (ADS)

    de Urquijo, J.; Ruiz-Vargas, G.

    2016-04-01

    The mobility of negative ions in H2O-Ar mixtures has been measured with a pulsed Townsend technique. It has been found that for a fixed value of the density-normalized electric field strength, E/N, the mobility of the H2O anions is strongly pressure dependent. We have also found that even for a single, total gas mixture pressure, even though at first sight the mobility of the anions seems to follow Blanc’s relation closely, a closer view indicates that the mobilities tend to shift to higher values as the water vapour concentration decreases. In spite of the lack of mass spectrometry to assess the mass and abundance of the drifting anions under specific conditions of E/N, water vapour concentration and gas pressure, the present measurements are strongly indicative of a complex ion transport and ion-molecule reaction scheme of daughter H2O anions in the H2O-Ar mixture.

  18. Developing Fieldable Systems for Chemical Sensing Using Field Asymmetric Ion Mobility Spectrometry and Mass Spectrometry

    SciTech Connect

    Kevin Kyle, Stephan Weeks, R. Trainham

    2008-03-01

    Currently, there is an urgent need for field-rugged and field-programmable sensor systems that provide highly selective, universal monitoring of vapors and aerosols at detectable levels from persons or areas involved with illicit chemical/biological/explosives (CBE) production. These devices must be portable, low cost, robust, and provide accurate measurements to avoid both false positive and negative results. Furthermore, the information provided by the devices must be received in a timely manner so that informed decisions can be immediately made and the appropriate actions taken. Two technologies that are unparalleled in their sensitivity, selectivity, and trace-level detection capabilities are field asymmetric ion mobility spectrometry (FAIMS) and mass spectrometry. Here, we will show progress that has been made toward developing fieldable FAIMS systems and mass spectrometers. Working in collaboration with Sionex Corporation, the microDMx detector was equipped with a continuous air sampling system to develop selective methods for the analysis of compounds of interest. A microdiaphragm pump (KNF Neuberger, Inc.) is used to pull in gas-phase analytes directly from the air for separation and detection with the FAIMS system. The FAIMS evaluation platform (SVAC) unit currently measures 9.8-inch x 4.6-inch x 3.2-inch, weighs 3.1 lb, and utilizes a {sup 63}Ni source to ionize incoming compounds. Analytes entering the unit are separated and identified by their characteristic response to the compensation voltage (V{sub c}) at a given rf field strength (V{sub rf}). This response has been observed to be unique for a wide range of substances studied. If additional verification were required or a targeted analyte present in a complex chemical matrix, a FAIMS unit equipped with a fast gas chromatography column has been evaluated. The unit combines the separation capabilities of gas chromatography with the selectivity of FAIMS. It measures 9.5-inch x 5.25-inch x 3.5-inch

  19. Enhanced sensitivity and selectivity in a dual cell ion mobility spectrometer

    NASA Astrophysics Data System (ADS)

    Griffin, Matthew T.; Fulton, Jack E., Jr.; McAtee, Robert F.; Gao, Rong; Tsoukalas, Lefteri H.

    2003-08-01

    While ion mobility spectrometry (IMS) has been used as a portable trace vapor detector, these handheld systems suffer from poor selectivity. Their low resolution makes confident identification of chemical species difficult. One major application for these IMS systems is in Homeland Defense. IMS systems are fielded for the detection of chemical warfare agents, explosives, narcotics, and other hazardous chemicals. Recently, a novel signal processing methodology using wavelet filtering, statistical evaluators, and genetic algorithms was demonstrated to improve sensitivity and specificity of an ion mobility spectrometer. Previous work involved a single (single polarity) IMS cell. Since both positive and negative ions are created in the same environment and a common sample interface is used for the dual IMS system, there is cross talk between the positive and negative cell. Typically, this cross talk provides little information on the identity of the chemical species present. However, using this new methodology, valuable sample information is obtained. Moreover, ion beam modulation has been incorporated to allow for the ion beam to be broken up into discrete packets. The modulation allows the rejection of common background interferents. This paper will present the process of using cell cross talk, ion beam modulation, and application and extension of the signal processing methodology. The application to field instrumentation will also be discussed.

  20. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    SciTech Connect

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    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.

  1. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Oberreit, Derek; Rawat, Vivek K.; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H.; Hogan, Christopher J.

    2015-09-01

    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)xM+ (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.

  2. Analysis of heterogeneous water vapor uptake by metal iodide cluster ions via differential mobility analysis-mass spectrometry.

    PubMed

    Oberreit, Derek; Rawat, Vivek K; Larriba-Andaluz, Carlos; Ouyang, Hui; McMurry, Peter H; Hogan, Christopher J

    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)xM(+) (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. PMID:26374028

  3. Experimental Ion Mobility measurements in Ne-CO2 and CO2-N2 mixtures

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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 second peak, with higher mobility, was attributed to CO2+ ions. The mobility values of the main peak range between 2.11 ± 0.04 and 1.10 ± 0.03 cm2V‑1s‑1 in the 1%–99% interval of CO2, while the second peak's from 2.26 ± 0.02 and 1.95 ± 0.04 cm2V‑1s‑1 (1%–10% of CO2). The inverse of the mobility displays an aproximately linear dependence on the CO2 concentration in the mixture.

  4. Classification of Ion Mobility Data Using the Neural Network Approach

    NASA Technical Reports Server (NTRS)

    Duong, T. A.; Kanik, I.

    2005-01-01

    Determination of atmospheric and surface elemental and molecular composition of various solar system bodies is essential to the development of a firm understanding of the origin and evolution of the solar system. Furthermore, such data is needed to address the intriguing question of whether or not life exists or once existed elsewhere in the Solar System. As such, these measurements are among the primary scientific goals of NASA s current and future planetary missions. In recent years, significant progress toward both miniaturization and field portability of in situ analytical separation and detection devices have been made with future planetary explorations in mind. However, despite all these advances, accurate in situ identification of atmospheric and surface compounds remains a big challenge. In response to that we are developing various hardware and software tools which would enable us to uniquely identify species of interest in a complex chemical environment.

  5. Synthesis of Anomeric Methyl Fructofuranosides and Their Separation on an Ion-Exchange Resin

    ERIC Educational Resources Information Center

    Nurminen, Erkki; Poijarvi, Paivi; Koskua, Katja; Hovinen, Jari

    2007-01-01

    Treatment of d-fructose with methanol in the presence of acid as a catalyst gives a mixture of methyl-[beta]-d-fructopyranoside, methyl-[alpha]-D-fructofuranoside, and methyl-[beta]-d-fructofuranoside, which were separated on an ion exchange column and characterized polarimetrically.

  6. Ion mobility imaging and contrast mechanism of apparent conductivity in MREIT.

    PubMed

    Oh, Tong In; Kim, Young Tae; Minhas, Atul; Seo, Jin Keun; Kwon, Oh In; Woo, Eung Je

    2011-04-01

    Magnetic resonance electrical impedance tomography (MREIT) aims to produce high-resolution cross-sectional images of conductivity distribution inside the human body. Injected current into an imaging object induces a distribution of internal magnetic flux density, which is measured by using an MRI scanner. We can reconstruct a conductivity image based on its relation with the measured magnetic flux density. In this paper, we explain the contrast mechanism in MREIT by performing and analyzing a series of numerical simulations and imaging experiments. We built a stable conductivity phantom including a hollow insulating cylinder with holes. Filling both inside and outside the hollow cylinder with the same saline, we controlled ion mobilities to create a conductivity contrast without being affected by the ion diffusion process. From numerical simulations and imaging experiments, we found that slopes of induced magnetic flux densities change with hole diameters and therefore conductivity contrasts. Associating the hole diameter with apparent conductivity of the region inside the hollow cylinder with holes, we could experimentally validate the contrast mechanism in MREIT. Interpreting reconstructed apparent conductivity images of the phantom as ion mobility images, we discuss the meaning of the apparent conductivity seen by a certain probing method. In designing MREIT imaging experiments, the ion mobility imaging method using the proposed stable conductivity phantom will enable us to estimate a distinguishable conductivity contrast for a given set of imaging parameters. PMID:21411866

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Comparison of reactant and analyte ions for ⁶³Nickel, corona discharge, and secondary electrospray ionization sources with ion mobility-mass spectrometry.

    PubMed

    Crawford, C L; Hill, H H

    2013-03-30

    (63)Nickel radioactive ionization ((63)Ni) is the most common and widely used ion source for ion mobility spectrometry (IMS). Regulatory, financial, and operational concerns with this source have promoted recent development of non-radioactive sources, such as corona discharge ionization (CD), for stand-alone IMS systems. However, there has been no comparison of the negative ion species produced by all three sources in the literature. This study compares the negative reactant and analyte ions produced by three sources on an ion mobility-mass spectrometer: conventional (63)Ni, CD, and secondary electrospray ionization (SESI). Results showed that (63)Ni and SESI produced the same reactant ion species while CD produced only the nitrate monomer and dimer ions. The analyte ions produced by each ion source were the same except for the CD source which produced a different ion species for the explosive RDX than either the (63)Ni or SESI source. Accurate and reproducible reduced mobility (K0) values, including several values reported here for the first time, were found for each explosive with each ion source. Overall, the SESI source most closely reproduced the reactant ion species and analyte ion species profiles for (63)Ni. This source may serve as a non-radioactive, robust, and flexible alternative for (63)Ni. PMID:23598216

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

    NASA Astrophysics Data System (ADS)

    Titov, Vladimir V.

    1995-01-01

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

  10. Separation of hemicellulose-derived saccharides from wood hydrolysate by lime and ion exchange resin.

    PubMed

    Wang, Xiaojun; Zhuang, Jingshun; Fu, Yingjuan; Tian, Guoyu; Wang, Zhaojiang; Qin, Menghua

    2016-04-01

    A combined process of lime treatment and mixed bed ion exchange was proposed to separate hemicellulose-derived saccharides (HDS) from prehydrolysis liquor (PHL) of lignocellulose as value added products. The optimization of lime treatment achieved up to 44.2% removal of non-saccharide organic compounds (NSOC), mainly colloidal substances, with negligible HDS degradation at 0.5% lime level and subsequent neutralization by phosphoric acid. The residual NSOC and calcium ions in lime-treated PHL were eliminated by mixed bed ion exchange. The breakthrough curves of HDS and NSOC showed selective retention toward NSOC, leading to 75% HDS recovery with 95% purity at 17 bed volumes of exchange capacity. In addition, macroporous resin showed higher exchange capacity than gel resin as indicated by the triple processing volume. The remarkable selectivity of the combined process suggested the feasibility for HDS separation from PHL. PMID:26859331

  11. Separation of ions on the front of a shock wave in a multicomponent plasma

    NASA Astrophysics Data System (ADS)

    Glazyrin, S. I.; Kuratov, A. S.; Bychenkov, V. Yu.

    2016-02-01

    The structure of a shock wave propagating in a plasma with two types of ions has been studied within the model of multifluid hydrodynamics based on the 13-moment system of Grad's equations. Although the averaged dynamics of the shock front coincides with the single-component variant of the average-ion model, its structure is different at a noticeable difference between charge-to-mass ratios of different ions, demonstrating their separation on the shock front. For the problem of inertial confinement fusion, the range of parameters for which such a separation is important, as well as physical processes determining the two-component structure of the shock front, has been established.

  12. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    USGS Publications Warehouse

    Ball, J.W.; Bassett, R.L.

    2000-01-01

    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  13. Mobility and fluorescence of barium ions in xenon gas for the exo experiment

    NASA Astrophysics Data System (ADS)

    Benitez Medina, Julio Cesar

    The Enriched Xenon Observatory (EXO) is an experiment which aims to observe the neutrinoless double beta decay of 136Xe. The measurement of this decay would give information about the absolute neutrino mass and whether or not the neutrino is its own antiparticle. Since this is a very rare decay, the ability to reject background events by detecting the barium ion daughter from the double beta decay would be a major advantage. EXO is currently operating a detector with 200 kg of enriched liquid xenon, and there are plans to build a ton scale xenon detector. Measurements of the purity of liquid xenon in our liquid xenon test cell are reported. These results are relevant to the research on detection of single barium ions by our research group at Colorado State University. Details of the operation of the purity monitor are described. The effects of using a purifier, recirculation and laser ablation on the purity of liquid xenon are discussed. Mobility measurements of barium in xenon gas are reported for the first time. The variation of mobility with xenon gas pressure suggests that a significant fraction of molecular ions are formed when barium ions interact with xenon gas at high pressures. The measured mobility of Ba+ in Xe gas at different pressures is compared with the predicted theoretical value, and deviations are explained by a model that describes the fraction of molecular ions in Xe gas as a function of pressure. The results are useful for the analysis of experiments of fluorescence of Ba+ in xenon gas. It is also important to know the mobility of the ions in order to calculate the time they interact with an excitation laser in fluorescence experiments and in proposed 136 Ba+ daughter detection schemes. This thesis presents results of detection of laser induced fluorescence of Ba+ ions in Xe gas. Measurements of the pressure broadening of the excitation spectra of Ba+ in xenon gas are presented. Nonradiative decays due to gas collisions and optical pumping

  14. Accurate Quantification of High Density Lipoprotein Particle Concentration by Calibrated Ion Mobility Analysis

    PubMed Central

    Hutchins, Patrick M.; Ronsein, Graziella E.; Monette, Jeffrey S.; Pamir, Nathalie; Wimberger, Jake; He, Yi; Anantharamaiah, G.M.; Kim, Daniel Seung; Ranchalis, Jane E.; Jarvik, Gail P.; Vaisar, Tomas; Heinecke, Jay W.

    2015-01-01

    Background It is critical to develop new metrics to determine whether high density lipoprotein (HDL) is cardioprotective in humans. One promising approach is HDL particle concentration (HDL-P) – the size and concentration of HDL in plasma or serum. However, the two methods currently used to determine HDL-P yield concentrations that differ more than 5-fold. We therefore developed and validated an improved approach to quantify HDL-P, termed calibrated ion mobility analysis (calibrated IMA). Methods HDL was isolated from plasma by ultracentrifugation, introduced into the gas phase with electrospray ionization, separated by size, and quantified by particle counting. A calibration curve constructed with purified proteins was used to correct for the ionization efficiency of HDL particles. Results The concentrations of gold nanoparticles and reconstituted HDLs measured by calibrated IMA were indistinguishable from concentrations determined by orthogonal methods. In plasma of control (n=40) and cerebrovascular disease (n=40) subjects, three subspecies of HDL were reproducibility measured, with an estimated total HDL-P of 13.4±2.4 µM (mean±SD). HDL-C accounted for 48% of the variance in HDL-P. HDL-P was significantly lower in subjects with cerebrovascular disease, and this difference remained significant after adjustment for HDL cholesterol levels. Conclusions Calibrated IMA accurately and reproducibly determined the concentration of gold nanoparticles and synthetic HDL, strongly suggesting the method could accurately quantify HDL particle concentration. Importantly, the estimated stoichiometry of apoA-I determined by calibrated IMA was 3–4 per HDL particle, in excellent agreement with current structural models. Furthermore, HDL-P associated with cardiovascular disease status in a clinical population independently of HDL cholesterol. PMID:25225166

  15. Peak Detection Method Evaluation for Ion Mobility Spectrometry by Using Machine Learning Approaches

    PubMed Central

    Hauschild, Anne-Christin; Kopczynski, Dominik; D’Addario, Marianna; Baumbach, Jörg Ingo; Rahmann, Sven; Baumbach, Jan

    2013-01-01

    Ion mobility spectrometry with pre-separation by multi-capillary columns (MCC/IMS) has become an established inexpensive, non-invasive bioanalytics technology for detecting volatile organic compounds (VOCs) with various metabolomics applications in medical research. To pave the way for this technology towards daily usage in medical practice, different steps still have to be taken. With respect to modern biomarker research, one of the most important tasks is the automatic classification of patient-specific data sets into different groups, healthy or not, for instance. Although sophisticated machine learning methods exist, an inevitable preprocessing step is reliable and robust peak detection without manual intervention. In this work we evaluate four state-of-the-art approaches for automated IMS-based peak detection: local maxima search, watershed transformation with IPHEx, region-merging with VisualNow, and peak model estimation (PME). We manually generated a gold standard with the aid of a domain expert (manual) and compare the performance of the four peak calling methods with respect to two distinct criteria. We first utilize established machine learning methods and systematically study their classification performance based on the four peak detectors’ results. Second, we investigate the classification variance and robustness regarding perturbation and overfitting. Our main finding is that the power of the classification accuracy is almost equally good for all methods, the manually created gold standard as well as the four automatic peak finding methods. In addition, we note that all tools, manual and automatic, are similarly robust against perturbations. However, the classification performance is more robust against overfitting when using the PME as peak calling preprocessor. In summary, we conclude that all methods, though small differences exist, are largely reliable and enable a wide spectrum of real-world biomedical applications. PMID:24957992

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

    SciTech Connect

    Jha, Manis Kumar 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.

  17. Properties of solvate shells and the mobility of ions, according to molecular dynamics data

    NASA Astrophysics Data System (ADS)

    Lankin, A. V.; Norman, G. E.; Orekhov, M. A.

    2016-05-01

    The solvate shells of an ion, its velocity autocorrelation function, and diffusion coefficient D are found, and the interrelations between them are analyzed. A single ion in the system of atoms of a liquid is considered a model system. The interaction between the ion and atoms of the liquid is described by polarization potential U( r); the interaction between atoms of the liquid alone is described by the Lennard-Jones potential. A classical molecular dynamics method is used. Five solvate shells around the ion are found, and the lifetimes of atoms on each shell are calculated. It is found that the velocity autocorrelation function is of a vibrating nature. The spectrum of the autocorrelator and the frequency of cluster vibrations in a linear approximation are compared. Dependences D on parameters of potential U( r) are found. No dependence D on the ion mass is found; this is explained by solvation. The Einstein-Stokes formula and the HSK approximation are used in discussing the results. It is shown that at small radii of the ion, dependence D on parameters U( r) is described by such a model. When the ion radius is increased, the deviation from this dependence and an increase in D are observed. The results are compared to experimental mobilities of O 2 - and Ar 2 + ions in liquid argon.

  18. Electrokinetic power generation by means of streaming potentials: a mobile-ion-drain method to increase the streaming potentials.

    PubMed

    Yang, Jun; Lu, Fuzhi; Kostiuk, Larry W; Kwok, Daniel Y

    2005-04-01

    We show, by natural occurring phenomena of charge separation near the solid-liquid interface in microchannels, that electricity can be generated by forcing water through a ceramic rod with no moving part and emission. A single hand push on a syringe is our source of power which easily generates a streaming potential of over 20 V and a streaming current of 30 microA. By means of streaming potentials, two capacitors were charged and discharged alternatively to light-up two Light-Emitting-Diodes in every ten seconds. From our specific choice of liquid/solid pair, an efficiency of 0.8% was obtained. A mobile-ion-drain method is also demonstrated to increase the streaming potential. PMID:16004133

  19. Selective pretreatment and determination of phenazopyridine using an imprinted polymer-electrospray ionization ion mobility spectrometry system.

    PubMed

    Rezaei, B; Jafari, M T; Rahmanian, O

    2011-01-15

    In this research, selective separation and determination of phenazopyridine (PAP) is demonstrated using molecular imprinted polymer (MIP) coupled with electrospray ionization ion mobility spectrometry (ESI-IMS). In the non-covalent approach, selective MIP produced using PAP and methacrylic acid (MAA) as a template molecule and monomer, respectively. The created polymer is utilized as a media for solid-phase extraction (SPE), revealing selective binding properties for the analyte from pharmaceutical and serum samples. A coupled MIP-IMS makes it possible to quantitize PAP in the range of 1-100 ng mL(-1) and with a 0.2 ng mL(-1) detection limit. Furthermore, the MIP selectivity is evaluated by application of some substances with analogous and different molecular structures to that of PAP. This method is successfully applied for the determination of PAP in pharmaceutical and serum samples. PMID:21147318

  20. Express analysis of explosives, chemical warfare agents and drugs with multicapillary column gas chromatography and ion mobility increment spectrometry.

    PubMed

    Buryakov, Igor A

    2004-02-01

    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. PMID:14698239

  1. Changes in mobile phase ion distribution when combining pressurized flow and electric field.

    PubMed

    Eriksson, Björn O; Dahl, Magnus; Andersson, Magnus B O; Blomberg, Lars G

    2004-10-01

    The distribution of ions in a capillary with both pressurized flow and an electric field has been studied. We have earlier reported that the overall concentration of ions increase in a capillary with high electric field and a pressurized flow. Now we describe how the ions are distributed in the capillary both along the capillary length and in the radial direction as a result of the parabolic flow profile. We have combined current measurements with finite element techniques in order to get better understanding of the system. We have found that the concentration of the ions that because of the electric mobility moves towards the flow primarily increases at the beginning of the electric field and close to the capillary wall. In view of the results we have proposed an alterative explanation of earlier published results concerning voltage-induced variation in capacity factors. PMID:15472979

  2. Synergistic thermal stabilization of ceramic/co-polyimide coated polypropylene separators for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Yunju; Lee, Hoogil; Lee, Taejoo; Ryou, Myung-Hyun; Lee, Yong Min

    2015-10-01

    To improve the safety of lithium-ion batteries (LIBs), co-polyimide (PI) P84 was introduced as a polymeric binder for Al2O3/polymer composite surface coatings on polypropylene (PP) separators. By monitoring the dimensional shrinkage of the PP separators at high temperatures, we verified a synergistic thermal stabilization effect between the Al2O3 ceramic and the PI polymeric binder. Although PI was thermally stable up to 300 °C, a coating consisting solely of PI did not impede the PP separator dimensional changes (-22% at 150 °C). On the other hand, the Al2O3/PI-coated PP separators efficiently impeded the thermal shrinkage (-10% at 150 °C). In contrast, an Al2O3/poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) combination lowered the thermal stability of the PP separators (-33% at 150 °C). As a result, the Al2O3/PI-coated PP separators remarkably suppressed the internal short-circuit of the unit half-cells associated with separator thermal shrinkage (100 min at 160 °C), whereas the PVdF-HFP retained only 40 min under identical conditions. The Al2O3/PI-coated PP separators achieved rate capabilities and cell performances similar to those of the bare PP separators.

  3. Thermomechanical analysis and durability of commercial micro-porous polymer Li-ion battery separators

    NASA Astrophysics Data System (ADS)

    Love, Corey T.

    2011-03-01

    Static and dynamic thermomechanical analysis was performed with a dynamic mechanical analyzer (DMA) to identify thermal and mechanical transitions for commercially available polymer separators under mechanical loading. Clear transitions in deformation mode were observed at elevated temperatures. These transitions identified the onset of separator "shutdown" which occurred at temperatures below the polymer melting point. Mechanical loading direction was critical to the overall integrity of the separator. Anisotropic separators (Celgard 2320, 2400 and 2500) were mechanically limited when pulled in tensile in the transverse direction. The anisotropy of these separators is a result of the dry technique used to manufacture the micro-porous membranes. Separators prepared using the wet technique (Entek Gold LP) behaved more uniformly, or biaxially, where all mechanical properties were nearly identical within the separator plane. The information provided by the DMA can also be useful for predicting the long-term durability of polymer separators in lithium-ion batteries exposed to electrolyte (solvent and salt), thermal fluctuations and electrochemical cycling. Small losses in mechanical integrity were observed for separators exposed to the various immersion environments over the 4-week immersion time.

  4. A Critical Review of Ion Mobility Spectrometry for the Detection of Explosives and Explosive Related Compounds

    SciTech Connect

    Ewing, Robert Gordon; Atkinson, David Alan; Eiceman, G. A.; Ewing, G. J.

    2001-05-01

    Ion mobility spectrometry has become the most successful and widely used technology for the detection of trace levels of nitro-organic explosives on handbags and carry on-luggage in airports throughout the US. The low detection limits are provided by the efficient ionization process, namely, atmospheric pressure chemical ionization (APCI) reactions in negative polarity. An additional level of confidence in a measurement is imparted by characterization of ions for mobilities in weak electric fields of a drift tube at ambient pressure. Findings from over 30 years of investigations into IMS response to these explosives have been collected and assessed to allow a comprehensive view of the APCI reactions characteristic of nitro-organic explosives. Also, the drift tube conditions needed to obtain particular mobility spectra have been summarized. During the past decade, improvements have occurred in IMS on the understanding of reagent gas chemistries, the influence of temperature on ion stability, and sampling methods. In addition, commercial instruments have been refined to provide fast and reliable measurements for on-site detection of explosives. The gas phase ion chemistry of most explosives is mediated by the fragile C---ONO2 bonds or the acidity of protons. Thus, M- or M·Cl- species are found with only a few explosives and loss of NO2, NO3 and proton abstraction reactions are common and complicating pathways. However, once ions are formed, they appear to have stabilities on time scales equal to or longer than ion drift times from 5–20 ms. As such, peak shapes in IMS are suitable for high selectivity and sensitivity.

  5. Diurnal variation in the concentration of air ions of different mobility classes in a rural area

    NASA Astrophysics Data System (ADS)

    Hõrrak, Urmas; Salm, Jaan; Tammet, Hannes

    2003-10-01

    Analyzed data consist of 8900 hourly average mobility distributions measured in the mobility range of 0.00041-3.2 cm2 V-1 s-1 (diameter range 0.36-79 nm) at Tahkuse Observatory, Estonia, in 1993-1994. The average diurnal variation in the concentration of cluster ions is typical for continental stations: the maximum in the early morning hours and the minimum in the afternoon. This is explained by variations in radon concentration. The diurnal variation for big cluster ions (0.5-1.3 cm2 V-1 s-1) differs from that for small cluster ions (1.3-3.14 cm2 V-1 s-1). The size distribution of intermediate and light large ions in the range of 1.6-22 nm is strongly affected by nucleation bursts of nanometer particles. On the burst days, the maximum concentration of intermediate ions (1.6-7.4 nm) is about the noontime and that of light large ions (7.4-22 nm) about 2 hours later. The concentration of heavy large ions (charged Aitken particles of diameters of 22-79 nm) is enhanced in the afternoon and this is explained by the bursts of nanometer particles and the subsequent growth of particles by condensation and coagulation. If the burst days are excluded, then in the warm season the concentration of Aitken particles increases during night. In the cold season, the diurnal variation is different and all the classes of aerosol ions (2.1-79 nm) show similar variation with the minimum at 0600 LT and the maximum in the afternoon; exceptions are the rare nucleation burst days.

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

    PubMed

    Lee, Jihyeon; Park, Sehwan; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sung-Suk; Kim, Jeongkwon

    2014-03-01

    Corona discharge ionization combined with ion mobility spectrometry-mass spectrometry (IMS-MS) was utilized to investigate five common explosives: cyclonite (RDX), trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotetramethylenetetranitramine (HMX), and 2,4-dinitrotoluene (DNT). The MS scan and the selected ion IMS analyses confirmed the identities of the existing ion species and their drift times. The ions observed were RDX·NO3(-), TNT(-), PETN·NO3(-), HMX·NO3(-), and DNT(-), with average drift times of 6.93 ms, 10.20 ms, 9.15 ms, 12.24 ms, 11.30 ms, and 8.89 ms, respectively. The reduced ion mobility values, determined from a standard curve calculated by linear regression of (normalized drift times)(-1) versus literature K0 values, were 2.09, 1.38, 1.55, 1.15, 1.25, and 1.60 cm(2) V(-1) s(-1), respectively. The detection limits were found to be 0.1 ng for RDX, 10 ng for TNT, 0.5 ng for PETN, 5.0 ng for HMX, and 10 ng for DNT. Simplified chromatograms were observed when nitrogen, as opposed to air, was used as the drift gas, but the detection limits were approximately 10 times worse (i.e., less sensitivity of detection). PMID:24468343

  7. Linking molecular models with ion mobility experiments. Illustration with a rigid nucleic acid structure

    PubMed Central

    D'Atri, Valentina; Porrini, Massimiliano; Rosu, Frédéric; Gabelica, Valérie

    2015-01-01

    Ion mobility spectrometry experiments allow the mass spectrometrist to determine an ion's rotationally averaged collision cross section ΩEXP. Molecular modelling is used to visualize what ion three-dimensional structure(s) is(are) compatible with the experiment. The collision cross sections of candidate molecular models have to be calculated, and the resulting ΩCALC are compared with the experimental data. Researchers who want to apply this strategy to a new type of molecule face many questions: (1) What experimental error is associated with ΩEXP determination, and how to estimate it (in particular when using a calibration for traveling wave ion guides)? (2) How to generate plausible 3D models in the gas phase? (3) Different collision cross section calculation models exist, which have been developed for other analytes than mine. Which one(s) can I apply to my systems? To apply ion mobility spectrometry to nucleic acid structural characterization, we explored each of these questions using a rigid structure which we know is preserved in the gas phase: the tetramolecular G-quadruplex [dTGGGGT]4, and we will present these detailed investigation in this tutorial. © 2015 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26259654

  8. Preparation of high-purity Cu films by non-mass separated ion beam deposition

    NASA Astrophysics Data System (ADS)

    Lim, J.-W.; Mimura, K.; Miyake, K.; Yamashita, M.; Isshiki, M.

    2003-05-01

    Cu films were deposited on Si(1 0 0) substrates by applying a negative substrate bias voltage using non-mass separated ion beam deposition (IBD) method. By the SIMS results with Cs + ion beam, the Cu film deposited at VS=0 V was found to contain more impurities than the Cu film deposited at VS=-50 V. On the other hand, from the SIMS results with O 2+ ion beam, it was found that elements which are easy to be positive ions such as B, Mg, Na, Al, K, Ca and Fe seem to be increased slightly as compared to the those of the Cu film deposited at VS=0 V. As a result, higher-purity Cu film deposited at VS=-50 V could be obtained in comparison with the film deposited at VS=0 V. The purification effect of the Cu film deposited at VS=-50 V was described in details.

  9. Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

    NASA Astrophysics Data System (ADS)

    Yang, Ruidong

    Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than

  10. Design and implementation of embedded ion mobility spectrometry instrument based on SOPC

    NASA Astrophysics Data System (ADS)

    Zhang, Genwei; Zhao, Jiang; Yang, Liu; Liu, Bo; Jiang, Yanwei; Yang, Jie

    2015-02-01

    On the hardware platform with single CYCLONE IV FPGA Chip based on SOPC technology, the control functions of IP cores of a Ion Mobility Spectrometry instrument was tested, including 32 bit Nios II soft-core processor, high-voltage module, ion gate switch, gas flow, temperature and pressure sensors, signal acquisition and communication protocol. Embedded operating system μCLinux was successfully transplanted to the hardware platform, used to schedule all the tasks, such as system initialization, parameter setting, signal processing, recognition algorithm and results display. The system was validated using the IMS diagram of Acetone reagent, and the instrument was proved to have a strong signal resolution.

  11. Fragmentation of molecular ions in differential mobility spectrometry as a method for identification of chemical warfare agents.

    PubMed

    Maziejuk, M; Puton, J; Szyposzyńska, M; Witkiewicz, Z

    2015-11-01

    The subject of the work is the use of differential mobility spectrometry (DMS) for the detection of chemical warfare agents (CWA). Studies were performed for mustard gas, i.e., bis(2-chloroethyl)sulfide (HD), sarin, i.e., O-isopropyl methylphosphonofluoridate (GB) and