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Sample records for ion mobility separations

  1. Method and device for ion mobility separations

    DOEpatents

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

    2017-07-11

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

  2. Gas Phase Chiral Separations By Ion Mobility Spectrometry

    PubMed Central

    Dwivedi, Prabha; Wu, Ching; Hill, Herbert H.

    2013-01-01

    This manuscript introduces the concept of Chiral Ion Mobility Spectrometry (CIMS) and presents examples demonstrating the gas phase separation of enantiomers of a wide range of racemates including pharmaceuticals, amino acids and carbohydrates. CIMS is similar to traditional ion mobility spectrometry (IMS), where gas phase ions, when subjected to a potential gradient are separated at atmospheric pressure due to differences in their shapes and sizes. In addition to size and shape, CIMS separates ions based on their stereospecific interaction with a chiral gas. In order to achieve chiral discrimination by CIMS, an asymmetric environment was provided by doping the drift gas with a volatile chiral reagent. In this study S-(+)-2-butanol was used as a chiral modifier to demonstrate enantiomeric separations of atenolol, serine, methionine, threonine, methyl-α-glucopyranoside, glucose, penicillamine, valinol, phenylalanine, and tryptophan from their respective racemic mixtures. PMID:17165808

  3. 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).

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Isotopic effect on ion mobility and separation of isotopomers by high-field ion mobility spectrometry.

    PubMed

    Shvartsburg, Alexandre A; Clemmer, David E; Smith, Richard D

    2010-10-01

    Distinguishing and separating isotopic molecular variants is important across many scientific fields. However, discerning such variants, especially those producing no net mass difference, has been challenging. For example, single-stage mass spectrometry is broadly employed to analyze isotopes but is blind to isotopic isomers (isotopomers) and, except at very high resolution, species of the same nominal mass (isobars). Here, we report separation of isotopic ions, including isotopomers and isobars, using ion mobility spectrometry (IMS), specifically, the field asymmetric waveform IMS (FAIMS). The effect is not based on the different reduced masses of ion-gas molecule pairs previously theorized to cause isotopic separations in conventional IMS, but appears related to the details of energetic ion-molecule collisions in strong electric fields. The observed separation qualitatively depends on the gas composition and may be improved using gas mixtures. Isotopic shifts depend on the position of the labeled site, which allows its localization and contains information about the ion geometry, potentially enabling a new approach to molecular structure characterization.

  9. Isotopic Effect on Ion Mobility and Separation of Isotopomers by High-Field Ion Mobility Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.; Clemmer, David E.; Smith, Richard D.

    2010-10-01

    Since early 1900-s, when vacuum techniques and ion detectors first enabled investigations of gas-phase ions, two approaches to their separation and characterization have emerged - mass spectrometry (MS) and ion mobility spectrometry (IMS).1,2 Though both exploit that distinct charged species move in electric fields differently, MS is performed in vacuum and is based only on the ion mass/charge (m/q) ratio while IMS involves sufficiently dense buffer gases and relies on ion transport properties. The first major discovery enabled by MS was the existence of isotopes by Thomson and Aston,3 and isotopic analyses have since been integral to MS. In particular, the preparative separation of U isotopes using Lawrence’s Calutron was the first industrial application of MS,4 and isotopic labeling is key to MS quantification methods. With IMS, the issue of isotopes was largely ignored as the resolving power (R) was generally too low for their separation. Here, we demonstrate that recently developed high-resolution differential IMS can separate isotopic molecular ions, including nominal isobars with different isotopic content and isotopomers. This capability may enable a new method for isotope separation in a small-scale format at ambient pressure and aid localization of labeled sites in various molecules. Perhaps most importantly, the isotopic shifts depend on the labeled atom position and thus may contain the kind of detailed structural information that is available in solution or solid state using tools such as NMR but has not generally been obtainable for gas-phase ions.

  10. 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

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

    SciTech Connect

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

    2011-04-12

    Correlations between the dimensions of a 2-D separation create trend lines that normally depend on structural or functional 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 much less correlated to MS and thus should better separate the trend lines and associated domains. We report the first observation of chemical class separation by trend lines using FAIMS, here for lipids. For all 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 positions of fatty acid attachment can be resolved. These results open the door for lipidomics application of FAIMS, particularly shotgun lipidomics and targeted analyses of bioactive lipids.

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

    PubMed

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

    2017-06-26

    Differential ion mobility spectrometry (DIMS) devices separate ions on the basis of differences in ion mobility in low and high electric fields, and can be used as a stand-alone analytical method or as a separation step before further analysis. As with other ion mobility separation techniques, the ability of DIMS separations to retain the structural characteristics of analytes has been of concern. For DIMS separations, this potential loss of ion structure originates from the fact that the separations occur at atmospheric pressure and the ions, during their transit through the device, undergo repeated collisions with the DIMS carrier gas while being accelerated by the electric field. These collisions have the ability to increase the internal energy distribution of the ions, which can cause isomerization or fragmentation. The increase in internal energy of the ions is based on a number of variables, including the dispersion field and characteristics of the carrier gas such as temperature and composition. The effects of these parameters on the intra-DIMS fragmentation of multiply charged ions of the peptides bradykinin (RPPGFSPFR) and GLISH are discussed herein. Furthermore, similarities and differences in the internal energy deposition that occur during collisional activation in tandem mass spectrometry experiments are discussed, as the fragmentation pathways accessed by both are similar. Graphical Abstract ᅟ.

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

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

    PubMed

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

    2011-11-30

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

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

    DOE PAGES

    Hamid, Ahmed M.; Ibrahim, Yehia M.; Garimella, Venkata BS; ...

    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. 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.

  18. 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.

  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.

    2016-05-01

    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.

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

    SciTech Connect

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

    2016-11-02

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

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

    PubMed

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

    2016-12-06

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

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

    SciTech Connect

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

    2016-09-20

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

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

    PubMed Central

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

    2015-01-01

    Multidimensional high throughput separations are ideal for analyzing distinct ion characteristics simultaneously in one analysis. We report on 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 FAIMS compensation fields, IMS drift times, and accurate ion masses for the detected features. These separations thereby increased the overall measurement separation power, resulting in greater information content and more complete characterization of the 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 improving isomeric separations and allowing detection of species obscured by interfering peaks. PMID:26140287

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

    SciTech Connect

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

    2016-10-18

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

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

    PubMed

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

    2016-10-07

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

  6. 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.

  7. 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

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

    PubMed

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

    2013-06-01

    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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  11. 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

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

    SciTech Connect

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

    2016-07-01

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

  13. 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.

  14. Ion Separation in Air Using a Three-Dimensional Printed Ion Mobility Spectrometer.

    PubMed

    Hollerbach, Adam; Baird, Zane; Cooks, R Graham

    2017-05-02

    The performance of a small, plastic drift tube ion mobility spectrometer (DT-IMS) is described. The IMS was manufactured using three-dimensional (3D) printing techniques and operates in the open air at ambient pressure, temperature, and humidity. The IMS housing and electrodes were printed from nonconductive polylactic acid (PLA, housing) and conductive polyethylene terephthalate glycol-modified polymer containing multiwalled carbon nanotubes (PETG-CNT, electrodes). Ring electrodes consisting of both an inner disk and an outer ring were used to prevent neutral transmission while maximizing ion transmission. As a stand-alone instrument, the 3D printed IMS is shown to achieve resolving powers of between 24 and 50 in positive ion mode using tetraalkylammonium bromide salts (TAA), benzylamines (mono-, di-, and tri-), and illicit drugs (MA, MDEA, and haloperidol). Resolving powers of between 29 and 42 were achieved in negative ion mode using sodium alkyl sulfates (C8, C12, C16, and C18). Reduced ion mobilities of TAA cations (C2-C8) were calculated at 14% relative humidity in air to be 1.36, 1.18, 1.03, 0.90, 0.80, 0.73, and 0.67, respectively. The effect of humidity on reduced ion mobilities of TAA cations is discussed. 3D printing is shown to be a quick and cost-effective way to produce small IMS instruments that can compete in performance with conventionally manufactured IMS instruments that also operate in the open air. An important difference between this IMS and other instruments is the absence of a counter gas flow.

  15. 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

  16. Ion Mobility Separation of Isomeric Phosphopeptides from a Protein with Variant Modification of Adjacent Residues

    PubMed Central

    Singer, David; Smith, Richard D.; Hoffmann, Ralf

    2011-01-01

    Ion mobility spectrometry (IMS), and particularly differential or field asymmetric waveform IMS (FAIMS), was recently shown capable of separating post-translationally modified peptides with variant PTM localization. However, that work was limited to a model peptide with Ser phosphorylation on fairly distant alternative sites. Here, we demonstrate that FAIMS (coupled to ESI/MS) can broadly baseline-resolve variant phosphopeptides from a biologically modified human protein, including those involving phosphorylation of different residues and adjacent sites that challenge existing MS/MS methods most. Singly and doubly phosphorylated variants can be resolved equally well and identified without dissociation, based on accurate separation properties. The spectra change little over a range of infusion solvent pH, hence the present approach should be viable in conjunction with chromatographic separations using mobile phase gradients. PMID:21667994

  17. Variable-Velocity Traveling-Wave Ion Mobility Separation Enhancing Peak Capacity for Data-Independent Acquisition Proteomics.

    PubMed

    Haynes, Sarah E; Polasky, Daniel A; Dixit, Sugyan M; Majmudar, Jaimeen D; Neeson, Kieran; Ruotolo, Brandon T; Martin, Brent R

    2017-06-06

    High mass accuracy, data-dependent acquisition is the current standard method in mass spectrometry-based peptide annotation and quantification. In high complexity samples, limited instrument scan speeds often result in under-sampling. In contrast, all-ion data-independent acquisition methods bypass precursor selection, alternating high and low collision energies to analyze product and precursor ions across wide mass ranges. Despite capturing data for all events, peptide annotation is limited by inadequate alignment algorithms or overlapping ions. Ion mobility separation can add an orthogonal analytical dimension, reducing ion interference to improve reproducibility, peak capacity, and peptide identifications to rival modern hybrid quadrupole orbitrap systems. Despite the advantages of ion mobility separation in complex proteomics analyses, there has been no quantitative measure of ion mobility resolution in a complex proteomic sample. Here, we present TWIMExtract, a data extraction tool to export defined slices of liquid chromatography/ion mobility/mass spectrometry (LC-IM-MS) data, providing a route to quantify ion mobility resolution from a commercial traveling-wave ion mobility time-of-flight mass spectrometer. Using standard traveling-wave ion mobility parameters (600 m/s, 40 V), 90% of the annotated peptides occupied just 23% of the ion mobility drift space, yet inclusion of ion mobility nearly doubled the overall peak capacity. Relative to fixed velocity traveling-wave ion mobility settings, ramping the traveling-wave velocity increased drift space occupancy, amplifying resolution by 16%, peak capacity by nearly 50%, and peptide/protein identifications by 40%. Overall, variable-velocity traveling-wave ion mobility-mass spectrometry significantly enhances proteomics analysis in all-ion fragmentation acquisition.

  18. 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.

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

    DOE PAGES

    Baker, Erin Shammel; Burnum-Johnson, Kristin E.; Ibrahim, Yehia M.; ...

    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

  20. 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.

  1. 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

  2. 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.

  3. 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

    2011-09-07

    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.

  4. Separation and Identification of Isomeric Glycopeptides by High Field Asymmetric Waveform Ion Mobility Spectrometry

    PubMed Central

    2012-01-01

    The analysis of intact glycopeptides by mass spectrometry is challenging due to the numerous possibilities for isomerization, both within the attached glycan and the location of the modification on the peptide backbone. Here, we demonstrate that high field asymmetric wave ion mobility spectrometry (FAIMS), also known as differential ion mobility, is able to separate isomeric O-linked glycopeptides that have identical sequences but differing sites of glycosylation. Two glycopeptides from the glycoprotein mucin 5AC, GT(GalNAc)TPSPVPTTSTTSAP and GTTPSPVPTTST(GalNAc)TSAP (where GalNAc is O-linked N-acetylgalactosamine), were shown to coelute following reversed-phase liquid chromatography. However, FAIMS analysis of the glycopeptides revealed that the compensation voltage ranges in which the peptides were transmitted differed. Thus, it is possible at certain compensation voltages to completely separate the glycopeptides. Separation of the glycopeptides was confirmed by unique reporter ions produced by supplemental activation electron transfer dissociation mass spectrometry. These fragments also enable localization of the site of glycosylation. The results suggest that glycan position plays a key role in determining gas-phase glycopeptide structure and have implications for the application of FAIMS in glycoproteomics. PMID:22280549

  5. Preparation, Separation, and Conformational Analysis of Differentially Sulfated Heparin Octasaccharide Isomers using Ion Mobility Mass Spectrometry

    PubMed Central

    Seo, Youjin; Andaya, Armann; Leary, Julie A.

    2012-01-01

    Heparin is a linear sulfated polysaccharide widely used in medicine because of its anticoagulant properties. The various sulfation and/or acetylation patterns on heparin impart different degrees of conformational change around the glycosidic bonds and subsequently alter its function as an anticoagulant, anticancer, or antiviral drug. Characterization of these structures is important for eventual elucidation of its function but presents itself as an analytical challenge due to the inherent heterogeneity of the carbohydrates. Heparin octasaccharide structural isomers of various sulfation patterns were investigated using ion mobility mass spectrometry (IMMS). In addition to distinguishing the isomers, we report the preparation and tandem mass spectrometry analysis for multiple sulfated or acetylated oligosaccharides. Herein, our data indicate that heparin octasaccharide isomers were separated based on their structural conformations in the ion mobility cell. Subsequent to this separation, isomers were further distinguished using product ions resulting from tandem mass spectrometry. Overall, IMMS analysis was used to successfully characterize and separate individual isomers and subsequently measure their conformations. PMID:22283665

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

    PubMed

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

    2016-07-01

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

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

    PubMed Central

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

    2017-01-01

    We report on ion mobility (IM) separations achievable using traveling waves (TW) in a Structures for Lossless Ion Manipulations (SLIM) module having a 44 cm path length and 16 90° turns. The performance of the TW-SLIM module was evaluated for ion transmission and IM separations with different RF, TW parameters, and SLIM surface gaps in conjunction with mass spectrometry. In this work, TWs were created by the transient and dynamic application of DC potentials. The module demonstrated highly robust performance and, even with 16 closely spaced turns, achieving IM resolution performance and ion transmission comparable to a similar straight path module. We found an IM peak capacity of ~31 and peak generation rate of 780 s−1 for TW speeds of ~80 m/s using the current multi-turn TW-SLIM module. The separations achieved for isomers of peptides and tetrasaccharides were found to be comparable to those from a ~0.9-m drift tube-based IM-MS platform operated at the same pressure (4 Torr). The combined attributes of flexible design, low voltage requirements and lossless ion transmission through multiple turns for the present TW-SLIM module provides a basis for SLIM devices capable of achieving much greater IM resolution via greatly extended ion path lengths and using compact serpentine designs. PMID:27479234

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

    PubMed

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

    2016-09-20

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

  9. Structural separations by Ion Mobility-MS for Glycomics and Glycoproteomics

    PubMed Central

    Fenn, Larissa S.; McLean, John A.

    2016-01-01

    This chapter describes the utility of ion mobility-mass spectrometry (IM-MS) for the detection and characterization of glycoproteins and associated glycoconjugates. IM-MS provides separations in two dimensions, one on the basis of molecular surface area, or structure, and the other on molecular mass which creates the ability to differentiate biomolecular classes and isobaric species. When applied to the characterization of glycoproteins, IM-MS separates peptides from the associated glycans in the same digest without purification, and can also be used to separate different isomeric glycans which is a significant challenge in current glycomic studies. The chapter will detail the methodologies to use IM-MS for the study of glycans and glycoproteins for an audience ranging from new and potential practitioners to those already utilizing the technique. PMID:23296531

  10. 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

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

    PubMed

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

    2014-03-01

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

  12. UV photodissociation of trapped ions following ion mobility separation in a Q-ToF mass spectrometer.

    PubMed

    Bellina, Bruno; Brown, Jeffery M; Ujma, Jakub; Murray, Paul; Giles, Kevin; Morris, Michael; Compagnon, Isabelle; Barran, Perdita E

    2014-12-21

    An ion mobility mass spectrometer has been modified to allow optical interrogation of ions with different mass-to-charge (m/z) ratios and/or mobilities (K). An ion gating and trapping procedure has been developed which allows us to store ions for several seconds enabling UV photodissociation (UVPD).

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

    SciTech Connect

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

    2017-01-01

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

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

    PubMed

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

    2017-01-01

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

  15. 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

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

    PubMed

    Wojcik, Roza; Webb, Ian K; Deng, Liulin; Garimella, Sandilya V B; Prost, Spencer A; Ibrahim, Yehia M; Baker, Erin S; Smith, Richard D

    2017-01-18

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

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

    PubMed Central

    Wojcik, Roza; Webb, Ian K.; Deng, Liulin; Garimella, Sandilya V. B.; Prost, Spencer A.; Ibrahim, Yehia M.; Baker, Erin S.; Smith, Richard D.

    2017-01-01

    Understanding the biological roles and mechanisms of lipids and glycolipids is challenging due to the vast number of possible isomers that may exist. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid presence and changes. However, difficulties in distinguishing the many structural isomers, due to the distinct lipid acyl chain positions, double bond locations or specific glycan types, inhibit the delineation and assignment of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations by applying traveling waves in a serpentine multi-pass Structures for Lossless Ion Manipulations (SLIM) platform to enhance the separation of selected lipid and glycolipid isomers. The multi-pass arrangement allowed the investigation of paths ranging from ~16 m (one pass) to ~60 m (four passes) for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer-specific biological activities and disease processes. PMID:28106768

  18. 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.

  19. Lipid and glycolipid isomer analyses using ultra-high resolution ion mobility spectrometry separations

    DOE PAGES

    Wojcik, Roza; Webb, Ian K.; Deng, Liulin; ...

    2017-01-18

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

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

    SciTech Connect

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

    2016-09-07

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

  1. 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.

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

    PubMed Central

    Zheng, Xueyun; Wojcik, Roza; Zhang, Xing; Ibrahim, Yehia M.; Burnum-Johnson, Kristin E.; Orton, Daniel J.; Monroe, Matthew E.; Moore, Ronald J.; Smith, Richard D.; Baker, Erin S.

    2017-01-01

    Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. Though IMS alone is useful, its coupling with mass spectrometry (MS) and front-end separations is extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information available from biological and environmental sample analyses. In fact, multiple disease screening and environmental evaluations have illustrated that the IMS-based multidimensional separations extract information that cannot be acquired with each technique individually. This review highlights three-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography, supercritical fluid chromatography, liquid chromatography, solid-phase extractions, capillary electrophoresis, field asymmetric ion mobility spectrometry, and microfluidic devices. The origination, current state, various applications, and future capabilities of these multidimensional approaches are described in detail to provide insight into their uses and benefits. PMID:28301728

  3. 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.

  4. Surface-induced dissociation of ion mobility-separated noncovalent complexes in a quadrupole/time-of-flight mass spectrometer.

    PubMed

    Zhou, Mowei; Huang, Chengsi; Wysocki, Vicki H

    2012-07-17

    A custom in-line surface-induced dissociation (SID) device has been incorporated into a commercial ion mobility quadrupole/time-of-flight mass spectrometer in order to provide an alternative and potentially more informative activation method than the commonly used collision-induced dissociation (CID). Complicated sample mixtures can be fractionated by ion mobility (IM) and then dissociated by CID or SID for further structural analysis. Interpretation of SID spectra for cesium iodide clusters was greatly simplified with IM prior to dissociation because products originating from different precursors and overlapping in m/z but separated in drift time can be examined individually. Multiple conformations of two protein complexes, source-activated transthyretin tetramer and nativelike serum amyloid P decamer, were separated in ion mobility and subjected to CID and SID. CID spectra of the mobility separated conformations are similar. However, drastic differences can be observed for SID spectra of different conformations, implying different structures in the gas phase. This work highlights the potential of utilizing IM-SID to study quaternary structures of protein complexes and provides information that is complementary to our recently reported SID-IM approach.

  5. A multicomponent mobile phase for ion chromatography applied to the separation of anions from the residue of low explosives

    PubMed

    Doyle; Miller; McCord; McCollam; Mushrush

    2000-05-15

    A multicomponent mobile phase utilizing ion-exchange, ion-exclusion, and ion-pairing principles for the rapid isocratic separation of anions in low explosives residue by ion chromatography (IC) has been developed. The notable feature of this system is that an ion-pairing reagent and an ion-exclusion reagent are combined in the same mobile phase. Contrary to expectation, these reagents act independently of each other in solution. The stock mobile-phase composition consisted of boric acid, D-gluconic acid, lithium hydroxide, and glycerol. Tetrapropylammonium hydroxide, an ion-interaction reagent was used to achieve pH 8.5. Acetonitrile (ACN) was added to enhance resolution and octanesulfonic acid, an ion-exclusion reagent, was added to adjust the retention time of perchlorate. Separation of a mixture of anions common to low explosives residue was achieved in less than 16 min using a Waters IC-Pak Anion HR column. Optimization studies were performed by changing the concentration of the ACN and by altering the pH or the type of ion-interaction or -exclusion agents. Simulated case studies were performed using postblast residues from pipe bombs. The results show this method to be a valid and reproducible procedure for forensic casework analysis. The practical significance of this system is that a reduction in the analysis time and an improvement in efficiency of late-eluting peaks can be achieved without resorting to gradient elution techniques. For the analysis of anions detected in explosives residue, the Waters IC-Pak Anion HR column has proven to be a suitable replacement for the Vydac 300IC405 column, which has been discontinued by the manufacturer.

  6. Ion mobility spectrometry as a detector for molecular imprinted polymer separation and metronidazole determination in pharmaceutical and human serum samples.

    PubMed

    Jafari, M T; Rezaei, B; Zaker, B

    2009-05-01

    Application of ion mobility spectrometry (IMS) as the detection technique for a separation method based on molecular imprinted polymer (MIP) was investigated and evaluated for the first time. On the basis of the results obtained in this work, the MIP-IMS system can be used as a powerful technique for separation, preconcentration, and detection of the metronidazole drug in pharmaceutical and human serum samples. The method is exhaustively validated in terms of sensitivity, selectivity, recovery, reproducibility, and column capacity. The linear dynamic range of 0.05-70.00 microg/mL was obtained for the determination of metronidazole with IMS. The recovery of analyzed drug was calculated to be above 89%, and the relative standard deviation (RSD) was lower than 6% for all experiments. Various real samples were analyzed with the coupled techniques, and the results obtained revealed the efficient cleanup of the samples using MIP separation before the analysis by IMS as a detection technique.

  7. 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.

  8. Targeted high-resolution ion mobility separation coupled to ultrahigh-resolution mass spectrometry of endocrine disruptors in complex mixtures.

    PubMed

    Benigni, Paolo; Thompson, Christopher J; Ridgeway, Mark E; Park, Melvin A; Fernandez-Lima, Francisco

    2015-04-21

    Traditional separation and detection of targeted compounds from complex mixtures from environmental matrices requires the use of lengthy prefractionation steps and high-resolution mass analyzers due to the large number of chemical components and their large structural diversity (highly isomeric). In the present work, selected accumulation trapped ion mobility spectrometry (SA-TIMS) is coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct separation and characterization of targeted endocrine-disrupting compounds (EDC) from a complex environmental matrix in a single analysis. In particular, targeted identification based on high-resolution mobility (R ∼ 70-120) and ultrahigh-resolution mass measurements (R > 400 000) of seven commonly targeted EDC and their isobars (e.g., bisphenol A, (Z)- and (E)-diethylstilbestrol, hexestrol, estrone, α-estradiol, and 17-ethynylestradiol) is shown from a complex mixture of water-soluble organic matter (e.g., Suwannee River Fulvic Acid Standard II) complemented with reference standard measurements and theoretical calculations (<3% error).

  9. Energy-Resolved Ion Mobility-Mass Spectrometry—A Concept to Improve the Separation of Isomeric Carbohydrates

    NASA Astrophysics Data System (ADS)

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3 %. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  10. Energy-resolved ion mobility-mass spectrometry--a concept to improve the separation of isomeric carbohydrates.

    PubMed

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3%. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  11. Three-dimensional enhanced lipidomics analysis combining UPLC, differential ion mobility spectrometry, and mass spectrometric separation strategies1[S

    PubMed Central

    Baker, Paul R. S.; Armando, Aaron M.; Campbell, J. Larry; Quehenberger, Oswald; Dennis, Edward A.

    2014-01-01

    Phospholipids serve as central structural components in cellular membranes and as potent mediators in numerous signaling pathways. There are six main classes of naturally occurring phospholipids distinguished by their distinct polar head groups that contain many unique molecular species with distinct fatty acid composition. Phospholipid molecular species are often expressed as isobaric species that are denoted by the phospholipid class and the total number of carbon atoms and double bonds contained in the esterified fatty acyl groups (e.g., phosphatidylcholine 34:2). Techniques to separate these molecules exist, and each has positive and negative attributes. Hydrophilic interaction liquid chromatography uses polar bonded silica to separate lipids by polar head group but not by specific molecular species. Reversed phase (RP) chromatography can separate by fatty acyl chain composition but not by polar head group. Herein we describe a new strategy called differential ion mobility spectrometry (DMS), which separates phospholipid classes by their polar head group. Combining DMS with current LC methods enhances phospholipid separation by increasing resolution, specificity, and signal-to-noise ratio. Additional application of specialized information-dependent acquisition methodologies along with RP chromatography allows full isobaric resolution, identification, and compositional characterization of specific phospholipids at the molecular level. PMID:25225680

  12. Three-dimensional enhanced lipidomics analysis combining UPLC, differential ion mobility spectrometry, and mass spectrometric separation strategies.

    PubMed

    Baker, Paul R S; Armando, Aaron M; Campbell, J Larry; Quehenberger, Oswald; Dennis, Edward A

    2014-11-01

    Phospholipids serve as central structural components in cellular membranes and as potent mediators in numerous signaling pathways. There are six main classes of naturally occurring phospholipids distinguished by their distinct polar head groups that contain many unique molecular species with distinct fatty acid composition. Phospholipid molecular species are often expressed as isobaric species that are denoted by the phospholipid class and the total number of carbon atoms and double bonds contained in the esterified fatty acyl groups (e.g., phosphatidylcholine 34:2). Techniques to separate these molecules exist, and each has positive and negative attributes. Hydrophilic interaction liquid chromatography uses polar bonded silica to separate lipids by polar head group but not by specific molecular species. Reversed phase (RP) chromatography can separate by fatty acyl chain composition but not by polar head group. Herein we describe a new strategy called differential ion mobility spectrometry (DMS), which separates phospholipid classes by their polar head group. Combining DMS with current LC methods enhances phospholipid separation by increasing resolution, specificity, and signal-to-noise ratio. Additional application of specialized information-dependent acquisition methodologies along with RP chromatography allows full isobaric resolution, identification, and compositional characterization of specific phospholipids at the molecular level. Copyright © 2014 by the American Society for Biochemistry and Molecular Biology, Inc.

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

    PubMed

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

    2016-09-20

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

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

    SciTech Connect

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

    2016-09-20

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

  15. Enhancement of biological mass spectrometry by using separations based on changes in ion mobility (FAIMS and DMS).

    PubMed

    Purves, Randy W

    2013-01-01

    Analysis of complex biological samples for low-level analytes by liquid chromatography-tandem mass spectrometry (LC-MS/MS) often requires additional selectivity. Differential mobility techniques (FAIMS and DMS) have been shown to enhance LC-MS/MS analyses by separating ions in the gas-phase on a millisecond timescale by use of a mechanism that is complementary to both liquid chromatography and mass spectrometry. In this overview, a simplified description of the operation of these devices is given and an example presented that illustrates the utility of FAIMS (DMS) for solving a challenging analytical assay. Important recent advances in the field, including work with gas modifiers, are presented, along with an outlook for the technology.

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

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

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

  17. 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.

  18. 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.

  19. Ultrahigh-resolution differential ion mobility separations of conformers for proteins above 10 kDa: onset of dipole alignment?

    PubMed

    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 or field asymmetric waveform IMS (FAIMS) approach using hydrogen-rich gases was recently found to separate conformers of a small protein ubiquitin with the same peak width and resolving power up to ∼400 as for peptides. The 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 the present technique to proteins under ∼20 kDa. This capability may enable one to distinguish whole proteins with differing residue sequences or localizations of post-translational 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.

  20. 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.

  1. 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.

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

    SciTech Connect

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

    2015-09-09

    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. In this paper, 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

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

    DOE PAGES

    Li, Hang; Ha, Emmeline; Donaldson, Robert P.; ...

    2015-09-09

    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 pancreasmore » 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. In this paper, 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

  4. 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

    2015-10-06

    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

  5. Collision-Induced Release, Ion Mobility Separation, and Amino Acid Sequence Analysis of Subunits from Mass-Selected Noncovalent Protein Complexes

    NASA Astrophysics Data System (ADS)

    Rathore, Deepali; Dodds, Eric D.

    2014-09-01

    In recent years, mass spectrometry has become a valuable tool for detecting and characterizing protein-protein interactions and for measuring the masses and subunit stoichiometries of noncovalent protein complexes. The gas-phase dissociation of noncovalent protein assemblies via tandem mass spectrometry can be useful in confirming subunit masses and stoichiometries; however, dissociation experiments that are able to yield subunit sequence information must usually be conducted separately. Here, we furnish proof of concept for a method that allows subunit sequence information to be directly obtained from a protein aggregate in a single gas-phase analysis. The experiments were carried out using a quadrupole time-of-flight mass spectrometer equipped with a traveling-wave ion mobility separator. This instrument configuration allows for a noncovalent protein assembly to be quadrupole selected, then subjected to two successive rounds of collision-induced dissociation with an intervening stage of ion mobility separation. This approach was applied to four model proteins as their corresponding homodimers: glucagon, ubiquitin, cytochrome c, and β-lactoglobulin. In each case, b- and y-type fragment ions were obtained upon further collisional activation of the collisionally-released subunits, resulting in up to 50% sequence coverage. Owing to the incorporation of an ion mobility separation, these results also suggest the intriguing possibility of measuring complex mass, complex collisional cross section, subunit masses, subunit collisional cross sections, and sequence information for the subunits in a single gas-phase experiment. Overall, these findings represent a significant contribution towards the realization of protein interactomic analyses, which begin with native complexes and directly yield subunit identities.

  6. Collision-induced release, ion mobility separation, and amino acid sequence analysis of subunits from mass-selected noncovalent protein complexes.

    PubMed

    Rathore, Deepali; Dodds, Eric D

    2014-09-01

    In recent years, mass spectrometry has become a valuable tool for detecting and characterizing protein-protein interactions and for measuring the masses and subunit stoichiometries of noncovalent protein complexes. The gas-phase dissociation of noncovalent protein assemblies via tandem mass spectrometry can be useful in confirming subunit masses and stoichiometries; however, dissociation experiments that are able to yield subunit sequence information must usually be conducted separately. Here, we furnish proof of concept for a method that allows subunit sequence information to be directly obtained from a protein aggregate in a single gas-phase analysis. The experiments were carried out using a quadrupole time-of-flight mass spectrometer equipped with a traveling-wave ion mobility separator. This instrument configuration allows for a noncovalent protein assembly to be quadrupole selected, then subjected to two successive rounds of collision-induced dissociation with an intervening stage of ion mobility separation. This approach was applied to four model proteins as their corresponding homodimers: glucagon, ubiquitin, cytochrome c, and β-lactoglobulin. In each case, b- and y-type fragment ions were obtained upon further collisional activation of the collisionally-released subunits, resulting in up to 50% sequence coverage. Owing to the incorporation of an ion mobility separation, these results also suggest the intriguing possibility of measuring complex mass, complex collisional cross section, subunit masses, subunit collisional cross sections, and sequence information for the subunits in a single gas-phase experiment. Overall, these findings represent a significant contribution towards the realization of protein interactomic analyses, which begin with native complexes and directly yield subunit identities.

  7. Miniaturized Ion Mobility Spectrometer

    NASA Technical Reports Server (NTRS)

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

    2017-01-01

    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 (IMS) 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 degrees Centigrade, and is uniquely sensitive, particularly to explosive chemicals.

  8. 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.

  9. 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

  10. Evaluating the separation of amphetamines by electrospray ionization ion mobility spectrometry/MS and charge competition within the ESI process.

    PubMed

    Matz, Laura M; Hill, Herbert H

    2002-01-15

    The rapid increase in amphetamine abuse for recreational purposes has created a need for fast analysis and detection methodologies. For the first time, we show the separation of six amphetamines by ESI-IMS/MS. A complete analysis can be performed in 70 s, which is faster than traditional chromatographic techniques. In addition, ESI-IMS/MS was found to provide low detection limits for the six compounds (15.4 ppb for ethylamphetamine). Charge competition between amphetamines was found to occur at high amphetamine concentrations. The degree of preferential ionization was dependent on the functional group placed on the amine. Both one-analyte and two-analyte calibration curves were evaluated on the basis of the ion evaporation model. Evaporation rates were determined for the six amphetamines, and the rates were correlated with the degree of selective ionization. Evaluation of three typical ESI solvent compositions showed that the addition of a modifier (acetic acid and formic acid) enhanced the degree of preferential ionization for some amphetamines and increased the effect of charge competition. The solvent studies show the complexity of ESI and provide possible strategies for altering the amount of charge competition between analytes. Overall, ESI-IMS/MS appears to be a promising technique because of its sensitivity and rapid separation times for the amphetamines in aqueous samples; however, further research employing biological samples is required before it can be recommended as a mainstream technique.

  11. Mass analysis of mobility-selected ion populations using dual gate, ion mobility, quadrupole ion trap mass spectrometry.

    PubMed

    Clowers, Brian H; Hill, Herbert H

    2005-09-15

    An electrospray ionization, dual gate, ion mobility, quadrupole ion trap mass spectrometer (ESI-DG-IM-QIT-MS) was constructed and evaluated for its ability to select mobility-filtered ions prior to mass analysis. While modification of the common signal-averaged ion mobility experiment was required, no modifications to the QIT were necessary. The dual gate scanning mode of operation was used to acquire mobility spectra, whereas the single mobility monitoring experiment selectively filtered ions for concentration and subsequent fragmentation within the QIT. Ion mobility separation of positively charged peptides and negatively charged carbohydrates, followed by MS fragmentation, was demonstrated. For a 1-min acquisition time, it was possible to obtain complete de novo sequence information for the examined peptides. Fragmentation of the negative carbohydrate chlorine adducts yielded ions characteristic of cross-ring and glycosidic bond cleavage. Previous unions of atmospheric pressure ion mobility and mass spectrometry have been limited in their ability to reproducibly obtain MSn data for mobility separation ions. The union of high-pressure ion mobility with quadrupole ion trap mass spectrometry presents the unique opportunity to obtain more detailed information regarding the chemistries of gas-phase ions.

  12. Fundamentals of traveling wave ion mobility spectrometry.

    PubMed

    Shvartsburg, Alexandre A; Smith, Richard D

    2008-12-15

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

  13. 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.

  14. 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.

  15. 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.

  16. Fundamentals of trapped ion mobility spectrometry.

    PubMed

    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.

  17. 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

  18. Multiple enzymatic digestions and ion mobility separation improve quantification of bacterial ribosomal proteins by data independent acquisition liquid chromatography-mass spectrometry.

    PubMed

    Dator, Romel P; Gaston, Kirk W; Limbach, Patrick A

    2014-05-06

    Mass spectrometry-based quantification of ribosomal proteins (r-proteins) associated with mature ribosomes and ribosome assembly complexes is typically accomplished by relative quantification strategies. These strategies provide information on the relative stoichiometry of proteins within the complex compared to a wild-type strain. Here we have evaluated the applicability of a label-free approach, enhanced liquid chromatography-mass spectrometry (LC-MS(E)), for absolute "ribosome-centric" quantification of r-proteins in Escherichia coli mature ribosomes. Because the information obtained in this experiment is related to the number of peptides identified per protein, experimental conditions that allow accurate and reproducible quantification of r-proteins were found. Using an additional dimension of gas-phase separation through ion mobility and the use of multiple endoproteinase digestion significantly improved quantification of proteins associated with mature ribosomes. The actively translating ribosomes (polysomes) contain amounts of proteins consistent with their known stoichiometry within the complex. These measurements exhibited technical and biological reproducibilities at %CV less than 15% and 35%, respectively. The improved LC-MS(E) approach described here can be used to characterize in vivo ribosome assembly complexes captured during ribosome biogenesis and assembly under different perturbations (e.g., antibiotics, deletion mutants of assembly factors, oxidative stress, nutrient deprivation). Quantitative analysis of these captured complexes will provide information relating to the interplay and dynamics of how these perturbations interfere with the assembly process.

  19. 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.

  20. 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.

  1. The mobility and diffusion of ions in gases

    NASA Technical Reports Server (NTRS)

    Mcdaniel, E. W.; Mason, E. A.

    1973-01-01

    Experimental and theoretical aspects of the mobility and diffusion of ions in gases are studied in detail. Some of the subjects discussed include ion-ion interaction, boundary condition and ion and electron behavior. Also discussed in separate chapters are the problems of the diffusion coefficients and the afterglow techniques. Finally, a special chapter studies the kinetic theory of diffusion and mobility, stressing the low-, medium- and high-field theory.

  2. Correlation ion mobility spectrometry.

    PubMed

    Davis, Austen L; Liu, Wenjie; Siems, William F; Clowers, Brian H

    2017-01-16

    Using a linearly swept chirp function to modulate a Bradbury-Nielsen (BN) ion gate and application of a common signal processing technique (cross-correlation), we outline a method for obtaining high resolution IMS-MS spectra with ion gate duty cycles approaching 50%. Correlation IMS (CIMS) offers advantages over current multiplexing approaches in IMS-MS, which include the Hadamard and Fourier transforms, by minimizing transform artifacts while maintaining high ion throughput. Although cross-correlation techniques have been utilized previously in the field of IMS, to the best of our knowledge, this approach has not been utilized to obtain spectrum that resembles traditional IMS spectrum with resolving powers approaching the theoretical limit. This new approach relies on a linear sweep, which is a swept frequency signal, commonly utilized in different applications because of its compatibility with the fast Fourier transform (FFT). However, unlike spectra derived from Fourier transformation, CIMS yields data sampling rates that are not dependent upon terminal frequency and takes advantage of several factors unique to IMS operation; the non-linear response of ions at relatively low gate pulse widths, fluctuations in intensity, and peak profiles resembling the input gate pulse vector observed especially noted at low gating frequencies.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

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

    PubMed

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

    2014-12-01

    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.

  5. 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.

  6. Maximizing Ion Transmission in Differential Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Schneider, Bradley B.; Londry, Frank; Nazarov, Erkinjon G.; Kang, Yang; Covey, Thomas R.

    2017-06-01

    We provide modeling and experimental data describing the dominant ion-loss mechanisms for differential mobility spectrometry (DMS). Ion motion is considered from the inlet region of the mobility analyzer to the DMS exit, and losses resulting from diffusion to electrode surfaces, insufficient effective gap, ion fragmentation, and fringing field effects are considered for a commercial DMS system with 1-mm gap height. It is shown that losses due to diffusion and radial oscillations can be minimized with careful consideration of residence time, electrode spacing, gas flow rate, and waveform frequency. Fragmentation effects can be minimized by limitation of the separation field. When these parameters were optimized, fringing field effects at the DMS inlet contributed the most to signal reduction. We also describe a new DMS cell configuration that improves the gas dynamics at the mobility cell inlet. The new cell provides a gas jet that decreases the residence time for ions within the fringing field region, resulting in at least twofold increase in ion signal as determined by experimental data and simulations.

  7. Maximizing Ion Transmission in Differential Mobility Spectrometry.

    PubMed

    Schneider, Bradley B; Londry, Frank; Nazarov, Erkinjon G; Kang, Yang; Covey, Thomas R

    2017-06-29

    We provide modeling and experimental data describing the dominant ion-loss mechanisms for differential mobility spectrometry (DMS). Ion motion is considered from the inlet region of the mobility analyzer to the DMS exit, and losses resulting from diffusion to electrode surfaces, insufficient effective gap, ion fragmentation, and fringing field effects are considered for a commercial DMS system with 1-mm gap height. It is shown that losses due to diffusion and radial oscillations can be minimized with careful consideration of residence time, electrode spacing, gas flow rate, and waveform frequency. Fragmentation effects can be minimized by limitation of the separation field. When these parameters were optimized, fringing field effects at the DMS inlet contributed the most to signal reduction. We also describe a new DMS cell configuration that improves the gas dynamics at the mobility cell inlet. The new cell provides a gas jet that decreases the residence time for ions within the fringing field region, resulting in at least twofold increase in ion signal as determined by experimental data and simulations. Graphical Abstract ᅟ.

  8. Maximizing Ion Transmission in Differential Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Schneider, Bradley B.; Londry, Frank; Nazarov, Erkinjon G.; Kang, Yang; Covey, Thomas R.

    2017-10-01

    We provide modeling and experimental data describing the dominant ion-loss mechanisms for differential mobility spectrometry (DMS). Ion motion is considered from the inlet region of the mobility analyzer to the DMS exit, and losses resulting from diffusion to electrode surfaces, insufficient effective gap, ion fragmentation, and fringing field effects are considered for a commercial DMS system with 1-mm gap height. It is shown that losses due to diffusion and radial oscillations can be minimized with careful consideration of residence time, electrode spacing, gas flow rate, and waveform frequency. Fragmentation effects can be minimized by limitation of the separation field. When these parameters were optimized, fringing field effects at the DMS inlet contributed the most to signal reduction. We also describe a new DMS cell configuration that improves the gas dynamics at the mobility cell inlet. The new cell provides a gas jet that decreases the residence time for ions within the fringing field region, resulting in at least twofold increase in ion signal as determined by experimental data and simulations. [Figure not available: see fulltext.

  9. 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

  10. Biomolecule Analysis by Ion Mobility Spectrometry

    PubMed Central

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

    2013-01-01

    Although nonnative protein conformations, including intermediates along the folding pathway and kinetically trapped misfolded species that disfavor the native state, are rarely isolated in the solution phase, they are often stable in the gas phase, where macromolecular ions from electrospray ionization can exist in varying charge states. Differences in the structures of nonnative conformations in the gas phase are often large enough to allow different shapes and charge states to be separated because of differences in their mobilities through a gas. Moreover, gentle collisional activation can be used to induce structural transformations. These new structures often have different mobilities. Thus, there is the possibility of developing a multidimensional separation that takes advantage of structural differences of multiple stable states. This review discusses how nonnative states differ in the gas phase compared with solution and presents an overview of early attempts to utilize and manipulate structures in order to develop ion mobility spectrometry as a rapid and sensitive technique for separating complex mixtures of biomolecules prior to mass spectrometry. PMID:20636082

  11. 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

  12. Direct determination of 2,4,6-tricholoroanisole in wines by single-drop ionic liquid microextraction coupled with multicapillary column separation and ion mobility spectrometry detection.

    PubMed

    Márquez-Sillero, Isabel; Cárdenas, Soledad; Valcárcel, Miguel

    2011-10-21

    This article evaluates the capability of single drop ionic liquid microextraction coupled with multicapillary column (MCC) and ion mobility spectrometry (IMS) for the determination of 2,4,6-trichloroanisole (2,4,6-TCA) in wines. The proposed methodology permits the direct analysis of the samples without any additional treatment other than dilution. This is achieved thanks to the selectivity provided by the ionic liquid selected as extractant, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide, as well as the response of the analyte in the IMS working in negative ionization mode. Moreover, the multicapillary column avoids the interference of ethanol in the ion mobility spectra. The analysis of the sample takes ca. 35 min to be completed. The limit of detection was low as 0.01 ng L(-1) using 2 mL of wine sample. Different calibration curves were constructed using aqueous standards, red and white wines, being the signals comparable, with an RSD similar to the method variability. Finally, a set of samples of different nature and packed in different containers were analysed. It was found than those with cork stoppers presented the highest concentration of 2,4,6-TCA. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Buffer Gas Modifiers Effect Resolution in Ion Mobility Spectrometry through Selective Ion-Molecule Clustering Reactions

    PubMed Central

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

    2013-01-01

    RATIONALE When polar molecules (modifiers) are introduced into the buffer gas of an ion mobility spectrometer, most ion mobilities decrease due to the formation of ion-modifier clusters. METHODS We used ethyl lactate, nitrobenzene, 2-butanol, and tetrahydrofuran-2-carbonitrile as buffer gas modifiers and electrospray ionization ion mobility spectrometry (IMS) coupled to quadrupole mass spectrometry. Ethyl lactate, nitrobenzene, and tetrahydrofuran-2-carbonitrile had not been tested as buffer gas modifiers and 2-butanol had not been used with basic amino acids. RESULTS The ion mobilities of several diamines (arginine, histidine, lysine, and atenolol) were not affected or only slightly reduced when these modifiers were introduced into the buffer gas (3.4% average reduction in an analyte's mobility for the three modifiers). Intramolecular bridges caused limited change in the ion mobilities of diamines when modifiers were added to the buffer gas; these bridges hindered the attachment of modifier molecules to the positive charge of ions and delocalized the charge, which deterred clustering. There was also a tendency towards large changes in ion mobility when the mass of the analyte decreased; ethanolamine, the smallest compound tested, had the largest reduction in ion mobility with the introduction of modifiers into the buffer gas (61%). These differences in mobilities, together with the lack of shift in bridge-forming ions, were used to separate ions that overlapped in IMS, such as isoleucine and lysine, and arginine and phenylalanine, and made possible the prediction of separation or not of overlapping ions. CONCLUSIONS The introduction of modifiers into the buffer gas in IMS can selectively alter the mobilities of analytes to aid in compound identification and/or enable the separation of overlapping analyte peaks. PMID:22956312

  14. Two-Dimensional Ion Mobility Analyses of Proteins and Peptides

    SciTech Connect

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

    2008-09-01

    INTRODUCTION-Analytical methods based on ion transport in gases under the influence of electric field, known collectively as Ion Mobility Spectrometry (IMS), add major new capabilities to mass-spectrometric (MS) investigations. Separation of ion mixtures and characterization of ions by IMS are of particular utility in biological MS, where the sample complexity creates a virtually open-ended demand for separation power (1) while the ion size normally rules out structural elucidation by spectroscopic means. The use of IMS in mass spectrometry of proteins and peptides has expanded dramatically since the previous edition of this volume in 2000...

  15. 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"…

  16. 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"…

  17. Mothers' Mobility after Separation: Do Grandmothers Matter?

    PubMed Central

    de Valk, Helga; Merz, Eva‐Maria

    2016-01-01

    Abstract Starting from a life course perspective, this study aims to gain more insight into mobility patterns of recently separated mothers, focusing especially on moves to the location of their own mother: the maternal grandmother. Separated mothers, having linked lives with their own mothers, may benefit from their practical and emotional support. Additionally, the grandparents' home can be a (temporary) place to stay shortly after divorce. Data come from the System of social statistical datasets (Statistics Netherlands). This unique dataset combines longitudinal data from a vast number of administrative registers. It covers the complete Dutch population, making it exceptionally well suited for life course and mobility research. We studied mothers with minor children between 1/1/2008 and 31/12/2010. Our study included 579,500 mothers, of whom about 8,800 (1.5%) experienced a separation in 2008. Separated mothers moved to the grandmother's municipality more often than non‐separated mothers, which might be partially motivated by the need for childcare. They also coresided with the grandmother more than non‐separated movers, mostly because of a vulnerable socio‐economic position. Although often temporary, coresidence appears to have a prolonged impact on the mothers' location choice; mothers frequently stayed in the grandmother's municipality after moving out. Finally, our results indicated that some mothers seemed to use the parental home as a stepping stone to cohabit with a new partner. © 2016 The Authors. Population, Space and Place published by John Wiley & Sons Ltd. PMID:28356888

  18. 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

  19. Device for separating non-ions from ions

    DOEpatents

    Ibrahim, Yehia M.; Smith, Richard D.

    2017-01-31

    A device for separating non-ions from ions is disclosed. The device includes a plurality of electrodes positioned around a center axis of the device and having apertures therein through which the ions are transmitted. An inner diameter of the apertures varies in length. At least a portion of the center axis between the electrodes is non-linear.

  20. 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.

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

    DOE PAGES

    Webb, Ian K.; Garimella, Sandilya V. B.; Tolmachev, Aleksey V.; ...

    2014-09-15

    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 intomore » 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. Ultimately, 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.« less

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

    PubMed

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

    2014-10-07

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

  3. Metabolic profiling of Escherichia coli by ion mobility-mass spectrometry with MALDI ion source.

    PubMed

    Dwivedi, Prabha; Puzon, Geoffery; Tam, Maggie; Langlais, Denis; Jackson, Shelley; Kaplan, Kimberly; Siems, William F; Schultz, Albert J; Xun, Luying; Woods, Amina; Hill, Herbert H

    2010-12-01

    Comprehensive metabolome analysis using mass spectrometry (MS) often results in a complex mass spectrum and difficult data analysis resulting from the signals of numerous small molecules in the metabolome. In addition, MS alone has difficulty measuring isobars and chiral, conformational and structural isomers. When a matrix-assisted laser desorption ionization (MALDI) source is added, the difficulty and complexity are further increased. Signal interference between analyte signals and matrix ion signals produced by MALDI in the low mass region (<1500 Da) cause detection and/or identification of metabolites difficult by MS alone. However, ion mobility spectrometry (IMS) coupled with MS (IM-MS) provides a rapid analytical tool for measuring subtle structural differences in chemicals. IMS separates gas-phase ions based on their size-to-charge ratio. This study, for the first time, reports the application of MALDI to the measurement of small molecules in a biological matrix by ion mobility-time of flight mass spectrometry (IM-TOFMS) and demonstrates the advantage of ion-signal dispersion in the second dimension. Qualitative comparisons between metabolic profiling of the Escherichia coli metabolome by MALDI-TOFMS, MALDI-IM-TOFMS and electrospray ionization (ESI)-IM-TOFMS are reported. Results demonstrate that mobility separation prior to mass analysis increases peak-capacity through added dimensionality in measurement. Mobility separation also allows detection of metabolites in the matrix-ion dominated low-mass range (m/z < 1500 Da) by separating matrix signals from non-matrix signals in mobility space.

  4. Optimum Waveforms for Differential Ion Mobility Spectrometry (FAIMS)

    PubMed Central

    Shvartsburg, Alexandre A.; Smith, Richard D.

    2009-01-01

    Differential mobility spectrometry or field asymmetric waveform ion mobility spectrometry (FAIMS) is a new tool for separation and identification of gas-phase ions, particularly in conjunction with mass-spectrometry. In FAIMS, ions are filtered by the difference between mobilities in gases (K) at high and low electric field intensity (E) using asymmetric waveforms. An infinite number of possible waveform profiles make maximizing the performance within engineering constraints a major issue for FAIMS technology refinement. Earlier optimizations assumed the non-constant component of mobility to scale as E2, producing the same result for all ions. Here we show that the optimum profiles are defined by the full series expansion of K(E) that includes terms beyond the 1st that is proportional to E2. For many ion/gas pairs, the first two terms have different signs, and the optimum profiles at sufficiently high E in FAIMS may differ substantially from those previously reported, improving the resolving power by up to 2.2 times. This situation arises for some ions in all FAIMS systems, but becomes more common in recent miniaturized devices that employ higher E. With realistic K(E) dependences, the maximum waveform amplitude is not necessarily optimum and reducing it by up to ∼20 – 30% is beneficial in some cases. The present findings are particularly relevant to targeted analyses where separation depends on the difference between K(E) functions for specific ions. PMID:18585054

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. 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

    2013-03-05

    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.

  12. Separation of cyanide ions by foam fractionation

    SciTech Connect

    Moussavi, Mohsen )

    1992-05-01

    The technique of adsorption of cyanide ions on foam bubbles was studied as an alternative to chemical oxidation which is practiced in cyanide waste treatment. The technique of foam fractionation was previously applied to the removal of heavy metals and proved to be successful. The free cyanide ions and complex species both responded positively to the formation of a separate foam phase. The results obtained so far show that satisfactory separation of cyanide compounds is possible if certain parameters are properly selected. There are other factors which have not been investigated before, and they seem to have a major role in the performance of this operation.

  13. 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

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

    SciTech Connect

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

    2016-04-06

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

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

    SciTech Connect

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

    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 isolation and accumulation of mobility-separated species. The operation and optimization of the SLIM switch/tee and trap are described and demonstrated for the enrichment of the low abundance ions. 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.

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

    PubMed

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

    2016-02-02

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

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

    DOE PAGES

    Chen, Tsung-Chi; Ibrahim, Yehia M.; Webb, Ian K.; ...

    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. Differential Fragmentation of Mobility-Selected Glycans via Ultraviolet Photodissociation and Ion Mobility-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Morrison, Kelsey A.; Clowers, Brian H.

    2017-06-01

    The alternative dissociation pathways initiated by ultraviolet photodissociation (UVPD) compared with collision-induced dissociation (CID) may provide useful diagnostic fragments for biomolecule identification, including glycans. However, underivatized glycans do not commonly demonstrate strong UV absorbance, resulting in low fragmentation yields for UVPD spectra. In contrast to UVPD experiments that leverage covalent modification of glycans, we detail the capacity of metal adduction to yield comparatively rich UVPD fragmentation patterns and enhance separation factors for an isomeric glycan set in a drift tube ion mobility system. Ion mobility and UVPD-MS spectra for two N-acetyl glycan isomers were examined, each adducted with sodium or cobalt cations, with the latter providing fragment yield gains of an order of magnitude versus sodium adducts. Furthermore, our glycan analysis incorporated front-end ion mobility separation such that the structural glycan isomers could still be identified even as a mixture and not simply composite spectra of isomeric standards. Cobalt adduction proved influential in the glycan separation by yielding an isomer resolution of 0.78 when analyzed simultaneously versus no discernable separation obtained with the sodium adducts. It is the combined enhancement of both isomeric drift time separation and isomer distinction with improved UVPD fragment ion yields that further bolster multivalent metal adduction for advancing glycan IM-MS experiments. [Figure not available: see fulltext.

  19. 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.

  20. A novel approach to collision-induced dissociation (CID) for ion mobility-mass spectrometry experiments.

    PubMed

    Becker, Christopher; Fernandez-Lima, Francisco A; Gillig, Kent J; Russell, William K; Cologna, Stephanie M; Russell, David H

    2009-06-01

    Collision induced dissociation (CID) combined with matrix assisted laser desorption ionization-ion mobility-mass spectrometry (MALDI-IM-MS) is described. In this approach, peptide ions are separated on the basis of mobility in a 15 cm drift cell. Following mobility separation, the ions exit the drift cell and enter a 5 cm vacuum interface with a high field region (up to 1000 V/cm) to undergo collisional activation. Ion transmission and ion kinetic energies in the interface are theoretically evaluated accounting for the pressure gradient, interface dimensions, and electric fields. Using this CID technique, we have successfully fragmented and sequenced a number of model peptide ions as well as peptide ions obtained by a tryptic digest. This instrument configuration allows for the simultaneous determination of peptide mass, peptide-ion sequence, and collision-cross section of MALDI-generated ions, providing information critical to the identification of unknown components in complex proteomic samples.

  1. 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.

  2. Metal ion separations by supported liquid membranes

    SciTech Connect

    Gyves, J. de; San Miguel, E.R. de

    1999-06-01

    Carrier-mediated transport through supported liquid membranes is currently recognized as a potentially valuable technology for selective separation and concentration of toxic and valuable metal ions. In this paper, a review of the fundamental aspects concerning metal ion transport and the influencing factors are surveyed in terms of data modeling, membrane efficiency (permeability, selectivity, stability), and data acquisition and evaluation. An account of the information reviewed demonstrates the need for critical reflection on system performances in order to accomplish scaling up operations. On the same basis, an attempt to outline some future trends in the field is presented.

  3. 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.

  4. 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.

  5. Experimental signal analysis in ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Goubran, R. A.; Lawrence, A. H.

    1991-03-01

    The mathematical differentiation of experimental signals is often used as a resolution enhancement technique, to facilitate the detection and location of partially overlapped gaussian peaks in a multi-component signal. In this paper the analysis of the peak shapes of real ion mobility spectrometry (IMS) signals indicated that a gaussian approximation leads to less than 0.035% of mean square error (using a window of ± 3[sigma] around the peak) while the analysis of the noise signal (performed both in the time and frequency domains) showed that it could be modelled as filtered white gaussian noise. The experimental signal data were provided through the IMS sampling of the chemicals diazepam, lorazepam and bromazepan. Given these findings, a model capable of simulating IMS peaks with any desired time separation, relative amplitude, or additive noise level was developed. It then became possible to quantitatively evaluate the performance and limitations of the second derivative peak detection algorithm. Peak resolution down to 0.27 ms and signal-to-noise ratios down to 18 d[circle dot operator]B were achieved. Some preliminary results obtained with higher order derivative algorithms are also presented.

  6. 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

  7. Acylpyrazolones: Synthesis, self-assembly and lanthanide metal ion separation

    NASA Astrophysics Data System (ADS)

    Yang, Jun

    The central hypothesis that nanoscale self-assemblies can provide excellent metal ion recognition has been substantiated by employing acylpyrazolones and trivalent lanthanide metal ions as model systems. Several novel acylpyrazolones and their amphiphilic analogs have been designed, synthesized, and characterized. Their lanthanide metal ion recognition efficacies have been demonstrated through baseline separations of a mixture of light, middle, and heavy lanthanide metal ions by employing them in the aqueous mobile phase of high performance liquid chromatography (HPLC) with octadecylsilanized silica (ODS) as the stationary phase. The complex separation mechanism is influenced by the structures of acylpyrazolone and amphiphilic moieties, and spontaneous self-assembly of the ligand in the aqueous and on the stationary phases. Transmission electron microscopy (TEM) studies of the ligand self-assemblies in the aqueous phase in the absence and presence of lanthanide metal ions reveal spherical, dendritic, and linear (nanofibers, nanorods, and nanotubes) nanoscale structures. Such structures have also been observed when chloromethylated acylpyrazolones are stimulated to self-assemble by a base in nonaqueous solvents and when silica nanoparticles derivatized with them spontaneously self-assemble in aqueous and nonaqueous solvents.

  8. Travelling-wave ion mobility and negative ion fragmentation of high mannose N-glycans

    PubMed Central

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

    2016-01-01

    The isomeric structure of high-mannose N-glycans can significantly impact biological recognition events. Here, the utility of travelling-wave ion mobility-mass spectrometry (TW IM-MS)for isomer separation of high-mannose N-glycans is investigated. Negative ion fragmentation using collision-induced dissociation (CID) 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 were being separated. Collision cross sections (CCSs) of the isomers in positive and negative fragmentation mode were estimated from TW IM-MS data using dextran glycans as calibrant. More complete CCS 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 (CID) spectra of all resolved isomers are discussed. PMID:26956389

  9. Differentiation of prototropic ions in regioisomeric caffeoyl quinic acids by electrospray ion mobility mass spectrometry.

    PubMed

    Kuhnert, Nikolai; Yassin, Ghada H; Jaiswal, Rakesh; Matei, Marius F; Grün, Christian H

    2015-04-15

    A series of dietary important regioisomeric chlorogenic acids were investigated by ion mobility mass spectrometry (IM-MS). The existence of prototropic isomers separated in the drift dimension was observed and investigated further using tandem mass spectrometry (MS/MS) and compared with suitable synthetic analogues. Using a quadrupole ion mobility time-of-flight mass spectrometer, the IM-MS and IM-MS/MS spectra of selected chlorogenic acids were recorded in the negative ion mode and compared with synthetic analogues. Regioisomeric di- and monocaffeoyl quinic acids can be readily separated and investigated using IM-MS. Comparison of drift times allows assignment of the regiochemistry of precursor ions as well as for fragment ions. For 5-caffeoyl quinic acid the existence of prototropic ions was suggested and probed using synthetic analogues, unable to show this type of isomerism. These investigations suggest the presence of prototropic isomers with carboxylate and phenolate sites, respectively. We report on IM-MS measurements on regioisomeric mono- and dicaffeoyl quinic acids, which are important dietary natural products. Both classes of compounds can be readily separated by IM-MS in the drift time dimension and, following MS(2) experiments, fragment ion regiochemistry unambiguously determined. 5-Caffeoyl quinic acid shows two IM-MS signals, which we assign to prototropic isomers after comparison with suitable synthetic analogues, with a negative charge located at the carboxalate or phenolate functionality, respectively. Copyright © 2015 John Wiley & Sons, Ltd.

  10. The development of ion mobility technology

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  11. 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.

  12. 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.

  13. Radio-Frequency (rf) Confinement in Ion Mobility Spectrometry: Apparent Mobilities and Effective Temperatures.

    PubMed

    Allen, Samuel J; Bush, Matthew F

    2016-12-01

    Ion mobility is a powerful tool for separating and characterizing the structures of ions. Here, a radio-frequency (rf) confining drift cell is used to evaluate the drift times of ions over a broad range of drift field strengths (E/P, V cm(-1) Torr(-1)). The presence of rf potentials radially confines ions and results in excellent ion transmission at low E/P (less than 1 V cm(-1) Torr(-1)), thereby reducing the dependence of ion transmission on the applied drift voltage. Non-linear responses between drift time and reciprocal drift voltages are observed for extremely low E/P and high rf amplitudes. Under these conditions, pseudopotential wells generated by the rf potentials dampen the mobility of ions. The effective potential approximation is used to characterize this mobility dampening behavior, which can be mitigated by adjusting rf amplitudes and electrode dimensions. Using SIMION trajectories and statistical arguments, the effective temperatures of ions in an rf-confining drift cell are evaluated. Results for the doubly charged peptide GRGDS suggest that applied rf potentials can result in a subtle increase (2 K) in effective temperature compared to an electrostatic drift tube. Additionally, simulations of native-like ions of the protein complex avidin suggest that rf potentials have a negligible effect on the effective temperature of these ions. In general, the results of this study suggest that applied rf potentials enable the measurement of drift times at extremely low E/P and that these potentials have negligible effects on ion effective temperature. Graphical Abstract ᅟ.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Ion Optics Simulation for Fragment Separator

    NASA Astrophysics Data System (ADS)

    Kawada, Yosuke; Nakamura, Takashi; Kubo, Toshiyuki; Takeda, Hiroyuki; Sumikama, Toshiyuki

    2009-10-01

    We have developed a Monte-Carlo simulation code for unstable-nuclear beam experiments using a fragment-separator. This code primarily aims at calculating beam traces in the fragment separator BigRIPS and ZeroDegree Spectrometer (ZDS) at RIBF(RIKEN RI-Beam Factory). This code uses externally given transfer-matrices of ion optics such as an output of COSY Infinity[1]. We have applied this code to recent campaign of experiments using ^48Ca at 345MeV/u as primary beam. In the experiments, two modes of ion optical settings , namely ``Standard'' and ``High Brho'' modes were used. The former is an ordinary used starndard setteing, which has a limit in the maximum rigidity (Bρ<9.2Tm). On the other hand, the ``High Brho'' setting has been developed for a secondary beam with higher rigidity, such as for very neutron rich nuclei ^22C (A/Z=3.67). In this talk, we compare properties of these two optics settings and evaluate beam traces, emittances, and transmissions.[4pt] [1] K. Makino, M. Berz Nucl. Instr. Meth. A 558 (2005)

  19. Gas-phase separations of protein and peptide ion fragments generated by collision-induced dissociation in an ion trap.

    PubMed

    Badman, Ethan R; Myung, S; Clemmer, David E

    2002-10-01

    Ion mobility/time-of-flight mass spectrometry techniques have been used to examine distributions of fragment ions generated by collision-induced dissociation (CID) in a quadrupole ion trap. The mobility-based separation step prior to mass-to-charge (m/z) analysis reduces spectral congestion and provides information that complements m/z-based assignments of peaks. The approach is demonstrated by examining fragmentation patterns of insulin chain B (a 30-residue peptide), and ubiquitin (a protein containing 76 amino acids). Some fragments of ubiquitin show evidence for multiple stable conformations.

  20. 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.

  1. How hot are your ions in TWAVE ion mobility spectrometry?

    PubMed

    Merenbloom, Samuel I; Flick, Tawnya G; Williams, Evan R

    2012-03-01

    Effective temperatures of ions during traveling wave ion mobility spectrometry (TWIMS) analysis were measured using singly protonated leucine enkephalin dimer as a chemical thermometer by monitoring dissociation of the dimer into monomer, as well as the subsequent dissociation of monomer into a-, b-, and y-ions, as a function of instrumental parameters. At fixed helium cell and TWIMS cell gas flow rates, the extent of dissociation does not vary significantly with either the wave velocity or wave height, except at low (<500 m/s) wave velocities that are not commonly used. Increasing the flow rate of nitrogen gas into the TWIMS cell and decreasing the flow rate of helium gas into the helium cell resulted in greater dissociation. However, the mobility distributions of the fragment ions formed by dissociation of the dimer upon injection into the TWIMS cell are nearly indistinguishable from those of fragment ions formed in the collision cell prior to TWIMS analysis for all TWIMS experiments. These results indicate that heating and dissociation occur when ions are injected into the TWIMS cell, and that the effective temperature subsequently decreases to a point at which no further dissociation is observed during the TWIMS analysis. An upper limit to the effective ion temperature of 449 K during TWIMS analysis is obtained at a helium flow rate of 180 mL/min, TWIMS flow rate of 80 mL/min, and traveling wave height of 40 V, which is well below previously reported values. Effects of ion heating in TWIMS on gas-phase protein conformation are presented.

  2. How Hot are Your Ions in TWAVE Ion Mobility Spectrometry?

    PubMed Central

    Merenbloom, Samuel I.; Flick, Tawnya G.; Williams, Evan R.

    2012-01-01

    Effective temperatures of ions during traveling wave ion mobility spectrometry (TWIMS) analysis were measured using singly protonated leucine enkephalin dimer as a chemical thermometer by monitoring dissociation of the dimer into monomer, as well as the subsequent dissociation of monomer into a-, b-, and y-ions, as a function of instrumental parameters. At fixed helium cell and TWIMS cell gas flow rates, the extent of dissociation does not vary significantly with either the wave velocity or wave height, except at low (<500 m/s) wave velocities that are not commonly used. Increasing the flow rate of nitrogen gas into the TWIMS cell and decreasing the flow rate of helium gas into the helium cell resulted in greater dissociation. However, the mobility distributions of the fragment ions formed by dissociation of the dimer upon injection into the TWIMS cell are nearly indistinguishable from those of fragment ions formed in the collision cell prior to TWIMS analysis for all TWIMS experiments. These results indicate that heating and dissociation occur when ions are injected into the TWIMS cell, and that the effective temperature subsequently decreases to a point at which no further dissociation is observed during the TWIMS analysis. An upper limit to the effective ion temperature of 449 K during TWIMS analysis is obtained at a helium flow rate of 180 mL/min, TWIMS flow rate of 80 mL/min and traveling wave height of 40 V, which is well below previously reported values. Effects of ion heating in TWIMS on gas-phase protein conformation are presented. PMID:22203576

  3. 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

  4. 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

  5. Analysis of black powder by ion mobility-time-of-flight mass spectrometry.

    PubMed

    Crawford, Christina L; Boudries, Hacene; Reda, Ralph J; Roscioli, Kristyn M; Kaplan, Kimberly A; Siems, William F; Hill, Herbert H

    2010-01-01

    Ion mobility-time-of-flight mass spectrometry (IM-TOFMS) was used to identify and correlate response ions associated with three black powder samples by mass and mobility. Vapors produced by thermal desorption of the black powders were ionized by a (63)Ni source; subsequent response ions were separated and identified using IM-TOFMS. The same response ions were found for each black powder regardless of geographic origin. The most intense mass and mobility peaks were attributed to ionic forms of sulfur allotropes ((32)S(n)(-), where n = 1-5). Vapor samples from GOEX black powder were also analyzed by two stand-alone ion mobility spectrometry systems, yielding an average reduced mobility value (K(o)) of 2.28 +/- 0.02 cm(2) V(-1) s(-1) for black powder across all three instruments.

  6. Ion mobility analysis of molecular dynamics.

    PubMed

    Wyttenbach, Thomas; Pierson, Nicholas A; Clemmer, David E; Bowers, Michael T

    2014-01-01

    The combination of mass spectrometry and ion mobility spectrometry (IMS) employing a temperature-variable drift cell or a drift tube divided into sections to make IMS-IMS experiments possible allows information to be obtained about the molecular dynamics of polyatomic ions in the absence of a solvent. The experiments allow the investigation of structural changes of both activated and native ion populations on a timescale of 1-100 ms. Five different systems representing small and large, polar and nonpolar molecules, as well as noncovalent assemblies, are discussed in detail: a dinucleotide, a sodiated polyethylene glycol chain, the peptide bradykinin, the protein ubiquitin, and two types of peptide oligomers. Barriers to conformational interconversion can be obtained in favorable cases. In other cases, solution-like native structures can be observed, but care must be taken in the experimental protocols. The power of theoretical modeling is demonstrated.

  7. Separation of metal ions in nitrate solution by ultrasonic atomization

    NASA Astrophysics Data System (ADS)

    Sato, Masanori; Ikeno, Masayuki; Fujii, Toshitaka

    2004-11-01

    In the ultrasonic atomization of metal nitrate solutions, the molar ratio of metal ions is changed between solution and mist. Small molar metal ions tend to be transferred to mist by ultrasonic wave acceleration, while large molar ions tend to remain in solution. As a result, metal ions can be separated by ultrasonic atomization. We show experimental data and propose a conceptual mechanism for the ultrasonic separation of metal ions.

  8. Separation of metal ions in nitrate solution by ultrasonic atomization.

    PubMed

    Sato, Masanori; Ikeno, Masayuki; Fujii, Toshitaka

    2004-11-15

    In the ultrasonic atomization of metal nitrate solutions, the molar ratio of metal ions is changed between solution and mist. Small molar metal ions tend to be transferred to mist by ultrasonic wave acceleration, while large molar ions tend to remain in solution. As a result, metal ions can be separated by ultrasonic atomization. We show experimental data and propose a conceptual mechanism for the ultrasonic separation of metal ions.

  9. 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

  10. 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.

  11. Toward Plasma Proteome Profiling with Ion Mobility-Mass Spectrometry

    SciTech Connect

    Valentine, Stephen J.; Plasencia, Manolo D.; Liu, Xiaoyun; Krishnan, Meera; Naylor, Stephen; Udseth, Harold R.; Smith, Richard D.; Clemmer, David E.

    2006-11-01

    Differential, functional, and mapping proteomic analyses of complex biological mixtures suffer from a lack of component resolution. Here we describe the application of ion mobility-mass spectrometry (IMSMS) to this problem. With this approach, components that are separated by liquid chromatography are dispersed based on differences in their mobilities through a buffer gas prior to being analyzed by MS. The inclusion of the gas-phase dispersion provides more than an order of magnitude enhancement in component resolution at no cost to data acquisition time. Additionally, the mobility separation often removes high-abundance species from spectral regions containing low-abundance species, effectively increasing measurement sensitivity and dynamic range. Finally, collision-induced dissociation of all ions can be recorded in a single experimental sequence while conventional MS methods sequentially select precursors. The approach is demonstrated in a single, rapid (3.3 h) analysis of a plasma digest sample where abundant proteins have not been removed. Protein database searches have yielded 731 high confidence peptide assignments corresponding to 438 unique proteins. Results have been compiled into an initial analytical map to be used -after further augmentation and refinement- for comparative plasma profiling studies.

  12. 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.

  13. Dielectric properties and ion mobility in erythrocytes.

    PubMed

    Pauly, H; Schwan, H P

    1966-09-01

    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.

  14. [Simultaneous separation of organic acid and organic salts by electrostatic ion chromatography].

    PubMed

    Shen, G J; Yang, R F; Yu, A M

    2001-09-01

    The electrostatic ion chromatographic column was prepared by coating conjugated acid salt micelles on the surface of octadecyl silica stationary phase. Pure water was used as mobile phase, and the conductance detector was connected on-line to electrostatic ion chromatograph. The conditions under which organic acid and organic salts were detected were studied. The mechanism for the above separation is discussed. Sodium benzoate and citric acid in Lichee drink were separated and determined. This method is rapid, simple with little interference and good reproducibility without any pollution since the mobile phase is water. This is an environmental friendly analytical method.

  15. Ion mobility spectrometry for detection of skin volatiles.

    PubMed

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

    2012-12-12

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

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. Acoustophoretic Mobility and Its Role in Optimizing Acoustofluidic Separations.

    PubMed

    Williams, Philip Stephen; Martin, Michel; Hoyos, Mauricio

    2017-06-20

    In the separation sciences, sample species are separated according to their physicochemical properties, the nature of the selective field, and, if present, the properties of the medium in which they are dissolved or suspended. Separations may be carried out on a continuous basis in microfluidic devices or split-flow thin channel (SPLITT) devices by selectively transporting species in a direction transverse to the direction of flow of the suspending fluid. Separation is achieved in the so-called transport mode according to relative differences in mobility of the species under the influence of the applied field. Gravitational, centrifugal, thermal gradient, magnetic, electric, and dielectric fields may all be used for continuous SPLITT fractionation. We present here the theory for optimizing the operation of the relatively new technique of acoustic SPLITT fractionation for the continuous separation of non-Brownian materials. The theory is based on a quantitatively defined acoustophoretic mobility that is consistent with the generalized concept of mobility proposed by Giddings. Until now, acoustophoretic mobility has almost exclusively been used as a qualitative descriptor for velocity induced by an acoustic field. The quantitative definition presented here will contribute to the advancement of all forms of acoustofluidic separations.

  1. Theory for inverse pulsing of the shutter grid in ion mobility spectrometry.

    PubMed

    Spangler, Glenn E

    2010-10-01

    The fundamental transport theory for ion mobility spectrometry is modified to include effects of space charge. The new theory is then applied to describing the performance of "inverse ion mobility spectrometry" recently reported in Tabrizchi, M.; Jazan, E. Anal. Chem. 2010, 82, 746-750 using a discharge ionization source. The improved separation capabilities arise from space charge repulsion of the greater number of ions that are introduced into the drift tube by the technique. A larger effective diffusion coefficient and additional displacement velocities for the leading and trailing edges of the ion mobility peak account for the results. Performance is compared to conventional linear ion mobility spectrometry, with and without a radioactive source for ionization.

  2. Analysis of phthalate esters by ion mobility spectrometry

    SciTech Connect

    Giam, C.S.; Reed, G.E.; Holliday, T.L.

    1995-12-31

    Esters of phthalic acid can be detected by IMS (ion mobility spectrometry). The six phthalates in the EPA`s Priority Pollutant List can be detected in both modes--positive as well as negative mode. In the positive mode, a characteristic reduced mobility was obtained for each phthalate; thus the different esters can be distinguished, including the isomeric di-n-octyl- and di-2-ethylhexyl phthalate. Phthalates can be detected in the low nanogram range; detection sensitivity is comparable or better than those found by gas chromatography using different detectors, including by GC-ECD, GC-FID or GC-MS. Direct Monitoring of environmental phthalates by IMS possess several advantages, e.g., without the usual separation protocols for ubiquitous interferants, faster instrumental analysis time (minutes instead of hours), and lower cost. Thus, IMS of phthalates has a great potential as an environmental monitor.

  3. Separation Principle and Monte Carlo Studies for Differential Mobility Spectrometry

    SciTech Connect

    Han, Fenglei; Li, Haiyang; Xu, Jun

    2012-01-01

    Differential Mobility Spectrometry (DMS), which ionizes analyte and uses asymmetric field waveforms to identify the ions, is increasingly used for detection of trace chemicals. In this work, we reveal the linear relation between DMS compensation voltage and the nonlinear mobility coefficient ( ) and consider mobility difference induced by clustering in low-field and de-clustering in high field. A program for Monte Carlo simulation of ion transport in practical DMS analyzers has been developed. Practical factors considered in this simulation mainly include a realistic sine-based asymmetric waveform and the clustering and de-clustering associated with this asymmetric waveform. Using this program, DMS compensation spectra, RF-CV dispersion plots, and transport efficiencies are predicted. Some experiments are done for validating the simulations and show consistency with the predictions.

  4. 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.

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

    PubMed

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

    2017-06-20

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

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

    PubMed

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

    2015-02-17

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

  7. 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.

  8. 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.

  9. High-performance liquid chromatography with electrospray ionization ion mobility spectrometry: Characterization, data management, and applications.

    PubMed

    Zühlke, Martin; Riebe, Daniel; Beitz, Toralf; Löhmannsröben, Hans-Gerd; Andreotti, Sandro; Reinert, Knut; Zenichowski, Karl; Diener, Marc

    2016-12-01

    The combination of high-performance liquid chromatography and electrospray ionization ion mobility spectrometry facilitates the two-dimensional separation of complex mixtures in the retention and drift time plane. The ion mobility spectrometer presented here was optimized for flow rates customarily used in high-performance liquid chromatography between 100 and 1500 μL/min. The characterization of the system with respect to such parameters as the peak capacity of each time dimension and of the 2D spectrum was carried out based on a separation of a pesticide mixture containing 24 substances. While the total ion current chromatogram is coarsely resolved, exhibiting coelutions for a number of compounds, all substances can be separately detected in the 2D plane due to the orthogonality of the separations in retention and drift dimensions. Another major advantage of the ion mobility detector is the identification of substances based on their characteristic mobilities. Electrospray ionization allows the detection of substances lacking a chromophore. As an example, the separation of a mixture of 18 amino acids is presented. A software built upon the free mass spectrometry package OpenMS was developed for processing the extensive 2D data. The different processing steps are implemented as separate modules which can be arranged in a graphic workflow facilitating automated processing of data.

  10. A novel Laser Ion Mobility Spectrometer

    NASA Astrophysics Data System (ADS)

    Göbel, J.; Kessler, M.; Langmeier, A.

    2009-05-01

    IMS is a well know technology within the range of security based applications. Its main advantages lie in the simplicity of measurement, along with a fast and sensitive detection method. Contemporary technology often fails due to interference substances, in conjunction with saturation effects and a low dynamic detection range. High throughput facilities, such as airports, require the analysis of many samples at low detection limits within a very short timeframe. High detection reliability is a requirement for safe and secure operation. In our present work we developed a laser based ion-mobility-sensor which shows several advantages over known IMS sensor technology. The goal of our research was to increase the sensitivity compared to the range of 63Ni based instruments. This was achieved with an optimised geometric drift tube design and a pulsed UV laser system at an efficient intensity. In this intensity range multi-photon ionisation is possible, which leads to higher selectivity in the ion-formation process itself. After high speed capturing of detection samples, a custom designed pattern recognition software toolbox provides reliable auto-detection capability with a learning algorithm and a graphical user interface.

  11. Analysis of model Titan atmospheric components using ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Kojiro, D. R.; Cohen, M. J.; Wernlund, R. F.; Stimac, R. M.; Humphry, D. E.; Takeuchi, N.

    1991-01-01

    The Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS) was proposed as an analytical technique for the analysis of Titan's atmosphere during the Cassini Mission. The IMS is an atmospheric pressure, chemical detector that produces an identifying spectrum of each chemical species measured. When the IMS is combined with a GC as a GC-IMS, the GC is used to separate the sample into its individual components, or perhaps small groups of components. The IMS is then used to detect, quantify, and identify each sample component. Conventional IMS detection and identification of sample components depends upon a source of energetic radiation, such as beta radiation, which ionizes the atmospheric pressure host gas. This primary ionization initiates a sequence of ion-molecule reactions leading to the formation of sufficiently energetic positive or negative ions, which in turn ionize most constituents in the sample. In conventional IMS, this reaction sequence is dominated by the water cluster ion. However, many of the light hydrocarbons expected in Titan's atmosphere cannot be analyzed by IMS using this mechanism at the concentrations expected. Research at NASA Ames and PCP Inc., has demonstrated IMS analysis of expected Titan atmospheric components, including saturated aliphatic hydrocarbons, using two alternate sample ionizations mechanisms. The sensitivity of the IMS to hydrocarbons such as propane and butane was increased by several orders of magnitude. Both ultra dry (waterless) IMS sample ionization and metastable ionization were successfully used to analyze a model Titan atmospheric gas mixture.

  12. Correlation between the shape of the ion mobility signals and the stepwise folding process of polylactide ions.

    PubMed

    Duez, Q; Josse, T; Lemaur, V; Chirot, F; Choi, C M; Dubois, P; Dugourd, P; Cornil, J; Gerbaux, P; De Winter, J

    2017-03-01

    In the field of polymer characterization, the use of ion mobility mass spectrometry (IMMS) remains mainly devoted to the temporal separation of cationized oligomers according to their charge states, molecular masses and macromolecular architectures in order to probe the presence of different structures. When analyzing multiply charged polymer ions by IMMS, the most striking feature is the observation of breaking points in the evolution of the average collision cross sections with the number of monomer units. Those breaking points are associated to the folding of the polymer chain around the cationizing agents. Here, we scrutinize the shape of the arrival time distribution (ATD) of polylactide ions and associate the broadening as well as the loss of symmetry of the ATD signals to the coexistence of different populations of ions attributed to the transition from opened to folded stable structures. The observation of distinct distributions reveals the absence of folded/extended structure interconversion on the ion mobility time scale (1-10 ms) and then on the lifetime of ions within the mass spectrometer at room temperature. In order to obtain information on the possible interconversion between the different observed populations upon ion activation, we performed IM-IM-MS experiments (tandem ion mobility measurements). To do so, mobility-selected ions were activated by collisions before a second mobility measurement. Interestingly, the conversion by collisional activation from a globular structure into a (partially) extended structure, i.e. the gas phase unfolding of the ions, was not observed in the energetic regime available with the used experimental setup. The absence of folded/extended interconversion, even upon collisional activation, points to the fact that the polylactide ions are 'frozen' in their specific 3D structure during the desolvation/ionization electrospray processes. Copyright © 2017 John Wiley & Sons, Ltd.

  13. 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

  14. Reducing False Alarms in Ion Mobility Spectrometry Detectors Determination of Accurate and Precise Ion Mobility Spectrometry Constants

    DTIC Science & Technology

    2014-01-01

    Hard-Sphere and Ab Initio Potentials 22nd International Conference on Ion Mobility Spectrometry; Asheville , North Carolina; July 27- August 1, 2014...Spectrometer: Validation of Instrumental Parameters and Initial Results 22nd International Conference on Ion Mobility Spectrometry; Asheville , North

  15. Field screening of volatile organochlorine compounds using ion mobility spectrometry

    SciTech Connect

    Stach, J.; Brodacki, M.; Doering, H.R.; Flachowsky, J.

    1995-12-31

    Chlorinated alkanes and alkenes produce due to a dissociative charge transfer reaction strong signals of Cl{sup {minus}} ions in ion mobility spectra. This reaction can be used to analyze these compounds in on site analyses. The method is applicable to dump gases, soil air or soil using head space techniques and volatile halogen compounds dissolved in organic solvents. The results obtained by ion mobility spectrometry correlate with GC/MS or AOX measurements in most cases.

  16. 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. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. Shutterless ion mobility spectrometer with fast pulsed electron source

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  19. Structural resolution of 4-substituted proline diastereomers with ion mobility spectrometry via alkali metal ion cationization.

    PubMed

    Flick, Tawnya G; Campuzano, Iain D G; Bartberger, Michael D

    2015-03-17

    The chirality of substituents on an amino acid can significantly change its mode of binding to a metal ion, as shown here experimentally by traveling wave ion mobility spectrometry-mass spectrometry (TWIMS-MS) of different proline isomeric molecules complexed with alkali metal ions. Baseline separation of the cis- and trans- forms of both hydroxyproline and fluoroproline was achieved using TWIMS-MS via metal ion cationization (Li(+), Na(+), K(+), and Cs(+)). Density functional theory calculations indicate that differentiation of these diastereomers is a result of the stabilization of differing metal-complexed forms adopted by the diastereomers when cationized by an alkali metal cation, [M + X](+) where X = Li, Na, K, and Cs, versus the topologically similar structures of the protonated molecules, [M + H](+). Metal-cationized trans-proline variants exist in a linear salt-bridge form where the metal ion interacts with a deprotonated carboxylic acid and the proton is displaced onto the nitrogen atom of the pyrrolidine ring. In contrast, metal-cationized cis-proline variants adopt a compact structure where the carbonyl of the carboxylic acid, nitrogen atom, and if available, the hydroxyl and fluorine substituent solvate the metal ion. Experimentally, it was observed that the resolution between alkali metal-cationized cis- and trans-proline variants decreases as the size of the metal ion increases. Density functional theory demonstrates that this is due to the decreasing stability of the compact charge-solvated cis-proline structure with increased metal ion radius, likely a result of steric hindrance and/or weaker binding to the larger metal ion. Furthermore, the unique structures adopted by the alkali metal-cationized cis- and trans-proline variants results in these molecules having significantly different quantum mechanically calculated dipole moments, a factor that can be further exploited to improve the diastereomeric resolution when utilizing a drift gas with a

  20. 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

  1. 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)

  2. 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)

  3. 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.

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

    PubMed

    Huang, Yuting; Dodds, Eric D

    2013-10-15

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

  5. Mobilities of polyatomic ions in gases - Core model.

    NASA Technical Reports Server (NTRS)

    Mason, E. A.; O'Hara, H.; Smith, F. J.

    1972-01-01

    A core model, consisting of a (12-4) central potential displaced from the origin, is suggested as a representation of the interaction of polyatomic ions with neutral molecules. The diffusion collision integral, which describes ion mobility, is computed and tabulated as a function of temperature and core size. The addition of the core reduces the maximum in the mobility against temperature curve, and eventually reduces the mobility below its polarization limit at all temperatures. These results are in accord with limited available experimental data. Comparison is made with other models of ion-neutral interactions.

  6. 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.

  7. 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.

  8. Increasing the Performance of Portable Ion Mobility Analyzers: Development of the Periodic Focusing Differential Mobility Analyzer (PFDMA)

    PubMed Central

    Gillig, Kent J.; Chen, Chung-Hsuan

    2014-01-01

    Ion mobility spectrometry (IMS) as a stand-alone technique has become increasingly important for applications in security, defense, and environmental monitoring, and also in biological applications such as molecular structure and -omic analysis when combined with mass spectrometry. Yet, the majority of these devices are drift cell based and limited by low duty cycles because of ion gating. Differential Mobility Analyzers (DMAs) are attractive alternatives due to their continuous ion transmission and success in analyzing aerosol particles in real time environmental tests. But, the resolution of a DMA is low due to difficulties in achieving laminar gas flow, low sample gas flow to sheath gas flow ratio, and high velocity sheath gas using small pumps, if portability is a concern. To overcome these challenges, we will introduce a new ion mobility spectrometer that increases the amount of work done on the ions during separation by introducing an electric field opposing the gas flow direction while simultaneously preserving laminar gas flow. The development of the Periodic Focusing Differential Mobility Analyzer (PFDMA) can lead to a portable device that exhibits both high resolution and sensitivity, to meet the needs of today’s expanding applications. PMID:26819904

  9. 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.

  10. Application of PVDF composite for lithium-ion battery separator

    NASA Astrophysics Data System (ADS)

    Sabrina, Q.; Majid, N.; Prihandoko, B.

    2016-11-01

    In this study a composite observed in PVDF composite as lithium ion battery separator. Observation of performance cell battery with cyclic voltametry and charge discharge capacity. Surface morphology PVDF separator and commercial separator observed with Scanning electron microscopy (SEM). Cyclic Voltamerty test (CV) and Charge Discharge (CD) showed a capacity value on the coin cell. Coin cell is composed of material LiFePO4 cathode, anode material of lithium metal and varies as graphite, liquid electrolyte varied use LiBOB and LiPF6. While the PVDF as compared to the commercial separator. Coin cell commercial separator has a better high capacity value when compared with Coin cell with the PVDF separator. Life cycle coin cell with the commercial separator material is still longer than coin cell separator with PVDF Copolymer. Development of PVDF as separator remains to be done in order to improve the performance of the battery exceeds the usage of commercial material.

  11. 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.

  12. 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

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

    PubMed

    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.

  14. 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.

  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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Studies of peptide a- and b-type fragment ions using stable isotope labeling and integrated ion mobility/tandem mass spectrometry.

    PubMed

    Riba Garcia, Isabel; Giles, Kevin; Bateman, Robert H; Gaskell, Simon J

    2008-12-01

    The structures of peptide a- and b-type fragment ions were studied using synthetic peptides including a set of isomeric peptides, differing in the sequence location of an alanine residue labeled with (15)N and uniformly with (13)C. The pattern of isotope labeling of second-generation fragment ions derived via a(n) and b(n) ions (where n = 4 or 5) suggested that these intermediates existed in part as macrocyclic structures, where alternative sites of ring opening gave rise to different linear forms whose simple cleavage might give rise to the observed final products. Similar conclusions were derived from combined ion mobility/tandem MS analyses where different fragmentation patterns were observed for isomeric a- or b-type ions that display different ion mobilities. These analyses were facilitated by a new approach to the processing of ion mobility/tandem MS data, from which distinct and separate product ion spectra are derived from ions that are incompletely separated by ion mobility. Finally, an example is provided of evidence for a macrocyclic structure for b(n) ions where n = 8 or 9.

  1. Resolution concept for separation of curium from californium by ion-exchange chromatography.

    PubMed

    Aly, H F; Latimer, R M; Abdel-Rassoul, A A

    1970-04-01

    Different factors affecting separation of the tervalent actinides curium and californium by ion-exchange chromatography are discussed in the light of the resolution factor. The fact that resolution is inversely proportional to resin particle diameter and directly proportional to column length has been confirmed experimentally. The effects influencing resolution due to changes in flow-rate of the mobile phase used are dependent on resin particle diameter. Changes in temperature affect a number of variables influencing resolution.

  2. Experimental studies on ion mobility in xenon-trimethylamine mixtures

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

    In this paper we present experimental results for ion reduced mobilities (K0) in gaseous trimethylamine, TMA—(CH3)3N, and xenon-TMA mixtures for reduced electric fields E/N between 7.5 and 60 Td and in the pressure range from 0.5 to 10 Torr, at room temperature. Both in the mixtures and in pure TMA only one peak was observed in the time of arrival spectra, which is believed to be due to two TMA ions with similar mass, (CH3)3N+ (59 u) and (CH3)2CH2N+ (58 u), whose mobility is indistinguishable in our experimental system. The possibility of ion cluster formation is also discussed. In pure TMA, for the E/N range investigated, an average value of 0.56 cm2V-1s-1 was obtained for the reduced mobility of TMA ions. For the studied mixtures, it was observed that even a very small amount of gaseous TMA (~0.2%) in xenon leads to the production of the above referred TMA ions or clusters. The reduced mobility value of this ion or ions in Xe-TMA mixtures is higher than the value in pure TMA: around 0.8 cm2V-1s-1 for TMA concentrations from 0.2% to about 10%, decreasing for higher TMA percentages, eventually converging to the reduced mobility value in pure TMA.

  3. Separation of ions in acidic solution by capillary electrophoresis

    SciTech Connect

    Thornton, Michelle

    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.

  4. 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

  5. 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.

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

    DOEpatents

    Smith, R.D.; Wahl, J.H.; Hofstadler, S.A.

    1996-08-13

    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. 7 figs.

  7. 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

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  10. Monte Carlo simulation of ion trajectories of reacting chemical systems: mobility of small water clusters in ion mobility spectrometry.

    PubMed

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

    2013-04-01

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

  11. 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.

  12. Chromatographic separation of certain metal ions using a bifunctional quaternary ammonium-sulfonate mixed bed ion-exchanger.

    PubMed

    Lasheen, Y F; Seliman, A F; Abdel-Rassoul, A A

    2006-12-15

    The separation behaviour of Pb(2+), Cu(2+), Cd(2+), Co(2+), Zn(2+) and Ni(2+) on bifunctional quaternary ammonium-sulfonate mixed ion-exchangers (Dionex, IonPac CS5 and CG5) was studied using different eluents including solutions of oxalic acid, potassium oxalate, sodium oxalate and ammonium oxalate. Separated metal ions were followed by using 4-(2-pyridylazo) resorcinol (PAR) as post-colouring complex. The retention factors of different ions proved to be dependent on the pH, concentration, nature of each complexing agent, and to less extent on eluent flow rate. The retention behaviour and separation mechanism of complexed metal analytes are discussed in the light of the stability of metal complexes and the ligand complexing ability of used eluent. Comparison between various mobile phases is evaluated, and both sodium and potassium oxalate can be used successfully for simultaneous separation of studied metals with good resolution within short elution periods. The method can be used in different applications including analysis of bottled water from different resources.

  13. Size, weight and position: ion mobility spectrometry and imaging MS combined.

    PubMed

    Kiss, András; Heeren, Ron M A

    2011-03-01

    Size, weight and position are three of the most important parameters that describe a molecule in a biological system. Ion mobility spectrometry is capable of separating molecules on the basis of their size or shape, whereas imaging mass spectrometry is an effective tool to measure the molecular weight and spatial distribution of molecules. Recent developments in both fields enabled the combination of the two technologies. As a result, ion-mobility-based imaging mass spectrometry is gaining more and more popularity as a (bio-)analytical tool enabling the determination of the size, weight and position of several molecules simultaneously on biological surfaces. This paper reviews the evolution of ion-mobility-based imaging mass spectrometry and provides examples of its application in analytical studies of biological surfaces.

  14. 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.

  15. Ultrafast charge separation driven by differential particle and hole mobilities.

    PubMed

    Dutoi, Anthony D; Wormit, Michael; Cederbaum, Lorenz S

    2011-01-14

    The process of a local excitation evolving into an intramolecular charge-separated state is followed and compared for several systems by directly simulating the time propagation of the electronic wavefunction. The wavefunction and Hamiltonian are handled using the extended second-order algebraic diagrammatic construction (ADC(2)-x), which explicitly accounts for electron correlation in the dynamic many-particle state. The details of the charge separation can be manipulated according to the chemical composition of the system; atoms which dope the conjugated system with either particles or holes are shown to effect whether the particle or hole is more mobile. Initially, the charges oscillate between the ends of linear molecules (with different rates), separating periodically, but, at long times, both charges tend to spread over the whole molecule. Charge separation is also shown to occur for asymmetric systems, where it may eventually be experimentally feasible to excite a localized resonance (nonstationary state) on one end of the molecule preferentially and follow the ensuing dynamics.

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

    SciTech Connect

    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.

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

    PubMed

    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.

  18. Method of multiplexed analysis using ion mobility spectrometer

    DOEpatents

    Belov, Mikhail E [Richland, WA; Smith, Richard D [Richland, WA

    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.

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

    NASA Astrophysics Data System (ADS)

    Kuroboshi, Y.; Takemura, K.

    2016-12-01

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

  20. Ion-Molecule Clustering in Differential Mobility Spectrometry: Lessons Learned from Tetraalkylammonium Cations and their Isomers

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  1. 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.

  2. 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.

  3. 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.

  4. Anomalous Decline of Molecular Ion Mobility in Cooled Helium Gas

    NASA Astrophysics Data System (ADS)

    Ohtsuki, Kazumasa; Hananoe, Masatoshi; Matsuzawa, Michio

    2005-11-01

    We present a first successful theoretical account of the ion mobilities of N2+ and O2+ in helium gas at 4.3 K. Measured mobilities of various molecular ions at low effective temperatures reportedly tend to values smaller than their polarization limits, with the exception of N2+ [J. Sanderson , J. Phys. BJPAPEH0953-4075 26, L465 (1993)10.1088/0953-4075/26/15/006; J. SandersonJ. Phys. BJPAPEH0953-407527, L433 (1994)10.1088/0953-4075/27/14/021]. The present theoretical results obtained by the classical trajectory calculations agree with the experimental ones very well, and make it definitive that the anomalous decline of molecular ion mobility is caused by a Feshbach-like resonance due to the anisotropic interaction potential between a molecular ion and a helium atom. The mechanism thus revealed is supported by quantitative quantum mechanical calculations. The process appears very similar to that of laser cooling.

  5. 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.

  6. 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.

  7. 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.

  8. Cryogenic molecular separation system for radioactive (11)C ion acceleration.

    PubMed

    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 (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 (11)C ion beams. In the ISOL system, (11)CH4 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 (12)CH4 gases, which can simulate the chemical characteristics of (11)CH4 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

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

    PubMed

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

    2006-06-01

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

  14. X-ray ionization differential ion mobility spectrometry.

    PubMed

    Kuklya, Andriy; Reinecke, Tobias; Uteschil, Florian; Kerpen, Klaus; Zimmermann, Stefan; Telgheder, Ursula

    2017-01-01

    X-ray was utilized as an ionization source for differential ion mobility spectrometry (DMS) for the first time. The utilization of this ionization source increases the potential of DMS system for on-site based applications. The influence of experimental parameters (e.g. accelerating voltage, filament current, and separation field) on the analysis of model compounds was investigated and discussed. It was found that both the positive and the negative reactive ion peaks [RIP(+) and RIP(-)] formed during X-ray ionization are identical with those observed with the traditional (63)Ni radioactive ion source. This is especially notable for RIP(-), because the chemistry provided by other nonradioactive sources in the negative mode is more complicated or even different than that observed with a (63)Ni source. Increase of either filament current or accelerating voltage resulted in increased intensity of both RIP(+) and RIP(-). However, because of the materials used for construction of X-ray adapter the maximal level of filament current and accelerating voltage used in this study were limited to 700mA and 5kV, respectively. Analytical performance was determined with two model compounds (acetone and methyl salicylate) using X-ray and directly compared to (63)Ni ionization source. When X-ray was coupled to DMS, calculated LOD values were found to be within the range of 0.17-1.52ppbv/v (concentration in the carrier gas). These values are competitive with those calculated for DMS equipped with traditional (63)Ni radioactive ionization source. The obtained results are promising enough to ensure the potential of X-ray as ionization source for DMS. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. 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

  16. Detection of Biological Materials Using Ion Mobility Spectroscopy

    SciTech Connect

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

    1999-03-01

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

  17. Ion creation, ion focusing, ion/molecule reactions, ion separation, and ion detection in the open air in a small plastic device.

    PubMed

    Baird, Zane; Wei, Pu; Cooks, R Graham

    2015-02-07

    A method is presented in which ions are generated and manipulated in the ambient environment using polymeric electrodes produced with a consumer-grade 3D printer. The ability to focus, separate, react, and detect ions in the ambient environment is demonstrated and the data agree well with simulated ion behaviour.

  18. Entropic electrokinetics: recirculation, particle separation, and negative mobility.

    PubMed

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

    2014-09-19

    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.

  19. 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.

  20. 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.

  1. 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.

  2. How useful is molecular modelling in combination with ion mobility mass spectrometry for 'small molecule' ion mobility collision cross-sections?

    PubMed

    Lapthorn, Cris; Pullen, Frank S; Chowdhry, Babur Z; Wright, Patricia; Perkins, George L; Heredia, Yanira

    2015-10-21

    Ion mobility mass spectrometry is used to measure the drift-time of an ion. The drift-time of an ion can be used to calculate the collision cross-section (CCS) in travelling wave ion mobility (e.g. Waters Synapt and Vion instruments) or directly determine the experimental CCS (e.g. Agilent 6560 instrument and many drift-tube instruments). A comparison of the experimental CCS and theoretical CCS values obtained from trajectory method He(g) parameterised MOBCAL and N2(g) parameterised MOBCAL software, for a range of 20 'small molecules' is presented. This study utilises density functional theory B3LYP methods and the 6-31G+(d,p) basis set to calculate theoretical CCS values. This study seeks to assess the accuracy of a common procedure using CCS calibration with poly-(d/l)-alanine derived from drift-cell measurements and the original release of MOBCAL software and compare it with recent improvements with a drug-like molecule calibration set and a revision of MOBCAL parameterised for N2(g) drift gas. This study represents one of the first quantitative evaluations of the agreement between theoretical CCS and experimental CCS values for a range of small pharmaceutically relevant molecules using travelling wave ion mobility mass spectrometry. Accurate theoretical CCS may allow optimisation of ion mobility separations in silico, provide CCS databases that can confirm structures without the need for alternative analytical tools such as nuclear magnetic resonance spectroscopy (NMR) and assignment of unknowns and positional isomers without requiring reference materials.

  3. 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.

  4. 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.

  5. 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.

  6. Gated Trapped Ion Mobility Spectrometry Coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

    PubMed

    Ridgeway, Mark E; Wolff, Jeremy J; Silveira, Joshua A; Lin, Cheng; Costello, Catherine E; Park, Melvin A

    2016-09-01

    Analysis of molecules by ion mobility spectrometry coupled with mass spectrometry (IMS-MS) provides chemical information on the three dimensional structure and mass of the molecules. The coupling of ion mobility to trapping mass spectrometers has historically been challenging due to the large differences in analysis time between the two devices. In this paper we present a modification of the trapped ion mobility (TIMS) analysis scheme termed "Gated TIMS" that allows efficient coupling to a Fourier Transform Ion Cyclotron Resonance (FT-ICR) analyzer. Analyses of standard compounds and the influence of source conditions on the TIMS distributions produced by ion mobility spectra of labile ubiquitin protein ions are presented. Ion mobility resolving powers up to 100 are observed. Measured collisional cross sections of ubiquitin ions are in excellent qualitative and quantitative agreement to previous measurements. Gated TIMS FT-ICR produces results comparable to those acquired using TIMS/time-of-flight MS instrument platforms as well as numerous drift tube IMS-MS studies published in the literature.

  7. Ion chromatography for the separation of heparin and structurally related glycoaminoglycans: A review.

    PubMed

    Fasciano, Jennifer M; Danielson, Neil D

    2016-03-01

    The global crisis resulting from adulterated heparin in late 2007 and early 2008 revived the importance of analytical techniques for the purity analysis of heparin products. The utilization of ion chromatography techniques for the separation, detection, and structural determination of heparin and structurally related glycoaminoglycans, including their corresponding oligosaccharides, has become increasingly important. This review summarizes the primary HPLC approaches, particularly strong anion exchange, weak ion exchange, and reversed-phase ion-pair, used for heparin purity analysis as well as structural characterization. Strong anion exchange HPLC has been studied most extensively and currently offers the best separation of crude heparin and heparin-like compounds. Weak anion exchange HPLC has been shown to provide shorter analysis times with lower salt concentrations in the mobile phase but is not as widely developed for the separation of all glycoaminoglycans of interest. Reversed-phase ion-pair HPLC offers fast and effective separations of oligosaccharides derived from glycoaminoglycans that can be coupled to mass spectrometry for structural analysis. However, this method generally does not provide sufficient retention of intact glycoaminoglycans.

  8. Structural Dynamics of Native-Like Ions in the Gas Phase: Results from Tandem Ion Mobility of Cytochrome c.

    PubMed

    Allen, Samuel J; Eaton, Rachel M; Bush, Matthew F

    2017-07-18

    Ion mobility (IM) is a gas-phase separation technique that is used to determine the collision cross sections of native-like ions of proteins and protein complexes, which are in turn used as restraints for modeling the structures of those analytes in solution. Here, we evaluate the stability of native-like ions using tandem IM experiments implemented using structures for lossless ion manipulations (SLIM). In this implementation of tandem IM, ions undergo a first dimension of IM up to a switch that is used to selectively transmit ions of a desired mobility. Selected ions are accumulated in a trap and then released after a delay to initiate the second dimension of IM. For delays ranging from 16 to 33 231 ms, the collision cross sections of native-like, 7+ cytochrome c ions increase monotonically from 15.1 to 17.1 nm(2). The largest products formed in these experiments at near-ambient temperature are still far smaller than those formed in energy-dependent experiments (∼21 nm(2)). However, the collision cross section increases by ∼2% between delay times of 16 and 211 ms, which may have implications for other IM experiments on these time scales. Finally, two subpopulations from the full population were each mobility selected and analyzed as a function of delay time, showing that the three populations can be differentiated for at least 1 s. Together, these results suggest that elements of native-like structure can have long lifetimes at near-ambient temperature in the gas phase but that gas-phase dynamics should be considered when interpreting results from IM.

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

    PubMed Central

    2015-01-01

    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 ion mobility spectrometry (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. PMID:24786390

  10. Improving ion mobility measurement sensitivity by utilizing helium in an ion funnel trap.

    PubMed

    Ibrahim, Yehia M; Garimella, Sandilya V B; Tolmachev, Aleksey V; Baker, Erin S; Smith, Richard D

    2014-06-03

    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 ion mobility spectrometry (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.

  11. Corona discharge ion mobility spectrometry at reduced pressures

    NASA Astrophysics Data System (ADS)

    Tabrizchi, Mahmoud; Rouholahnejad, Fereshteh

    2004-11-01

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

  12. Experimental ion mobility measurements in Xe-CH4

    NASA Astrophysics Data System (ADS)

    Perdigoto, J. M. C.; Cortez, A. F. V.; Veenhof, R.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Conde, C. A. N.

    2017-09-01

    Data on ion mobility is important to improve the performance of large volume gaseous detectors. In the present work, the method, experimental setup and results for the ion mobility measurements in Xe-CH4 mixtures are presented. The results for this mixture show the presence of two distinct groups of ions. The nature of the ions depend on the mixture ratio since they are originated by both Xe and CH4. The results here presented were obtained for low reduced electric fields, E/N, 10–25 Td (2.4–6.1 kV ṡ cm‑1 ṡ bar‑1), at low pressure (8 Torr) (10.6 mbar), and at room temperature.

  13. 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.

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

    PubMed

    Ilbeigi, Vahideh; Tabrizchi, Mahmoud

    2015-01-06

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

  15. Characterization of a Distributed Plasma Ionization Source (DPIS) for Ion Mobility Spectrometry and Mass Spectrometry

    SciTech Connect

    Waltman, Melanie J.; Dwivedi, Prabha; Hill, Herbert; Blanchard, William C.; Ewing, Robert G.

    2008-10-15

    A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry and ion mobility spectrometry. The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions depending on the polarity of the applied potential. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H2O)nH+ with (H2O)2H+ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO3-, NO3-, NO2-, O3- and O2- of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and environmental pollutants were selected to evaluate the new ionization source. The source was operated continuously for several months and although deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions. The results indicated that the DPIS may have a longer operating life than a conventional corona discharge.

  16. Characterization of a distributed plasma ionization source (DPIS) for ion mobility spectrometry and mass spectrometry.

    PubMed

    Waltman, Melanie J; Dwivedi, Prabha; Hill, Herbert H; Blanchard, William C; Ewing, Robert G

    2008-10-19

    A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry (MS) and ion mobility spectrometry (IMS). The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H(2)O)(n)H(+) with (H(2)O)(2)H(+) as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO(3)(-), NO(3)(-), NO(2)(-), O(3)(-) and O(2)(-) of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and amines were selected to evaluate the new ionization source. The source was operated continuously for 3 months and although surface deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions.

  17. 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.

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

    PubMed

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

    2016-11-01

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

  19. 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.

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

    PubMed

    Michaelevski, Izhak; Kirshenbaum, Noam; Sharon, Michal

    2010-07-31

    Ion mobility (IM) is a method that measures the time taken for an ion to travel through a pressurized cell under the influence of a weak electric field. The speed by which the ions traverse the drift region depends on their size: large ions will experience a greater number of collisions with the background inert gas (usually N(2;)) and thus travel more slowly through the IM device than those ions that comprise a smaller cross-section. In general, the time it takes for the ions to migrate though the dense gas phase separates them, according to their collision cross-section (Omega). Recently, IM spectrometry was coupled with mass spectrometry and a traveling-wave (T-wave) Synapt ion mobility mass spectrometer (IM-MS) was released. Integrating mass spectrometry with ion mobility enables an extra dimension of sample separation and definition, yielding a three-dimensional spectrum (mass to charge, intensity, and drift time). This separation technique allows the spectral overlap to decrease, and enables resolution of heterogeneous complexes with very similar mass, or mass-to-charge ratios, but different drift times. Moreover, the drift time measurements provide an important layer of structural information, as Omega is related to the overall shape and topology of the ion. The correlation between the measured drift time values and Omega is calculated using a calibration curve generated from calibrant proteins with defined cross-sections(1). The power of the IM-MS approach lies in its ability to define the subunit packing and overall shape of protein assemblies at micromolar concentrations, and near-physiological conditions(1). Several recent IM studies of both individual proteins(2,3) and non-covalent protein complexes(4-9), successfully demonstrated that protein quaternary structure is maintained in the gas phase, and highlighted the potential of this approach in the study of protein assemblies of unknown geometry. Here, we provide a detailed description of IMS

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  2. Factors influencing the separation of oligonucleotides using reversed-phase/ion-exchange mixed-mode high performance liquid chromatography columns.

    PubMed

    Biba, Mirlinda; Jiang, Eileen; Mao, Bing; Zewge, Daniel; Foley, Joe P; Welch, Christopher J

    2013-08-23

    New mixed-mode columns consisting of reversed-phase and ion-exchange separation modes were evaluated for the analysis of short RNA oligonucleotides (∼20mers). Conventional analysis for these samples typically involves using two complementary methods: strong anion-exchange liquid chromatography (SAX-LC) for separation based on charge, and ion-pair reversed-phase liquid chromatography (IP-RPLC) for separation based on hydrophobicity. Recently introduced mixed-mode high performance liquid chromatography (HPLC) columns combine both reversed-phase and ion-exchange modes, potentially offering a simpler analysis by combining the benefits of both separation modes into a single method. Analysis of a variety of RNA oligonucleotide samples using three different mixed-mode stationary phases showed some distinct benefits for oligonucleotide separation and analysis. When using these mixed-mode columns with typical IP-RPLC mobile phase conditions, such as ammonium acetate or triethylammonium acetate as the primary ion-pair reagent, the separation was mainly based on the IP-RPLC mode. However, when changing the mobile phase conditions to those more typical for SAX-LC, such as salt gradients with NaCl or NaBr, very different separation patterns were observed due to mixed-mode interactions. In addition, the Scherzo SW-C18 and SM-C18 columns with sodium chloride or sodium bromide salt gradients also showed significant improvements in peak shape.

  3. Arrival time distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility-mass spectrometry of hyaluronan-derived oligosaccharides.

    PubMed

    Hermannová, Martina; Iordache, Andreea-Maria; Slováková, Kristína; Havlíček, Vladimír; Pelantová, Helena; Lemr, Karel

    2015-06-01

    Hyaluronic acid is a naturally occurring linear polysaccharide with substantial medical potential. In this work, discrimination of tyramine-based hyaluronan derivatives was accessed by ion mobility-mass spectrometry of deprotonated molecules and nuclear magnetic resonance spectroscopy. As the product ion mass spectra did not allow for direct isomer discrimination in mixture, the reductive labeling of oligosaccharides as well as stable isotope labeling was performed. The ion mobility separation of parent ions together with the characteristic fragmentation for reduced isomers providing unique product ions allowed us to identify isomers present in a mixture and determine their mutual isomeric ratio. The determination used simple recalculation of arrival time distribution areas of unique ions to areas of deprotonated molecules. Mass spectrometry data were confirmed by nuclear magnetic resonance spectroscopy.

  4. Computational exploration of mobile ion distributions around RNA duplex

    PubMed Central

    Kirmizialtin, Serdal; Elber, Ron

    2010-01-01

    Atomically detailed distributions of ions around an A-form RNA are computed. Different mixtures of monovalent and divalent ions are considered explicitly. Studies of tightly bound and of diffusive (but bound) ions around 25 base pairs RNA are conducted in explicit solvent. Replica exchange simulations provide detailed equilibrium distributions with moderate computing resources (20 nanoseconds of simulation using 64 replicas). The simulations show distinct behavior of single and doubly charged cations. Binding of Mg2+ ion includes tight binding to specific sites while Na+ binds only diffusively. The tight binding of Mg2+ is with a solvation shell while Na+ can bind directly to RNA. Negative mobile ions can be found near the RNA but must be assisted by proximate and mobile cations. At distances larger than 16Å from the RNA center, a model of RNA as charged rod in a continuum of ionic solution provides quantitative description of the ion density (the same as in atomically detailed simulation). At shorter distances, the structure of RNA (and ions) have significant impact on the pair correlation functions. Predicted binding sites of Mg2+ at the RNA surface are in accord with structures from crystallography. Electric field relaxation is investigated. The relaxation due to solution rearrangements is completed in tens of picoseconds, while the contribution of RNA tumbling continues to a few nanoseconds. PMID:20518549

  5. 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.

  6. 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.

  7. 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.

  8. Mobility resolution and mass analysis of ions from ammonia and hydrazine complexes with ketones formed in air at ambient pressure.

    PubMed

    Bollan, H R; Stone, J A; Brokenshire, J L; Rodriguez, J E; Eiceman, G A

    2007-05-01

    Protonated ammonia and hydrazines (MH(+)) form complexes with ketones and the differences in masses and mobilities of the resulting ions, MH(+)(ketone)(n), are sufficient for separation in an ion mobility spectrometer at ambient pressure. The highest mass ion for any of the protonated molecules is obtained when the ketone is present at elevated concentrations in the supporting atmosphere of both the source and drift regions of the spectrometer so that an ion maintains a discrete composition and mobility. The sizes of the ion-molecule complexes were found to depend on the number of H atoms on the protonated nitrogen atom--four for ammonia, three for hydrazine, two for monomethylhydrazine, and one for 1,1-dimethylhydrazine, and the drift times of these ions were proportional to the size of the ion-molecule complex. Unexpected side products, including protonated hydrazones and azines, and associated ketone clusters, were isolated to a single drift tube containing ceramic parts and could not, from CID studies, be attributed to gas-phase ion chemistry. These findings illustrate that mobility resolution of ions in IMS and IMS/MS experiments can be enhanced through chemical modification of the supporting gas atmosphere without changes in the core ion.

  9. Preparation and characterization of monoliths covalently bonded chelating groups for capillary electrochromatographic separation of metal ions.

    PubMed

    Wang, Guan-Ren; Huang, Kuan-Pin; Huang, Bao-Yu; Liu, Chuen-Ying

    2009-08-21

    In this work, a novel polymer-based monolithic column was prepared using an o-phthalaldehyde-l-phenylalanine Schiff base complex as the reactive center and a mixture of methanol and n-propanol as the porogen. The monolithic column was employed for the separation of a metal ion mixture including Pb(II), Mn(II), Cu(II), Ni(II), Cr(III), Fe(III) and Cr(VI). Tetrabutylammonium bromide (TBAB) was used as a mobile phase additive to enhance the separation efficiency of metal ions by EDTA precomplexation. Using a phosphate buffer (20 mM, pH 3.0), TBAB (10 mM), MeOH (15%, v/v), an applied voltage of -15 kV, and detection at 220 nm, the metal ion mixture was satisfactorily resolved. The average theoretical plate number was 17,900 plates/m. The separation was also carried out in the absence of TBAB, leading to dissimilar elution order and shorter retention time. The separation behavior of the monolithic column was also compared with that of the blank polymer. The unique properties of the monolithic column might be mediated by a combination of electrophoretic behavior and chromatographic retention involving hydrophobic and hydrophilic interactions, as well as ligand exchange.

  10. 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.

  11. Fast Screening of Polycyclic Aromatic Hydrocarbons using Trapped Ion Mobility Spectrometry - Mass Spectrometry

    PubMed Central

    Castellanos, A.; Benigni, P.; Hernandez, D. R.; DeBord, J. D.; Ridgeway, M. E.; Park, M. A.

    2014-01-01

    In the present paper, we showed the advantages of trapped ion mobility spectrometry coupled too mass spectrometry (TIMS-MS) combined with theoretical calculations for fast identification (millisecond timescale) of polycyclic aromatic hydrocarbons (PAH) compounds from complex mixtures. Accurate PAH collision cross sections (CCS, in nitrogen as a bath gas) are reported for the most commonly encountered PAH compounds and the ability to separate PAH geometric isomers is shown for three isobaric pairs with mobility resolution exceeding 150 (3–5 times higher than conventional IMS devices). Theoretical candidate structures (optimized at the DFT/B3LYP level) are proposed for the most commonly encountered PAH compounds showing good agreement with the experimental CCS values (<5%). The potential of TIMS-MS for the separation and identification of PAH compounds from complex mixtures without the need of lengthy pre-separation steps is illustrated for the case of a complex soil mixture. PMID:25558291

  12. 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.

  13. 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.

  14. 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.

  15. Multiplexed Ion Mobility Spectrometry - Orthogonal Time-Of-Flight Mass Spectrometry

    SciTech Connect

    Belov, Mikhail E.; Buschbach, Michael A.; Prior, David C.; Tang, Keqi; Smith, Richard D.

    2007-03-15

    Ion mobility spectrometry (IMS) coupled to orthogonal time-of-flight mass spectrometry (TOF) has shown significant promise for the characterization of complex biological mixtures. The enormous complexity of biological samples (e.g. from proteomics) and the need for both biological and technical analysis replicates imposes major challenges for multidimensional separation platforms in regard to both sensitivity and sample throughput. A major potential attraction of the IMS-TOF MS platform is separation speeds exceeding that of conventional condensed-phase separations by orders of magnitude. Known limitations of the IMS-TOF MS platforms that presently mitigate this attraction include the need for extensive signal averaging due to factors that include significant ion losses in the IMS-TOF interface and an ion utilization efficiency of less than ~1% with continuous ion sources (e.g. ESI). We have developed a new multiplexed ESI-IMS-TOF mass spectrometer that enables lossless ion transmission through the IMS-TOF as well as a utilization efficiency of >50% for ions from the ESI source. Initial results with a mixture of peptides show a ~10-fold increase in signal-to-noise ratio with the multiplexed approach compared to a signal averaging approach, with no reduction in either IMS or TOF MS resolution.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-04-01

    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.

  18. Fragmentation and ion mobility properties of negative ions from N-linked carbohydrates: Part 7. Reduced glycans.

    PubMed

    Harvey, David J; Abrahams, Jodie L

    2016-03-15

    Negative ion collision-induced dissociation (CID) spectra of released N-glycans provide very informative structural information relating to branching patterns and location of residues such as fucose. For some structural studies, particularly those involving chromatography, glycans are often reduced to avoid production of multiple peaks from α- and β-anomers. We examined the effect of reduction on the production of diagnostic fragment ions and on the ion mobility properties of N-glycans. Released N-glycans from the glycoproteins bovine fetuin, ribonuclease B, chicken ovalbumin, and porcine thyroglobulin were reduced with sodium cyanoborohydride and both negative ion CID spectra and ion mobility properties of their phosphate adducts were examined with a Waters Synapt G2Si travelling-wave ion mobility mass spectrometer with electrospray sample introduction. Estimated collisional cross sections were measured with dextran as the calibrant, Fragment ions were similar to those from the unreduced glycans with the exception that the prominent (2,4) A cleavage ion from the reducing terminus was replaced by a prominent [M-H3 PO4](-) ion. Other ions arising from the chitobiose core were of lower relative abundance than those from the unreduced glycans. Estimated collisional cross sections were similar to those of the unreduced compounds but with symmetrical arrival time distribution (ATD) profiles, unlike those of the unreduced glycans whose peaks often contained prominent asymmetry. This observation showed that this asymmetry was due to anomer separation. Reduction of the reducing terminal GlcNAc residue resulted in fewer diagnostic ions from the chitobiose core but fragmentation of the remainder of the molecules generally paralleled that of the unreduced glycans. Thus, most structural information, with the exception of the linkage position of fucose on the core GlcNAc, was available. ATD peaks were symmetrical with the result that cross sections were more appropriate for

  19. 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.

  20. Polymers for Traveling Wave Ion Mobility Spectrometry Calibration

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  1. 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.

  2. Correcting the fundamental ion mobility equation for field effects.

    PubMed

    Siems, William F; Viehland, Larry A; Hill, Herbert H

    2016-11-14

    The fundamental ion mobility equation computes the energy-averaged collision cross section as a function of measured drift velocity, electric field strength, ion and neutral masses, and drift gas state parameters. As field strength approaches zero, in particular when the drift velocity drops below about 4% of the average ion-neutral thermal speed, the fundamental equation takes on an especially simple form because the collision frequency and average momentum transfer become indistinguishable from their thermal values. However, in modern high-performance IMS-MS instruments, ion drift velocities may be 10-50% or more of thermal speed, and analysis using the zero-field equation gives rise to erroneously large cross sections. We address this problem by developing correction factors for the zero-field equation from an improved momentum-transfer (MT) theory for ion mobility, corrected and completed herein, and from the well-known two-temperature (2T) theory. The corrected and uncorrected equations are compared by their ability to recover known hard-sphere cross sections from accurately-computed mobility data. Both MT and 2T expressions adjust for the field-driven increase in collision frequency and are noticeably superior to zero-field expression whenever the ion drift velocity is greater than ∼4% of thermal speed. The MT expression also adjusts for the mass and field dependent change in average momentum transfer, and is more accurate than the 2T first approximation whenever the mass of the ionic species is greater than about four times that of drift gas molecules, as is the case in most analytical applications of IMS coupled to MS.

  3. Ion mobility analyzer - quadrupole mass spectrometer system design

    NASA Astrophysics Data System (ADS)

    Cuna, C.; Leuca, M.; Lupsa, N.; Mirel, V.; Bocos-Bintintan, V.; Cuna, Stela; Cosma, V.; Tusa, Florina

    2009-08-01

    Because of their extremely high sensitivity for chemicals with elevated electronegativity or high proton affinity the ion mobility analysers are ideal for the ultra-trace detection of toxic or explosive chemicals, most of these situated often at concentration levels of sub-ppb (parts-per-billion). Ion mobility spectrometers (IMS) can be used to identify illicit drugs or environmental pollutants. Since resolution of an IMS is relatively low, to achieve an accurate identification of target analyte it is recommended to couple the IMS with a quadrupole mass spectrometer (QMS) or a time of flight mass spectrometer, acquiring in this way confirmatory information. This coupling is made through a specific interface. In this paper, an experimental model of such a tandem instrument, IMS-QMS is described. Accomplishment of this general purpose will be done, overcoming a series of specific issues. This implies the solving, using innovative solutions, of a series of complex issues: ensuring the stability of the ions beam generated by ion source; transfer with a good efficiency of the ionic current from IMS analyser to QMS; and realization of a special electronic circuitry which will be able to detect both positive and negative ions.

  4. 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.

  5. Tandem ion mobility-mass spectrometry (IMS-MS) study of ion evaporation from ionic liquid-acetonitrile nanodrops.

    PubMed

    Hogan, Christopher J; Fernández de la Mora, Juan

    2009-09-28

    Ion evaporation is an essential step in the formation of charged ions from electrosprays, yet many aspects of the process are poorly understood. The ion evaporation kinetics of the 1-ethyl-3-methyl-imidazolium+ (EMI+) based ionic liquids (ILs) EMI-BF4, EMI-bis(perfluoroethylsulfonyl)imide, EMI-bis(trifluoromethylsulfonyl)imide and EMI-tris(trifluoromethylsulfonyl)methide (EMI-Methide) are studied by tandem ion mobility-mass spectrometry (IMS-MS) of IL nanodrop residues from positive and negative electrosprays of IL-acetonitrile solutions. Two-dimensional (2D) IMS-MS spectra are obtained using a differential mobility analyzer (DMA) coupled to a commercial quadrupole-time-of-flight mass spectrometer. Nanodrops of different charge states (z=1,2,...,10,...) are separated into distinct bands in 2D DMA-MS spectra, allowing for determination of both nanodrop size (radius) and charge. With the exception of negatively charged EMI-BF4, all clusters observed are charged below the Rayleigh limit of both the ILs and acetonitrile, showing that the charge loss mechanism is ion evaporation. Solvation energies, DeltaG, of evaporating ions from acetonitrile are inferred from radius and charge state data. With the exclusion of EMI-BF4 in negative mode (DeltaG>1.84 eV), all are in the 1.54-1.65 eV range, considerably lower than previously reported for tetra-alkyl ammonium salts in formamide. Measured size distributions of EMI-Methide nanodrops agree with those predicted by ion evaporation theory, though with narrower widths observed for doubly and singly charged nanodrops.

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    2016-03-28

    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 × 10{sup 6} cm{sup 2}/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.

  8. Increased Ion Transmission for Differential Ion Mobility Combined with Mass Spectrometry by Implementation of a Flared Inlet Capillary

    NASA Astrophysics Data System (ADS)

    Campbell, Matthew T.; Glish, Gary L.

    2017-01-01

    Differential ion mobility spectrometry (DIMS) is capable of separating components of complex mixtures prior to mass spectrometric analysis, thereby increasing signal-to-noise and signal-to-background ratios on millisecond timescales. However, adding a DIMS device to the front end of a mass spectrometer can reduce the signal intensity of subsequent mass spectrometric analysis. This is a result, in part, of ions lost due to inefficient transfer of ions from the DIMS device through the aperture leading into the mass spectrometer. This problem of transferring ions can be at least partially corrected by modifying the front end of the inlet capillary leading to the vacuum of the mass spectrometer. The inner diameter of the ion-sampling end of the inlet capillary was enlarged by drilling into the face. This results in a conical flare at the front end of the capillary, while the other end of the capillary remains unmodified. These flared capillaries allow for a greater number of ions from the DIMS device to be sampled relative to the unmodified standard capillary. Four flare dimensions were tested, differing by the angle between the wall of the flare and the outer wall of the inlet capillary. All flared capillaries showed greater signal intensity than the standard capillary with a DIMS device present without reducing the resolving power. It was also observed that the signal intensity increased as the flare angle decreased. The flared capillary with the smallest flare angle showed greater than a fivefold increase in signal intensity compared with the standard capillary.

  9. Selective detection of alkanolamine vapors by ion mobility spectrometry with ketone reagent gases.

    PubMed

    Gan, T H; Corino, G

    2000-02-15

    The ion mobility (IMS) spectra of the alkanolamines, monoethanolamine (MEA), 3-amino-1-propanol (PRA), 4-amino-1-butanol (BUA), and 5-amino-1-pentanol (PEA) with acetone and 4-heptanone reagent gases have been measured using a hand-held spectrometer. Monomer and dimer peak patterns were observed for all the alkanolamines with acetone reagent gas. Drift times of monomer and dimer ion clusters for each alkanolamine increased linearly in order of size of alkyl group. Ammonia, Freon 22, and F76 diesel vapors, having similar or coincident mobilities, caused severe interference. Replacement of acetone with 4-heptanone reagent gas resulted in good separation by the altering drift times of product ions. The limit of detection was 0.005 ppm having a linear range of 0.005-0.7 ppm, and signal saturation occurred above 0.88 ppm. Detection was reversible, with a response time of 4 min and a slower recovery time of > 60 min, at vapor levels of 0.7 ppm and ambient nozzle and drift-region temperatures. In contrast to acetone chemistry, single-peak patterns were observed for the alkanolamines with the 4-heptanone reagent. Further, drift times unexpectedly remained stagnant with increasing alkyl-group size. From atmospheric pressure chemical ionization (APcI) tandem mass spectral identifications and collision induced studies, dynamic changes in product-ion equilibria in the IMS drift region compensated by differences in collision cross sections were suggested as the governing causes of the unusual mobility effect.

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

    PubMed Central

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

    2014-01-01

    Rapid separation and independent analysis of isomeric species are needed for the structural characterization of carbohydrates in glycomics research. Ion mobility-mass spectrometry techniques were used to examine a series of isomeric neutral oligosaccharide-alditols derived from bovine submaxillary mucin. Several analytical techniques were employed: (1) off line separation of the oligosaccharide-alditol mixture by HPLC; (2) direct and rapid evaluation of isomeric heterogeneity of oligosaccharides by electrospray ionization-ion mobility-time of flight mass spectrometry; and (3) mobility-selected MS2 and MS3 to evaluate isomeric mobility peaks by dual gate ion mobility-tandem mass spectrometry. Multiple isomeric ion mobility peaks were observed for the majority of oligosaccharide-alditols, which was achieved on the millisecond time scale after LC separation. Fragmentation spectra obtained from the collision-induced dissociation of isomeric precursor ions could be essentially identical, or dramatically different for a given precursor m/z using the dual-gate ion mobility quadrupole ion trap mass spectrometer. This further confirmed the need for rapid physical resolution of isomeric precursor species prior to their tandem mass spectral analysis. PMID:24634605

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

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

    PubMed

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

    2015-02-01

    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.

  17. Separation of Aliphatic and Aromatic Carboxylic Acids by Conventional and Ultra High Performance Ion Exclusion Chromatography.

    PubMed

    Mansour, Fotouh R; Kirkpatrick, Christine L; Danielson, Neil D

    2013-06-01

    An ion exclusion chromatography (IELC) comparison between a conventional ion exchange column and an ultra-high performance liquid chromatography (UHPLC) dynamically surfactant modified C18 column for the separation of an aliphatic carboxylic acid and two aromatic carboxylic acids is presented. Professional software is used to optimize the conventional IELC separation conditions for acetylsalicylic acid and the hydrolysis products: salicylic acid and acetic acid. Four different variables are simultaneously optimized including H2SO4 concentration, pH, flow rate, and sample injection volume. Thirty different runs are suggested by the software. The resolutions and the time of each run are calculated and feed back to the software to predict the optimum conditions. Derringer's desirability functions are used to evaluate the test conditions and those with the highest desirability value are utilized to separate acetylsalicylic acid, salicylic acid, and acetic acid. These conditions include using a 0.35 mM H2SO4 (pH 3.93) eluent at a flow rate of 1 mL min(-1) and an injection volume of 72 μL. To decrease the run time and improve the performance, a UHPLC C18 column is used after dynamic modification with sodium dodecyl sulfate. Using pure water as a mobile phase, a shorter analysis time and better resolution are achieved. In addition, the elution order is different from the IELC method which indicates the contribution of the reversed-phase mode to the separation mechanism.

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

    PubMed

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

    2014-04-15

    Metabolomics is a rapidly evolving analytical approach in life and health sciences. The structural elucidation of the metabolites of interest remains a major analytical challenge in the metabolomics workflow. Here, we investigate the use of ion mobility as a tool to aid metabolite identification. Ion mobility allows for the measurement of the rotationally averaged collision cross-section (CCS), which gives information about the ionic shape of a molecule in the gas phase. We measured the CCSs of 125 common metabolites using traveling-wave ion mobility-mass spectrometry (TW-IM-MS). CCS measurements were highly reproducible on instruments located in three independent laboratories (RSD < 5% for 99%). We also determined the reproducibility of CCS measurements in various biological matrixes including urine, plasma, platelets, and red blood cells using ultra performance liquid chromatography (UPLC) coupled with TW-IM-MS. The mean RSD was < 2% for 97% of the CCS values, compared to 80% of retention times. Finally, as proof of concept, we used UPLC-TW-IM-MS to compare the cellular metabolome of epithelial and mesenchymal cells, an in vitro model used to study cancer development. Experimentally determined and computationally derived CCS values were used as orthogonal analytical parameters in combination with retention time and accurate mass information to confirm the identity of key metabolites potentially involved in cancer. Thus, our results indicate that adding CCS data to searchable databases and to routine metabolomics workflows will increase the identification confidence compared to traditional analytical approaches.

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

    PubMed

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

    2015-08-21

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

  20. 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

  1. Separation of phycocyanin from Spirulina platensis using ion exchange chromatography.

    PubMed

    Silveira, Silvana Terra; Quines, Luci Kelin de Menezes; Burkert, Carlos André Veiga; Kalil, Susana Juliano

    2008-08-01

    This paper presents the evaluation of some important parameters for the purification of phycocyanin using ion exchange chromatography. The influences of pH and temperature on the equilibrium partition coefficient were investigated to establish the best conditions for phycocyanin adsorption. The equilibrium isotherm for the phycocyanin-resin system was also determined. The separation of phycocyanin using the Q-Sepharose ion exchange resin was evaluated in terms of the pH and elution volume that improved the increase in purity and recovery. The highest partition coefficients were obtained in the pH range from 7.5 to 8.0 at 25 degrees C. Under these conditions the equilibrium isotherm for phycocyanin adsorption was well described by the Langmuir model, attaining a Q (m) of 22.7 mg/mL and K (d) of 3.1 x 10(-2) mg/mL. The best conditions for phycocyanin purification using the ion exchange column were at pH 7.5 with an elution volume of 36 mL, obtaining 77.3% recovery and a 3.4-fold increase in purity.

  2. 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.

  3. 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.

  4. 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.

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

    PubMed

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

    2017-04-05

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

  6. 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.

  7. 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.

  8. 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.

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

    DOE PAGES

    Prost, Spencer A.; Crowell, Kevin L.; Baker, Erin Shammel; ...

    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

  10. 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.

  11. Ion-Gated Gas Separation through Porous Graphene

    DOE PAGES

    Tian, Ziqi; Mahurin, Shannon M.; Dai, Sheng; ...

    2017-02-10

    Porous graphene holds great promise as an atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size at three to five angstroms proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise non-selective large pores on the order of 1 nm in size to be selective for gases whose diameters range from three to four angstroms. We show from molecular dynamics simulations that CO2, N2 and CH4 all can permeate through a 1-nmmore » pore in graphene without any selectivity. But when a monolayer of [emim][BF4] is deposited on the porous graphene, CO2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO2 while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO2/CH4 separation, with a CO2/CH4 selectivity of about 42 and CO2 permeance ~105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size. The present work points toward a promising direction of using the atom-thin ionic-liquid/porous-graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.« less

  12. Ion-Gated Gas Separation through Porous Graphene.

    PubMed

    Tian, Ziqi; Mahurin, Shannon M; Dai, Sheng; Jiang, De-En

    2017-03-08

    Porous graphene holds great promise as a one-atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size down to 3-5 Å proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid-coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise nonselective large pores on the order of 1 nm in size to be selective for gases whose diameters range from 3 to 4 Å. We show from molecular dynamics simulations that CO2, N2, and CH4 all can permeate through a 6 Å nanopore in graphene without any selectivity. But when a monolayer of [emim][BF4] ionic liquid (IL) is deposited on the porous graphene, CO2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO2, while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO2/CH4 separation, yielding a CO2/CH4 selectivity of about 42 and CO2 permeance of ∼10(5) GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size, pore size, and IL thickness. The present work points toward a promising direction of using the atom-thin ionic liquid/porous graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.

  13. 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

  14. 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.

  15. Entanglement-Based dc Magnetometry with Separated Ions*

    NASA Astrophysics Data System (ADS)

    Ruster, T.; Kaufmann, H.; Luda, M. A.; Kaushal, V.; Schmiegelow, C. T.; Schmidt-Kaler, F.; Poschinger, U. G.

    2017-07-01

    We demonstrate sensing of inhomogeneous dc magnetic fields by employing entangled trapped ions, which are shuttled in a segmented Paul trap. As sensor states, we use Bell states of the type |↑↓ ⟩ +ei φ|↓↑ ⟩ encoded in two 40Ca+ ions stored at different locations. The linear Zeeman effect leads to the accumulation of a relative phase φ , which serves for measuring the magnetic-field difference between the constituent locations. Common-mode magnetic-field fluctuations are rejected by the entangled sensor state, which gives rise to excellent sensitivity without employing dynamical decoupling and therefore enables accurate dc sensing. Consecutive measurements on sensor states encoded in the S1 /2 ground state and in the D5 /2 metastable state are used to separate an ac Zeeman shift from the linear dc Zeeman effect. We measure magnetic-field differences over distances of up to 6.2 mm, with accuracies down to 300 fT and sensitivities down to 12 pT /√{Hz }. Our sensing scheme features spatial resolutions in the 20-nm range. For optimizing the information gain while maintaining a high dynamic range, we implement an algorithm for Bayesian frequency estimation.

  16. 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

  17. 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.

  18. 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

    2016-02-07

    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.

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

    PubMed

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

    2011-02-01

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

  20. 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.

  1. MALDI-MS/MS with traveling wave ion mobility for the structural analysis of N-linked glycans.

    PubMed

    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.

  2. Accurate Drift Time Determination by Traveling Wave Ion Mobility Spectrometry: The Concept of the Diffusion Calibration.

    PubMed

    Kune, Christopher; Far, Johann; De Pauw, Edwin

    2016-12-06

    Ion mobility spectrometry (IMS) is a gas phase separation technique, which relies on differences in collision cross section (CCS) of ions. Ionic clouds of unresolved conformers overlap if the CCS difference is below the instrumental resolution expressed as CCS/ΔCCS. The experimental arrival time distribution (ATD) peak is then a superimposition of the various contributions weighted by their relative intensities. This paper introduces a strategy for accurate drift time determination using traveling wave ion mobility spectrometry (TWIMS) of poorly resolved or unresolved conformers. This method implements through a calibration procedure the link between the peak full width at half-maximum (fwhm) and the drift time of model compounds for wide range of settings for wave heights and velocities. We modified a Gaussian equation, which achieves the deconvolution of ATD peaks where the fwhm is fixed according to our calibration procedure. The new fitting Gaussian equation only depends on two parameters: The apex of the peak (A) and the mean drift time value (μ). The standard deviation parameter (correlated to fwhm) becomes a function of the drift time. This correlation function between μ and fwhm is obtained using the TWIMS calibration procedure which determines the maximum instrumental ion beam diffusion under limited and controlled space charge effect using ionic compounds which are detected as single conformers in the gas phase. This deconvolution process has been used to highlight the presence of poorly resolved conformers of crown ether complexes and peptides leading to more accurate CCS determinations in better agreement with quantum chemistry predictions.

  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. The periodic focusing ion funnel: theory, design, and experimental characterization by high-resolution ion mobility-mass spectrometry.

    PubMed

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

    2013-10-15

    Simulation-based development and experimental characterization of a DC-only ion funnel is described herein. Radial ion confinement is achieved via periodic focusing whereby a collisionally dampened effective potential is generated in the inertial frame of an ion traversing the device with appreciable velocity. The new device, termed a periodic focusing ion funnel (PF IF), provides an efficient alternative to the rf ion funnel providing high ion transmission with fewer electrodes, simplified electrical circuitry, and reduced power supply requirements. The utility of the PF IF for structural ion mobility-mass spectrometry (IM-MS) studies is demonstrated using model peptide ions (bradykinin, gramicidin S, and trpzip 1).

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

    PubMed

    Van der Rest, Guillaume; Halgand, Frédéric

    2017-09-20

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

  6. Retention behavior of isomeric triacylglycerols in silver-ion HPLC: effects of mobile phase composition and temperature.

    PubMed

    Lísa, Miroslav; Denev, Rumen; Holčapek, Michal

    2013-09-01

    A systematic study of the retention behavior of isomeric triacylglycerols (TGs) in silver-ion HPLC on a ChromSpher Lipids column has been performed between 10 to 40°C using the most widespread hexane- and dichloromethane-based mobile phases. The randomization of mono-acyl TG standards and the random esterification of glycerol with fatty acids are employed to produce mixtures of TG isomers. The mobile phase composition has no influence on the general retention pattern, but significant differences in the retention order of double bond (DB) positional isomers in hexane and dichloromethane mobile phases are described and compared with the previous literature data. Saturated TGs with fatty acyl chain length from C7:0 to C22:0 are partially separated using the hexane mobile phase but not at all with the dichloromethane mobile phase. The hexane mobile phase enables at least partial resolution of TG regioisomers with up to seven DBs, while the resolution of only ALA/AAL and ALnA/AALn isomers is achieved with the dichloromethane mobile phase. The effect of temperature differs significantly depending on the mobile phase composition. Retention times of TGs increase with increasing temperature in the hexane mobile phase, while an opposite effect is observed for the dichloromethane mobile phase.

  7. 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.

  8. 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.

  9. 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.

  10. Electrospray ionization high-resolution ion mobility spectrometry for the detection of organic compounds, 1. Amino acids.

    PubMed

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

    2001-07-01

    Our aim in this investigation was to demonstrate the potential of the high-resolution electrospray ionization ion mobility spectrometry (ESI-IMS) technique as an analytical separation tool in analyzing biomolecular mixtures to pursue astrobiological objectives of searching for the chemical signatures of life during an in-situ exploration of solar system bodies. Because amino acids represent the basic building blocks of life, we used common amino acids to conduct the first part of our investigation, which is being reported here, to demonstrate the feasibility of using the ESI-IMS technique for detection of the chemical signatures of life. The ion mobilities of common amino acids were determined by electrospray ionization ion mobility spectrometry using three different drift gases (N2, Ar, and CO2). We demonstrated that the selectivity can be vastly improved in ion mobility spectroscopy (IMS) in detecting organic molecules by using different drift gases. When a judicial choice of drift gas is made, a vastly improved separation of two different amino acid ions resulted. It was found that each of the studied amino acids could be uniquely identified from the others, with the exception of alanine and glycine, which were never separable by more then 0.1 ms. This unique identification is a result of the different polarizabilities of the various drift gases. In addition, a better separation was achieved by changing the drift voltage in successive experimental runs without significantly degrading the resolution. We also report the result of our analysis of liquid samples containing mixtures of amino acids.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

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

    PubMed

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

    2013-01-02

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

  17. 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.

  18. Miniaturized low-cost ion mobility spectrometer for fast detection of chemical warfare agents.

    PubMed

    Zimmermann, Stefan; Barth, Sebastian; Baether, Wolfgang K M; Ringer, Joachim

    2008-09-01

    Ion mobility spectrometry (IMS) is a well-known method for detecting hazardous compounds in air. Typical applications are the detection of chemical warfare agents, highly toxic industrial compounds, explosives, and drugs of abuse. Detection limits in the low part per billion range, fast response times, and simple instrumentation make this technique more and more popular. In particular, there is an increasing demand for miniaturized low-cost IMS for hand-held devices and air monitoring of public areas by sensor networks. In this paper, we present a miniaturized aspiration condenser type ion mobility spectrometer for fast detection of chemical warfare agents. The device is easy to manufacture and allows single substance identification down to low part per billion-level concentrations within seconds. The improved separation power results from ion focusing by means of geometric constraints and fluid dynamics. A simple pattern recognition algorithm is used for the identification of trained substances in air. The device was tested at the German Armed Forces Scientific Institute for Protection Technologies-NBC-Protection. Different chemical warfare agents, such as sarin, tabun, soman, US-VX, sulfur mustard, nitrogen mustard, and lewisite were tested. The results are presented here.

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

    PubMed

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

    2017-02-01

    Ion mobility-mass spectrometry (IM-MS) has recently seen increased use in the analysis of small molecules, especially in the field of metabolomics, for increased breadth of information and improved separation of isomers. In this study, steroid epimers androsterone and trans-androsterone were analyzed with IM-MS to investigate differences in their relative mobilities. Although sodiated monomers exhibited very similar collision cross-sections (CCS), baseline separation was observed for the sodiated dimer species (RS = 1.81), with measured CCS of 242.6 and 256.3 Å(2), respectively. Theoretical modeling was performed to determine the most energetically stable structures of solution-phase and gas-phase monomer and dimer structures. It was revealed that these epimers differ in their preferred dimer binding mode in solution phase: androsterone adopts a R=O - Na(+) - OH-R' configuration, whereas trans-androsterone adopts a R=O - Na(+) - O=R' configuration. This difference contributes to a significant structural variation, and subsequent CCS calculations based on these structures relaxed in the gas phase were in agreement with experimentally measured values (ΔCCS ~ 5%). Additionally, these calculations accurately predicted the relative difference in mobility between the epimers. This study illustrates the power of combining experimental and theoretical results to better elucidate gas-phase structures. Graphical Abstract ᅟ.

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  1. 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.

  2. 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.

  3. Analyzing complex mixtures of drug-like molecules: Ion mobility as an adjunct to existing liquid chromatography-(tandem) mass spectrometry methods.

    PubMed

    Boschmans, Jasper; Lemière, Filip; Sobott, Frank

    2017-03-24

    The use of traveling wave ion mobility mass spectrometry (TWIMS) is evaluated in conjunction with, and as a possible alternative to, conventional LC-MS(/MS) methods for the separation and characterization of drug-like compounds and metabolites. As a model system we use an in vitro incubation mixture of the chemotherapeutic agent melphalan, which results in more than ten closely related hydrolysis products and chain-like oligomers. Ion mobility as a filtering tool results in the separation of ions of interest from interfering ions, based on charge state and shape/size. Different classes of chemical compounds often display different mobilities even if they show the same LC behavior - thereby providing an orthogonal separation dimension. Small molecules with identical or similar m/z that only differ in shape/size (e.g. isomers and isobars, monomers/dimers) can also be distinguished using ion mobility. Similar to retention times and mass-to-charge ratios, drift times are analyte-dependent and can be used as an additional identifier. We find that the compound melphalan shows two different drift times due to the formation of gas-phase charge isomers (protomers). The occurrence of protomers has important implications for ion mobility characterization of such analytes, and also for the interpretation of their fragmentation behavior (CID) in the gas phase.

  4. 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.

  5. Tandem mass spectrometry in combination with product ion mobility for the identification of phospholipids

    DOE PAGES

    Berry, Karin A. Zemski; Barkley, Robert M.; Berry, Joseph J.; ...

    2016-11-29

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

  6. Tandem mass spectrometry in combination with product ion mobility for the identification of phospholipids

    SciTech Connect

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

    2016-11-29

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

  7. Precise determination of nonlinear function of ion mobility for explosives and drugs at high electric fields for microchip FAIMS.

    PubMed

    Guo, Dapeng; Wang, Yonghuan; Li, Lingfeng; Wang, Xiaozhi; Luo, Jikui

    2015-01-01

    High-field asymmetric waveform ion mobility spectrometry (FAIMS) separates ions by utilizing the characteristics of nonlinear ion mobility at high and low electric fields. Accurate ion discrimination depends on the precise solution of nonlinear relationships and is essential for accurate identification of ion species for applications. So far, all the nonlinear relationships of ion mobility obtained are based at low electric fields (E/N <65 Td). Microchip FAIMS (μ-FAIMS) with small dimensions has high electric field up to E/N = 250 Td, making the approximation methods and conclusions for nonlinear relationships inappropriate for these systems. In this paper, we deduced nonlinear functions based on the first principle and a general model. Furthermore we considered the hydrodynamics of gas flow through microchannels. We then calculated the specific alpha coefficients for cocaine, morphine, HMX, TNT and RDX, respectively, based on their FAIMS spectra measured by μ-FAIMS system at ultra-high fields up to 250 Td. The results show that there is no difference in nonlinear alpha functions obtained by the approximation and new method at low field (<120 Td), but the error induced by using approximation method increases monotonically with the increase in field, and could be as much as 30% at a field of 250 Td.

  8. 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.

  9. 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

  10. 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.

  11. Conductometric determination of ammonium ion with a mobile drop.

    PubMed

    Jaikang, Pheeraya; Grudpan, Kate; Kanyanee, Tinakorn

    2015-01-01

    A mobile drop based approach was utilized for the conductometric determination of aqueous ammonium ion. A liquid drop was manipulated by gravity to remain or move out of a conductivity measurement zone located on a hydrophobic path. A dilute sulfuric acid drop functioned as a micro gas absorber. Gaseous NH3 was liberated from a sample containing NH4(+) by adding NaOH and purged to flow over the absorber drop. As H(+) in the absorber drop was converted to NH4(+), the conductivity decreased. The rate of the conductivity decrease thus ultimately depended on the NH4(+) concentration in the sample. While the sample could be complex, the liberation of NH3 gas essentially freed the analyte of interest from the matrix and allowed the use of an otherwise nonselective detector. The system was applied to the determination of NH4(+) in some natural waters without prior filtration; the results agreed well with those from a manual indophenol blue method. The approach exhibited a limit of detection (LOD) of 5 μM and a relative standard deviation (RSD) of<5%. The mobile drop gave a constant volume of the gas absorbing solution and provided a cost-effective and simple analytical platform.

  12. Quality issues in the use of ion mobility spectrometry

    NASA Astrophysics Data System (ADS)

    Poziomek, Edward J.; Homstead, Juliana; Almeer, Saeed H.

    1998-12-01

    Ion mobility spectrometry (IMS) is often used in the detection of explosives and drugs in the laboratory and field scenarios. It is gaining popularity in the semiquantitative analysis of these and related compounds. We have successfully used IMS in studies with cocaine, 2,4,6 trinitrotoluene (TNT) and similar chemicals, and have developed a protocol to access and ensure the quality of our data. This protocol employs TNT as the reference standard in the IMS negative mode and cocaine hydrochloride as the reference standard in the IMS positive mode. A five-point calibration curve is normally generated for each reference compound in order to determine a concentration level suitable for quality control (QC) check solutions. We have established peak amplitudes and reduced mobility constants for the QC solutions that must be met each day before proceeding with analyses. Any deviation from these criteria requires assessment of the problem and appropriate corrective action. We have found this procedure helpful in maintaining data quality, and in providing an early indication of potential problems. The present paper focuses on the use of IMS with explosives though several examples are given with cocaine hydrochloride.

  13. 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

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

    PubMed

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

    2010-12-01

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

  15. Examination of Organic Vapor Adsorption onto Alkali Metal and Halide Atomic Ions by using Ion Mobility Mass Spectrometry.

    PubMed

    Maiβer, Anne; Hogan, Christopher J

    2017-08-18

    We utilize ion mobility mass spectrometry with an atmospheric pressure differential mobility analyzer coupled to a time-of-flight mass spectrometer (DMA-MS) to examine the formation of ion-vapor molecule complexes with seed ions of K(+) , Rb(+) , Cs(+) , Br(-) , and I(-) exposed to n-butanol and n-nonane vapor under subsaturated conditions. Ion-vapor molecule complex formation is indicated by a shift in the apparent mobility of each ion. Measurement results are compared to predicted mobility shifts based upon the Kelvin-Thomson equation, which is commonly used in predicting rates of ion-induced nucleation. We find that n-butanol at saturation ratios as low as 0.03 readily binds to all seed ions, leading to mobility shifts in excess of 35 %. Conversely, the binding of n-nonane is not detectable for any ion for saturation ratios in the 0-0.27 range. An inverse correlation between the ionic radius of the initial seed and the extent of n-butanol uptake is observed, such that at elevated n-butanol concentrations, the smallest ion (K(+) ) has the smallest apparent mobility and the largest (I(-) ) has the largest apparent mobility. Though the differences in behavior of the two vapor molecules types examined and the observed effect of ionic seed radius are not accounted for by the Kelvin-Thomson equation, its predictions are in good agreement with measured mobility shifts for Rb(+) , Cs(+) , and Br(-) in the presence of n-butanol (typically within 10 % of measurements). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  16. Nanospray ion mobility mass spectrometry of selected high mass species.

    PubMed

    Campuzano, Iain; Giles, Kevin

    2011-01-01

    The introduction of electrospray ionization (ESI) and in particular nano-electrospray (nESI) has enabled the routine mass spectrometric (MS) analysis of large protein complexes in native aqueous buffers. Time-of-flight (ToF) mass spectrometers, in particular the hybrid quadrupole time-of-flight (Q-ToF) instruments, are well suited to the analysis of large protein complexes. When ionized under native-MS conditions, protein complexes routinely exhibit multiple charge states in excess of m/z 6,000, well above the standard mass range of many quadrupole or ion cyclotron-based instruments. The research area of native MS has expanded considerably in the last decade and has shown particular relevance in the area of protein structure determination. Researchers are now able to routinely measure intact MS spectra of protein complexes above 1 MDa in mass. The advent of ion mobility mass spectrometry (IM-MS), in combination with molecular dynamics (MD) studies, is now allowing researchers to infer the shape of the protein complex being analyzed. Herein, we describe how to acquire IM-MS data that ranges from inorganic salt clusters of caesium iodide (CsI) to large biomolecular complexes such as the chaperone protein GroEL.

  17. Rapid analysis of lubricants by atmospheric solid analysis probe-ion mobility mass spectrometry.

    PubMed

    Barrère, Caroline; Hubert-Roux, Marie; Afonso, Carlos; Racaud, Amandine

    2014-08-01

    Formulated lubricants are complex mixtures composed of base oil(s) and additives with various functions (detergents, corrosion inhibiter, antioxidant, viscosity modifiers, etc.). Because of the aliphatic nature of base oil and the chemical diversity of additives, the characterization of lubricant is currently a long and complex process. The comprehensive analysis of lubricant samples involves several techniques such as nuclear magnetic resonance, mass spectrometry, chromatography and infrared spectroscopy. The coupling of atmospheric solid analysis probe (ASAP) with ion mobility-mass spectrometry (IM-MS) has been shown to be an efficient tool for the characterization of complex mixture containing vaporizable polar to non-polar compounds. This approach affords the coupling of a direct ionization technique that does not require sample preparation, with a bi-dimensional separation method with high peak capacity. In this work, we show that ASAP-IM-MS is a suitable method for rapid and direct characterization of lubricant samples. Indeed, base oil and additives yielded, by ASAP, ions series which could be separated by IM-MS. Molecular additives such as Zn-dithiocarbamate, phosphite, thiophosphate and Alkyl diphenylamine were ionized as molecular ions [M](+•) or protonated molecules [M + H](+), depending of their polarity. In some cases, fragment ions were observed, confirming the additive identification. In addition, high molecular weight polymeric additives such as poly(alkyl methacrylate) (PAM) were pyrolized in the ASAP source leading to characteristic fragment ions. ASAP-IM-MS is shown to be a powerful tool for studying complex mixtures, allowing the first comprehensive analysis of lubricants in just a few minutes. Copyright © 2014 John Wiley & Sons, Ltd.

  18. High efficiency noble gas electron impact ion source for isotope separation

    SciTech Connect

    Appelhans, A. D.; Olson, J. E.; Dahl, D. A.; Ward, M. B.

    2016-07-01

    An electron impact ion source has been designed for generation of noble gas ions in a compact isotope separator. The source utilizes a circular filament that surrounds an ionization chamber, enabling multiple passes of electrons through the ionization chamber. This report presents ion optical design and the results of efficiency and sensitivity measurements performed in an ion source test chamber and in the compact isotope separator. The cylindrical design produced xenon ions at an efficiency of 0.37% with a sensitivity of ~24 µA /Pa at 300 µA of electron current.

  19. Caffeine and glucosamine mobility shifts by adduction with 2-butanol depended on interaction energy, charge delocalization and steric hindrance in ion mobility spectrometry.

    PubMed

    Meza-Morelos, Dairo; Fernandez-Maestre, Roberto

    2017-09-06

    Ion mobility spectrometry (IMS) is an analytical technique that separates gas-phase ions drifting under an electric field according to their size to charge ratio. We used electrospray ionization-drift tube IMS coupled to quadrupole mass spectrometry to measure the mobilities of glucosamine (GH(+) ) and caffeine (CH(+) ) ions in pure nitrogen or when the shift reagent (SR) 2-butanol was introduced in the drift gas at 6.9 mmol m(-3) . Binding energies of 2-butanol-ion adducts were calculated using Gaussian 09 at the CAMB3LYP/6-311++G(d,p) level of theory. The mobility shifts with the introduction of 2-butanol in the drift gas were -2.4% (GH(+) ) and -1.7% (CH(+) ) and were due to clustering of GH(+) and CH(+) with 2-butanol. The formation of GBH(+) was favored over that of CBH(+) because GBH(+) formed more stable hydrogen bonds (83.3 kJ/mol) than CBH(+) (81.7 kJ/mol) for the reason that the positive charge on CH(+) is less sterically available than on GH(+) and the charge is stabilized by resonance in CH(+) . These results are a confirmation of the arguments used to explain the drift behavior of these ions when ethyl lactate SR was used (Bull Kor Chem Soc 2014, 1023-1028). This study is a step forward to predict IMS separations of overlapping peaks in IMS spectra, simplifying a procedure that is trial and error by now. This article is protected by copyright. All rights reserved.

  20. Kinetic model of phase separation in binary mixtures with hard mobile impurities.

    PubMed

    Ginzburg, V V; Peng, G; Qiu, F; Jasnow, D; Balazs, A C

    1999-10-01

    We develop a mean-field rate-equation model for the kinetics of phase separation in binary mixtures with hard mobile impurities. For impurities preferentially wet by one of the components, the phase separation is arrested in the late stage. The "steady-state" domain size depends strongly on both the particle diffusion constant and the particle concentration. We compare theoretical results with the simulation data and find good qualitative agreement.

  1. Improved identification of conjugated linoleic acid isomers using silver-ion HPLC separations.

    PubMed

    Delmonte, Pierluigi; Yurawecz, Martin P; Mossoba, Magdi M; Cruz-Hernandez, Cristina; Kramer, John K G

    2004-01-01

    Silver-ion high-performance liquid chromatography (Ag+-HPLC) has been shown to be effective in the resolution of most of the isomers of conjugated octadecadienoic acids (18:2), also known as conjugated linoleic acid (CLA). The CLA isomers identified in natural fats from ruminants are a mixture of numerous positional and geometric isomers from 7,9- to 12,14-18:2. Ag+-HPLC separates both geometric (trans,trans < cis/trans < cis,cis) and positional CLA isomers using the mobile phase hexane/acetonitrile (99.9:0.1). The elution volumes for the CLA isomers were not only affected by the concentration of acetonitrile (in the prepared mobile phase) but also with successive runs during the day using a prepared mobile phase batch, due to the partial solubility of acetonitrile in hexane. However, this drift does not affect the relative resolution of the CLA isomers. The addition of diethyl ether to the mobile phase partly stabilizes the solvent mixture. In order to facilitate the interpretation of Ag-+HPLC chromatograms, the relative retention volumes (RRV) were calculated for each CLA isomer. Toluene was added to all the test portions and served as an estimator of dead volume, whereas the elution of the ubiquitous 9c,11t-CLA isomer was chosen as unity (1.00). Expressing the elution of all the CLA isomers as their RRV greatly helped to standardize each CLA isomer, resulting in relatively small coefficients of variation (% CV) for the trans,trans (<1.5%) and cis/trans (<0.5%) CLA isomers. The identification of the CLA isomers was further facilitated by synthesis of authentic CLA isomers. All the geometric CLA fatty acid methyl esters (FAME) from positions 6,8- to 13,15-CLA were commercially available or synthesized by a combination of partial hydrazine reduction of known polyunsaturated fatty acids followed by alkali isomerization, isolation of products, and further iodine-catalyzed geometric isomerization. Based on expressing the elution volume as RRV and the availability of

  2. Determination of metal ions by high-performance liquid chromatographic separation of their hydroxamic acid chelates

    SciTech Connect

    Palmieri, M.D.; Fritz, J.S.

    1987-09-15

    Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV), Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.

  3. 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

  4. Bradbury-Nielsen-gate-grid structure for further enhancing the resolution of ion mobility spectrometry.

    PubMed

    Du, Yongzhai; Wang, Weiguo; Li, Haiyang

    2012-07-03

    In our previous work we proposed a three-zone theory for the Bradbury-Nielsen (BN) gate and proved with a grid-BN structure ion mobility drift tube that enhancements of the three-zone features led to higher resolutions and sometimes higher sensitivities. In this work we continued to seek further improvements of the resolution performance by adopting a BN-grid structure in the same drift tube. The postgate grid works both for confinement of the BN gate induced electric field and for isolation of the injection field from the drift field. This makes it possible to obtain better resolutions by further enhancing the compression electric field and lowering the injection field. It was found in the following experiments that reducing the injection field led to higher resolutions yet lower sensitivities. At an injection field of 140 V/cm, the inverse compression coefficient was found to be much larger than that in the grid-BN structure at all gating voltage differences (GVDs). At GVD = 350 V and a gate pulse width of 0.34 ms, the ion mobility spectrometry efficiency R(m)/R(c) reached as high as 221% in the BN-grid structure, presenting a further increase compared to 182% in the grid-BN structure. Finally, two examples are given to show the separation power improvements with good resolutions.

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

    NASA Astrophysics Data System (ADS)

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

    2017-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  7. 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

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

    PubMed

    Fernández-Maestre, Roberto; Hill, Herbert H

    2009-08-01

    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.

  9. 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

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

    PubMed

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

    2014-09-16

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

  11. 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

  12. Determination of N-linked Glycosylation in Viral Glycoproteins by Negative Ion Mass Spectrometry and Ion Mobility.

    PubMed

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

    2015-01-01

    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.

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

    DOE PAGES

    Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan; ...

    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)more » 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. As a result, 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

  14. 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

  15. 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.

  16. 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.

  17. Eco-friendly separation of catechins using cyclodextrins as mobile phase additives in RP-HPLC.

    PubMed

    Bi, Wentao; Li, Shengnan; Row, Kyung Ho

    2012-01-01

    New mobile phases for RP-HPLC were developed for the separation of catechin compounds in tea. Cyclodextrin mobile phase additives decreased the use of toxic and inflammable organic solvents without compromising resolution or separation efficiency. To develop a simple greener method for analyzing five tea catechins in RP-HPLC, the mobile phase condition was optimized and the lowest organic modifier proportion with content resolutions and retention factors were obtained. Eco-friendly cyclodextrins were used as mobile phase additives to decrease the proportion of organic modifier and improve resolutions and retention factors. The effects of several physico-chemical parameters on the retention factors were investigate d and the optimum conditions were obtained on a conventional C₁₈ column, where the mobile phase consisted of acetonitrile/water (12/88, v/v) with 1.5 mmol/L β-cyclodextrin at a flow rate of 1.0 mL/min. Cyclodextrins can separate analytes through host-guest complexation, where a transient diastereomeric complex is formed between the cyclodextrin and the analyte. β-Cyclodextrin is the most accessible, the least expensive and generally the most useful cyclodextrin. This work developed a simple eco-friendly method with the lowest concentration of organic solvents. Under the optimal condition, five catechins could be baseline separated within 17 minutes in the isocratic mode. This research exhibited the potential for the separation and determination of other active compounds from natural plants by a greener method. Copyright © 2011 John Wiley & Sons, Ltd.

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

    PubMed

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

    2014-09-01

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

  19. Determination of E/N Influence on K0 Values within the Low Field Region of Ion Mobility Spectrometry.

    PubMed

    Hauck, Brian C; Siems, William F; Harden, Charles S; McHugh, Vincent M; Hill, Herbert H

    2017-03-23

    The established theory of ion motion within weak electric fields predicts that reduced ion mobility (K0) remains constant as a function of the ratio of electric field strength to drift gas number density (E/N). However, upon increasing the accuracy and precision of K0 value measurements during a previous study, a new relationship was seen in which the K0 values of ions decreased as a function of increasing E/N at field strengths below 4 Td. Here the effect of E/N on the K0 value of an ion has been investigated in order to validate the reality of the phenomenon and determine its cause. The pertinent measurements of voltage and drift time were verified in order to ensure the authenticity of the trend and that it was not a result of a systematic error in parametric measurements. The trend was also replicated on a separate ion mobility spectrometer drift tube in order to further validate its authenticity. As a result, the theory of ion motion within weak electric fields should be revised to reflect the behavior seen here.

  20. 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.

  1. 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.

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

    PubMed

    Kopczynski, Dominik; Rahmann, Sven

    2015-01-01

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

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

    PubMed

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

    2017-01-05

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

  4. Cocaine abuse determination by ion mobility spectrometry using molecular imprinting.

    PubMed

    Sorribes-Soriano, A; Esteve-Turrillas, F A; Armenta, S; de la Guardia, M; Herrero-Martínez, J M

    2017-01-20

    A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18μgL(-1) and quantitative recoveries for blank saliva samples spiked from 75 to 500μgL(-1) cocaine. Oral fluid samples were collected from cocaine consumers and analysed by the proposed MIP-IMS methodology. Results, ranging from below the LOD to 51±2mgL(-1), were statistically comparable to those obtained by a confirmatory gas chromatography-mass spectrometry method. Moreover, results were compared to a qualitative lateral flow immunoassay procedure providing similar classification of the samples. Thus, MIP-IMS can be considered an useful alternative that provided fast, selective and sensitive results with a cost affordable instrumentation that does not require skilled operators. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. 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.

  6. 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

  7. 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

  8. 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].

  9. Determination of C1-C4 alkanes by ion mobility spectrometry.

    PubMed

    Kojiro, D R; Cohen, M J; Stimac, R M; Wernlund, R F; Humphry, D E; Takeuchi, N

    1991-01-01

    Flight instrumentation for the analyses of extraterrestrial environments must often perform under severely restricted conditions. Often, the detection and identification of a multitude of chemical species is required to fulfill the scientific objectives of the mission. It is therefore important that the analytical instrumentation have universal response. The gas chromatograph-ion mobility spectrometer (GC-IMS) has the potential to provide the sample separation, identification and sensitivity necessary for a successful analysis. However, the IMS has poor sensitivity for the C1-C4 alkanes. The abundance of these molecules at various extraterrestrial sites is often of great importance to exobiologists. This study focuses on optimizing IMS sample ionization mechanisms for the C1-C4 alkanes and other hydrocarbons of interest to exobiology.

  10. High energy Li-ion rechargeable battery using thin lithium film composite separator

    NASA Astrophysics Data System (ADS)

    Zeng, Shuming; Moses, P. R.

    It has been demonstrated that small amounts of active lithium metal can be added to a lithium-ion (Li-ion) battery via the separator by using vacuum deposition techniques. Lithium films (4-8 μm) were deposited onto micro-porous polypropylene film that is used as the separator in Li-ion cells. We have demonstrated that the lithium electrochemically reacts with either electrode depending on the geometry of assembly. As a result, the intrinsic irreversible capacity of negative electrode can be compensated using volumetrically efficient lithium metal. Hence, Li-ion cells can be designed and constructed with significantly higher energy than those assembled with conventional techniques.

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

    PubMed

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

    2015-11-04

    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.

  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. In-line respeciation: an ion-exchange ion chromatographic method applied to the separation of degradation products of chemical warfare nerve agents in soil.

    PubMed

    Vermillion, W D; Crenshaw, M D

    1997-05-16

    The natural background of anions encountered when analyzing soil samples by ion chromatography (IC) present significant problems in the separation, detection and quantification of isopropyl methylphosphonic acid (IMPA) and methylphosphonic acid (MPA), the degradation products of sarin, a chemical warfare nerve agent. Using chemically-suppressed IC with conductivity detection, a commercially available ion-exchange column, and an isocratic binary eluent system, IMPA and MPA were determined in aqueous extracts of soil at sub-ppm (microgram/g) concentrations without the need for gradient elution or organic solvent eluent modifiers. Common soil anions such as chloride, nitrate, sulfate and phosphate do not interfere with the analysis method due to the composition of the binary eluent allowing for greater mobilization of multivalent anions (e.g., MPA, carbonate, and sulfate) while monovalent anions (e.g., IMPA and nitrate) are relatively unaffected. Carbonate is selectively removed by in-line respeciation to bicarbonate.

  14. Selective Separation of Metal Ions via Monolayer Nanoporous Graphene with Carboxyl Groups.

    PubMed

    Li, Zhan; Liu, Yanqi; Zhao, Yang; Zhang, Xin; Qian, Lijuan; Tian, Longlong; Bai, Jing; Qi, Wei; Yao, Huijun; Gao, Bin; Liu, Jie; Wu, Wangsuo; Qiu, Hongdeng

    2016-10-18

    Graphene-coated plastic substrates, such as polyethylene terephthalate (PET), are regularly used in flexible electronic devices. Here we demonstrate a new application of the graphene-coated nanoporous PET membrane for the selective separation of metal ions in an ion exchange manner. Irradiation with swift heavy ions is used to perforate graphene and PET substrate. This process could create graphene nanopores with carboxyl groups, thus forming conical holes in the PET after chemical etching to support graphene nanopores. Therefore, a monolayer nanoporous graphene membrane with a PET substrate is constructed successfully to investigate its ionic selective separation. We find that the permeation ratio of ions strongly depends on the temperature and H(+) concentration in the driving solution. An electric field can increase the permeation ratio of ions through the graphene nanopores, but it inhibits the ion selective separation. Moreover, the structure of the graphene nanopore with carboxyl groups is resolved at the density functional theory level. The results show the asymmetric structure of the nanopore with carboxyl groups, and the analysis indicates that the ionic permeation can be attributed to the ion exchange between metal ions and protons on the two sides of graphene nanopores. These results would be beneficial to the design of membrane separation materials made from graphene with efficient online and offline bulk separation.

  15. Separation and characterisation of beta2-microglobulin folding conformers by ion-exchange liquid chromatography and ion-exchange liquid chromatography-mass spectrometry.

    PubMed

    Bertoletti, Laura; Regazzoni, Luca; Aldini, Giancarlo; Colombo, Raffaella; Abballe, Franco; Caccialanza, Gabriele; De Lorenzi, Ersilia

    2013-04-10

    In this work we present for the first time the use of ion-exchange liquid chromatography to separate the native form and a partially structured intermediate of the folding of the amyloidogenic protein beta2-microglobulin. Using a strong anion-exchange column that accounts for the differences in charge exposure of the two conformers, a LC-UV method is initially optimised in terms of mobile phase pH, composition and temperature. The preferred mobile phase conditions that afford useful information were found to be 35 mM ammonium formate, pH 7.4 at 25°C. The dynamic equilibrium of the two species is demonstrated upon increasing the concentration of acetonitrile in the protein sample. Then, the chromatographic method is transferred to MS detection and the respective charge state distributions of the separated conformers are identified. The LC-MS results demonstrate that one of the conformers is partially unfolded, compared with the native and more compact species. The correspondence with previous results obtained in free solution by capillary electrophoresis suggest that strong ion exchange LC-MS does not alter beta2-microglobulin conformation and maintains the dynamic equilibrium already observed between the native protein and its folding intermediate.

  16. Distinguishing d - and l -aspartic and isoaspartic acids in amyloid β peptides with ultrahigh resolution ion mobility spectrometry

    SciTech Connect

    Zheng, Xueyun; Deng, Liulin; Baker, Erin S.; Ibrahim, Yehia M.; Petyuk, Vladislav A.; Smith, Richard D.

    2017-01-01

    Ion mobility spectrometry (IMS) was utilized to separate Aβ peptide variants containing isomeric asparic and isoaspartic acid residues with either al- ord-form. The abundance of each variant is of great interest in Alzheimer's disease studies and also to evaluate how often these modifications are occurring in other environmental and biological samples.

  17. Application of Ion Mobility Mass Spectrometry for Identification of Gas and Particulate Phase Organic Species in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Canagaratna, M. R.; Krechmer, J.; Groessl, M.; Junninen, H.; Kimmel, J.; Cubison, M.; Massoli, P.; Lin, Y. H.; Zhang, H.; Lambe, A. T.; Zhang, X.; Knochenmuss, R.; Surratt, J. D.; Jimenez, J. L.; Worsnop, D. R.

    2015-12-01

    We present recent results obtained from the application of an ion mobility time-of-flight mass spectrometer (IMS-TOF) to the detection of oxidized organic species in the atmosphere. Ion mobility mass spectrometry separates ions on the basis of their interactions with buffer gases on millisecond time scales and allows for detailed separation and identification of isomeric and isobaric molecules. Detection of highly oxidized gas phase organics is achieved by coupling the IMS-TOF to a chemical ionization scheme that utilized NO3- as the reagent ion. Oxidized gas phase molecules produced from biogenic precursors were chemically characterized with this technique during the Southern Oxidant and Aerosol Study (SOAS) field campaign as well as in laboratory experiments utilizing a potential aerosol mass (PAM) reactor. The application of IMS-TOF to aerosol phase organic species is also presented. While molecular composition of fine aerosol is often obtained by combining gas or liquid chromatography (GC or LC) with mass spectrometric detection, these techniques are limited in their ability to transfer, resolve and identify water soluble organic carbon (WSOC) species which account for a significant portion of aerosol mass. Here we demonstrate IMS as a promising alternative approach for obtaining detailed information about organic aerosol (OA) constituent species. We examine aerosol particles collected on filters during ambient and laboratory measurements. The filter extracts are subjected to electrospray ionization (ESI) before detection with the IMS-TOF. The capability of this technique to resolve WSOC species, isomers, and oligomers is highlighted.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Air ion mobility spectra and concentrations upwind and downwind of overhead AC high voltage power lines

    NASA Astrophysics Data System (ADS)

    Wright, Matthew D.; Buckley, Alison J.; Matthews, James C.; Shallcross, Dudley E.; Henshaw, Denis L.

    2014-10-01

    Corona ions produced by high-voltage power lines (HVPLs) can alter the nearby electrical environment, potentially increasing aerosol charge levels downwind. However, there is a lack of knowledge concerning the concentration and mobility of ions from AC HVPLs and their dispersion away from the line. We present ion concentration and mobility measurements made near AC HVPLs in South-West England. Examples of typical mobility spectra are shown highlighting features commonly observed. Corona was observed during 33 of 46 measurements, at 9 of 11 sites, with positive or ‘bipolar' (both polarities) ion production commonly seen. Ion production usually increases atmospheric concentrations by only a modest amount, but extreme cases can enhance concentration by an order of magnitude or more. A polarity imbalance is required to increase aerosol charge via ion attachment; this was observed on 15 of 24 days when positive corona was observed, but was not seen for negative ions. Ion mobility was higher downwind compared with upwind for both ion polarities, but the increase was not statistically significant. Future work should focus on identifying and characterising ‘heavy-producing' HVPLs, and obtaining results in conditions which may favour negative ion production e.g. high humidity, inclement weather or during nighttime.

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

    PubMed

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

    2010-11-07

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

  4. Surface mass spectrometry of two component drug-polymer systems: novel chromatographic separation method using gentle-secondary ion mass spectrometry (G-SIMS).

    PubMed

    Ogaki, Ryosuke; Gilmore, Ian S; Alexander, Morgan R; Green, Felicia M; Davies, Martyn C; Lee, Joanna L S

    2011-05-15

    In recent years, there has been an increase in the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for characterizing material surfaces. A great advantage of SIMS is that the analysis is direct and has excellent spatial resolution approaching a few hundred nanometers. However, the lack of the usual separation methods in mass spectrometry such as chromatography or ion mobility combined with the complexity of the heavily fragmented ions in the spectra means that the interpretation of multicomponent spectra in SIMS is very challenging indeed. The requirements for high-definition imaging, with say 256 × 256 pixels, in around 10 min analysis time places significant constraints on the instrument design so that separation using methods such as ion mobility with flight times of milliseconds are incompatible. Clearly, traditional liquid and gas chromatographies are not at all possible. Previously, we developed a method known as Gentle-SIMS (G-SIMS) that simplifies SIMS spectra so that the dominant ions are simply related to the structure of the substances analyzed. The method uses a measurement of the fragmentation behavior under two different primary ion source conditions and a control parameter known as the g-index. Here, we show that this method may be used "chromatographically" to separate the mass spectra of a drug molecule from the matrix polymer. The method may be used in real-time and is directly compatible with the majority of TOF-SIMS instruments. The applicability to other imaging mass spectrometeries is discussed.

  5. Continuous separation of carbohydrates by ion-exchange chromatography

    SciTech Connect

    Wolfgang, J.; Prior, A.; Bart, H.J.; Messenboeck, R.C.; Byers, C.H.

    1997-01-01

    A synthetic mixture of fructose, mannitol and sorbitol was continuously separated by a chromatographic method using a cation-exchange resin (Dowex 50W-X8) in its Ca{sup 2+}-form as the stationary phase. An annular chromatograph (AC) was used to achieve a continuous mode of operation. Distribution and mass transfer coefficients of the three substances as well as bed properties were obtained by batch chromatography. The separation was simulated mathematically in terms of an approximate linear chromatographic theory was applied to the modeling of the behavior of the continuous separations. The influence of rotation rate, column loading, eluent flow rate and feed concentration on the resolution of the individual peaks were investigated.

  6. 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

  7. Assessment of altered lipid homeostasis by HILIC-ion mobility-mass spectrometry-based lipidomics.

    PubMed

    Hines, Kelly M; Herron, Josi; Xu, Libin

    2017-04-01

    Ion mobility-mass spectrometry (IM-MS) has proven to be a highly informative technique for the characterization of lipids from cells and tissues. We report the combination of hydrophilic-interaction liquid chromatography (HILIC) with traveling-wave IM-MS (TWIM-MS) for comprehensive lipidomics analysis. Main lipid categories such as glycerolipids, sphingolipids, and glycerophospholipids are separated on the basis of their lipid backbones in the IM dimension, whereas subclasses of each category are mostly separated on the basis of their headgroups in the HILIC dimension, demonstrating the orthogonality of HILIC and IM separations. Using our previously established lipid calibrants for collision cross-section (CCS) measurements in TWIM, we measured over 250 CCS values covering 12 lipid classes in positive and negative modes. The coverage of the HILIC-IM-MS method is demonstrated in the analysis of Neuro2a neuroblastoma cells exposed to benzalkonium chlorides (BACs) with C10 or C16 alkyl chains, which we have previously shown to affect gene expression related to cholesterol and lipid homeostasis. We found that BAC exposure resulted in significant changes to several lipid classes, including glycerides, sphingomyelins, phosphatidylcholines, and phosphatidylethanolamines. Our results indicate that BAC exposure modifies lipid homeostasis in a manner that is dependent upon the length of the BAC alkyl chain. Copyright © 2017 by the American Society for Biochemistry and Molecular Biology, Inc.

  8. Isotopic separation of lithium ions by capillary zone electrophoresis.

    PubMed

    Kamencev, Mikhail; Yakimova, Nina; Moskvin, Leonid; Kuchumova, Irina; Tkach, Kirill; Malinina, Yulia; Tungusov, Oleg

    2015-12-01

    Separation of (6)Li and (7)Li isotopes by CZE was demonstrated. The BGE contained 5 mM 4-aminopyridine, 0.9 mM oxalic acid, 0.25 mM CTAB, and 0.25% w/v Tween 20 (рН = 9.2). The running conditions were +25 kV at 30°C with indirect photometric detection at 261 nm. Under optimal experimental conditions, the analysis time was less than 21 min. Separation of Li preparations with mole fraction of (6)Li ranging from 3.44 up to 90.38% was demonstrated.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  11. 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.

  12. 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

  13. 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.

  14. Laser fluorescence spectroscopy on fast ion beams at the Marburg separator

    NASA Astrophysics Data System (ADS)

    Wagner, H.; Dörschel, K.; Höhle, C.; Hühnermann, H.; Meier, Th.

    Optical hyperfine structure and isotope shift measurements have been performed on Xe +, Ba + and La +-ions using an electromagnetic mass separator for the preselection of the isotopes by fast ion beam laser spectroscopy. The different measuring techniques used are described and their precision and sensitivity are discussed.

  15. Development of optimized mobile phases for protein separation by high performance thin layer chromatography.

    PubMed

    Biller, Julia; Morschheuser, Lena; Riedner, Maria; Rohn, Sascha

    2015-10-09

    In recent years, protein chemistry tends inexorably toward the analysis of more complex proteins, proteoforms, and posttranslational protein modifications. Although mass spectrometry developed quite fast correspondingly, sample preparation and separation of these analytes is still a major issue and quite challenging. For many years, electrophoresis seemed to be the method of choice; nonetheless its variance is limited to parameters such as size and charge. When taking a look at traditional (thin-layer) chromatography, further parameters such as polarity and different mobile and stationary phases can be utilized. Further, possibilities of detection are manifold compared to electrophoresis. Similarly, two-dimensional separation can be also performed with thin-layer chromatography (TLC). As the revival of TLC developed enormously in the last decade, it seems to be also an alternative to use high performance thin-layer chromatography (HPTLC) for the separation of proteins. The aim of this study was to establish an HPTLC separation system that allows a separation of protein mixtures over a broad polarity range, or if necessary allowing to modify the separation with only few steps to improve the separation for a specific scope. Several layers and solvent systems have been evaluated to reach a fully utilized and optimized separation system.

  16. 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.

  17. Interaction between crystal lattice and mobile ions in copper selenides studied by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Asylgushina, G. N.; Bikkulova, N. N.; Titova, S. G.; Kochubey, D. I.

    2005-05-01

    Interaction between crystal lattice and mobile Cu ions has been studied in Cu 2-xSe in superionic and in normal state using EXAFS-spectroscopy. It has been found that the transition from normal to superionic state and change of mobile Cu ion concentration practically do not have an influence on local state of Cu atoms, but change of both these parameters is accompanied by a change of Se-sublattice state.

  18. On the role of local charge carrier mobility in the charge separation mechanism of organic photovoltaics.

    PubMed

    Yoshikawa, Saya; Saeki, Akinori; Saito, Masahiko; Osaka, Itaru; Seki, Shu

    2015-07-21

    Although the charge separation (CS) and transport processes that compete with geminate and non-geminate recombination are commonly regarded as the governing factors of organic photovoltaic (OPV) efficiency, the details of the CS mechanism remain largely unexplored. Here we provide a systematic investigation on the role of local charge carrier mobility in bulk heterojunction films of ten different low-bandgap polymers and polythiophene analogues blended with methanofullerene (PCBM). By correlating with the OPV performances, we demonstrated that the local mobility of the blend measured by time-resolved microwave conductivity is more important for the OPV output than those of the pure polymers. Furthermore, the results revealed two separate trends for crystalline and semi-crystalline polymers. This work offers guidance in the design of high-performance organic solar cells.

  19. Efficient separation of acetate and formate by ion chromatography: application to air samples in a cultural heritage environment.

    PubMed

    Kontozova-Deutsch, Velichka; Krata, Agnieszka; Deutsch, Felix; Bencs, László; Van Grieken, René

    2008-04-15

    A method for the separation of acetate and formate anions by ion chromatography has been optimized under various measurement conditions (e.g. the composition of the mobile phase, and the flow rate of the eluent). For this purpose, two different analytical columns were examined: the IonPac AS14 (250 mm x 4 mm i.d.; designed mostly for the separation of inorganic anions) and the Allsep A-2 (150 mm x 4.6 mm i.d.; designed for the separation of low-molecular mass organic acids). However, nearly baseline separation of acetate and formate has been found on each column using the following conditions: (i) IonPac AS14 column and 2.0 mM Na2B4O7 solution as an eluent with a flow rate of 1.0 ml/min, or (ii) Allsep A-2 column and an eluent containing a mixture of 1.2 mM Na2CO3 plus 1.5 mM NaHCO3 with a flow rate of 1.3 ml/min. Additionally, the separation of fluoride from acetate and formate on both columns was studied. On the IonPac AS14 column it was possible to separate all three investigated anions. However, on the Allsep A-2 column, when the concentration of fluoride was comparable to, or higher than acetate, it was impossible to achieve good separation of these two anions, even using the optimized elution procedure. Therefore, the measurements of real samples were carried out with the use of IonPac AS14 column. The concentrations of acetate and formate have been determined in the air samples of the Cathedral of Cologne (Germany), after sampling the corresponding acids by passive diffusion tubes. Average concentrations of 122 and 9 microg/m(3) for acetic and formic acids were found, respectively, inside the Cathedral and in a depot with medieval stained glass panels.

  20. A Langevin dynamics study of mobile filler particles in phase-separating binary systems

    NASA Astrophysics Data System (ADS)

    Laradji, Mohamed

    2004-05-01

    The dynamics of phase separation in a simple binary mixture containing mobile filler particles that are preferentially wet by one of the two components is investigated systematically via Langevin simulations in two dimensions. We found that while the filler particles reduce the growth rate of spinodal decomposition, the domain growth remains essentially identical to that of the pure binary mixture. The growth rate diminishes as either the filler particles concentration is increased or their diffusivity is decreased.

  1. 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

  2. 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.

  3. Robust creation of entanglement between ions in spatially separate cavities.

    PubMed

    Browne, Daniel E; Plenio, Martin B; Huelga, Susana F

    2003-08-08

    We present a protocol that allows the generation of a maximally entangled state between individual atoms held in spatially separate cavities. Assuming perfect detectors and neglecting spontaneous emission from the atoms, the resulting idealized scheme is deterministic. Under more realistic conditions, when the atom-cavity interaction departs from the strong coupling regime, and considering imperfect detectors, we show that the scheme is robust against experimental inefficiencies and yields probabilistic entanglement of very high fidelity.

  4. Thin film separators with ion transport properties for energy applications

    NASA Astrophysics Data System (ADS)

    Li, Zhongyuan

    2017-09-01

    Recent years, along with the increasing need of energy, energy storage also becomes a challenging problem which we need to deal with. The batterieshave a good developing prospect among energy storage system in storing energy such as wind, solar and geothermal energy. One hurdle between the lab-scale experiment and industry-scale application of the advanced batteries is the urgent need for limiting charging capacity degradation and improving cycling stability, known as the shuttle effect in lithium-sulfur batteries or electroosmotic drag coefficient in fuel-cell batteries. The microporous separator between the cathode and anode could be molecular engineered to possessesion selective permeation properties, which can greatly improves the energy efficiency and extends application range of the battery. The present review offers the fundamental fabrication methods of separator film with different material. The review also contains the chemical or physical structure of different materials which are used in making separator film. A table offers the reader a summary of properties such as ionic conductivity, ionic exchange capacity and current density etc.

  5. Probing the Electron Capture Dissociation Mass Spectrometry of Phosphopeptides with Traveling Wave Ion Mobility Spectrometry and Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Kim, Doyong; Pai, Pei-Jing; Creese, Andrew J.; Jones, Andrew W.; Russell, David H.; Cooper, Helen J.

    2015-06-01

    Electron capture dissociation mass spectrometry offers several advantages for the analysis of peptides, most notably that backbone c and z fragments typically retain labile modifications such as phosphorylation. We have shown previously that, in some cases, the presence of phosphorylation has a deleterious effect on peptide sequence coverage, and hypothesized that intramolecular interactions involving the phosphate group were preventing separation of backbone fragments. In the present work, we seek to rationalize the observed ECD behavior through a combination of ECD of model peptides, traveling wave ion mobility mass spectrometry and molecular dynamics simulations. The results suggest that for doubly protonated ions of phosphopeptide APLpSFRGSLPKSYVK a salt-bridge structure is favored, whereas for the doubly-protonated ions of APLSFRGSLPKpSYVK ionic hydrogen bonds predominate.

  6. 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. Published by Elsevier B.V.

  7. Separation and indirect detection of small-chain peptides using chromophoric mobile phase additives.

    PubMed

    Yuan, D X; Pietrzyk, D J

    1990-06-22

    Ruthenium(II) 1,10-phenanthroline, Ru(phen)3(2+), and ruthenium(II) 2,2'-bipyridyl, Ru(bipy)3(2+), salts were evaluated as mobile phase additives for the liquid chromatographic separation of small-chain peptides on a polystyrene-divinylbenzene copolymeric (Hamilton PRP-1) stationary phase. In a basic mobile phase peptides are anions, and retention, resolution and detection occur because of the interactions between the stationary phase, the RuII complex and the peptide anion. Since the RuII complex concentration changes in the analyte band relative to the background eluent RuII complex concentration, the peptide can be detected by indirect photometric detection using the wavelength where the RuII complex absorbs. Peptide analyte peaks may be positive or negative depending on the counter-anion and its concentration. Small-chain peptides that do not contain chromophoric side-chains are detected without derivatization at about 0.1 nmol injected at a 3:1 signal-to-noise ratio. Factors that affect retention, resolution and indirect photometric detection are the RuII complex, its mobile phase concentration, mobile phase pH and solvent composition, and the type and concentration of the mobile phase counter-anion and/or buffer anion.

  8. Advanced Separators for Lithium-Ion and Lithium-Sulfur Batteries: A Review of Recent Progress.

    PubMed

    Xiang, Yinyu; Li, Junsheng; Lei, Jiaheng; Liu, Dan; Xie, Zhizhong; Qu, Deyu; Li, Ke; Deng, Tengfei; Tang, Haolin

    2016-11-09

    Li-ion and Li-S batteries find enormous applications in different fields, such as electric vehicles and portable electronics. A separator is an indispensable part of the battery design, which functions as a physical barrier for the electrode as well as an electrolyte reservoir for ionic transport. The properties of the separators directly influence the performance of the batteries. Traditional polyolefin separators showed low thermal stability, poor wettability toward the electrolyte, and inadequate barrier properties to polysulfides. To improve the performance and durability of Li-ion and Li-S batteries, development of advanced separators is required. In this review, we summarize recent progress on the fabrication and application of novel separators, including the functionalized polyolefin separator, polymeric separator, and ceramic separator, for Li-ion and Li-S batteries. The characteristics, advantages, and limitations of these separators are discussed. A brief outlook for the future directions of the research in the separators is also provided. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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

    2015-03-04

    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.

  10. Reversed phase ion-pairing chromatography of an oligolysine mixture in different mobile phases: effort of searching critical chromatography conditions.

    PubMed

    Xie, Wenchun; Teraoka, Iwao; Gross, Richard A

    2013-08-23

    Our earlier study [J. Chromatogr. A 1218 (2011) 7765] on separation of an oligolysine mixture consisting of chains with 2-8 lysine residues (number of lysine residues, dp=2-8) by ion-pairing reversed-phase chromatography using heptafluorobutyric acid (HFBA) as an ion pairing reagent at fixed mobile phase acetonitrile (ACN) content was extended to isocratic elution conditions with different ACN percentages. The present work explored how manipulating the mobile phase HFBA concentration ([HFBA]) and %-ACN content influences separations of the oligolysine mixture. The closed pairing model was used to analyze variation of the retention factor as a function of [HFBA]. The partition coefficient of the paired peptide decreased with increasing %-ACN. Pairing of HFBA to oligolysine was cooperative, and the effect increased when %-ACN in the mobile phase was lowered. A plot of the partition coefficient as a function of %-ACN for oligolysines varying in dp converged at one ACN content, indicating a critical condition in which components of different dp co-elute.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  13. Separation of monovalent and divalent ions from aqueous solution by electrodialysis and nanofiltration.

    PubMed

    Van der Bruggen, B; Koninckx, A; Vandecasteele, C

    2004-03-01

    The possibilities of separating monovalent and multivalent ions by electrodialysis (ED) and nanofiltration (NF) are explored. Five synthetic single salt solutions were applied to ED and NF: NaCl, Na(2)SO(4), MgCl(2), MgSO(4) and NaNO(3). Two combinations of anionic and cationic exchange membranes were evaluated for ED (AMV/CMV Selemion membranes and ACS/CMS Tokuyama membranes), and two membranes were evaluated for NF (NTR 7450 and UTC-60). The separation was evaluated using an alternative parameter, the separation efficiency, in order to compare ED and NF. The separation efficiency ranges from 0% (no separation) to 100% (perfect separation). Both NF membranes had a good separation efficiency for the separation of monovalent and divalent anions (ca. 60%); the ED membranes performed worse. For the separation of monovalent and divalent cations, the UTC-60 membrane was the best for the considered separation because of size exclusion effects for the larger divalent ion. The ACS/CMS membranes had a similar separation efficiency (ca. 60%); the NTR 7540 membrane and AMV/CMV ED membranes showed only a small separation.

  14. 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.

  15. 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.

  16. 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.

  17. Method and system for producing hydrogen using sodium ion separation membranes

    SciTech Connect

    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.

  18. 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.

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

    SciTech Connect

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

    2016-12-20

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

  20. Development of a new ion mobility time-of-flight mass spectrometer

    SciTech Connect

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

    2015-02-01

    Complex samples require multidimensional measurements with high resolution for full characterization of biological and environmental systems. To address this challenge, we developed a drift tube-based ion mobility spectrometry-Orbitrap mass spectrometry (IMS-Orbitrap MS) platform. To circumvent the timing difference between the fast IMS separation and the slow Orbitrap MS acquisition, we utilized a dual gate and pseudorandom sequence to multiplex ions into the drift tube and Orbitrap. The instrument was designed to operate in signal averaging (SA), single multiplexing (SM) and double multiplexing (DM) IMS modes to fully optimize the signal-to-ratio of the measurements. For the SM measurements, a previously developed algorithm was used to reconstruct the IMS data, while a new algorithm was developed for the DM analyses. The new algorithm is a two-step process that first recovers the SM data from the encoded DM data and then decoded the SM data. The algorithm also performs multiple refining procedures in order to minimize the demultiplexing artifacts traditionally observed in such scheme. The new IMS-Orbitrap MS platform was demonstrated for the analysis of proteomic and petroleum samples, where the integration of IMS and high mass resolution proved essential for accurate assignment of molecular formulae.

  1. Observation of interspecies ion separation in inertial-confinement-fusion implosions

    SciTech Connect

    Hsu, Scott C.; Joshi, Tirtha Raj; Hakel, Peter; Vold, Erik Lehman; Schmitt, Mark J.; Hoffman, Nelson M.; Rauenzahn, Rick M.; Kagan, Grigory; Tang, Xianzhu; Mancini, Roberto C.; Kim, Yong Ho; Herrmann, Hans W.

    2016-10-24

    Here we report direct experimental evidence of interspecies ion separation in direct-drive, inertial-confinement-fusion experiments on the OMEGA laser facility. These experiments, which used plastic capsules with D2/Ar gas fill (1% Ar by atom), were designed specifically to reveal interspecies ion separation by exploiting the predicted, strong ion thermo-diffusion between ion species of large mass and charge difference. Via detailed analyses of imaging x-ray-spectroscopy data, we extract Ar-atom-fraction radial profiles at different times, and observe both enhancement and depletion compared to the initial 1%-Ar gas fill. The experimental results are interpreted with radiation-hydrodynamic simulations that include recently implemented, first-principles models of interspecies ion diffusion. Finally, the experimentally inferred Ar-atom-fraction profiles agree reasonably, but not exactly, with calculated profiles associated with the incoming and rebounding first shock.

  2. Observation of interspecies ion separation in inertial-confinement-fusion implosions

    DOE PAGES

    Hsu, Scott C.; Joshi, Tirtha Raj; Hakel, Peter; ...

    2016-10-24

    Here we report direct experimental evidence of interspecies ion separation in direct-drive, inertial-confinement-fusion experiments on the OMEGA laser facility. These experiments, which used plastic capsules with D2/Ar gas fill (1% Ar by atom), were designed specifically to reveal interspecies ion separation by exploiting the predicted, strong ion thermo-diffusion between ion species of large mass and charge difference. Via detailed analyses of imaging x-ray-spectroscopy data, we extract Ar-atom-fraction radial profiles at different times, and observe both enhancement and depletion compared to the initial 1%-Ar gas fill. The experimental results are interpreted with radiation-hydrodynamic simulations that include recently implemented, first-principles models ofmore » interspecies ion diffusion. Finally, the experimentally inferred Ar-atom-fraction profiles agree reasonably, but not exactly, with calculated profiles associated with the incoming and rebounding first shock.« less

  3. Observation of interspecies ion separation in inertial-confinement-fusion implosions

    NASA Astrophysics Data System (ADS)

    Hsu, S. C.; Joshi, T. R.; Hakel, P.; Vold, E. L.; Schmitt, M. J.; Hoffman, N. M.; Rauenzahn, R. M.; Kagan, G.; Tang, X.-Z.; Mancini, R. C.; Kim, Y.; Herrmann, H. W.

    2016-09-01

    We report direct experimental evidence of interspecies ion separation in direct-drive, inertial-confinement-fusion experiments on the OMEGA laser facility. These experiments, which used plastic capsules with D2/Ar gas fill (1% Ar by atom), were designed specifically to reveal interspecies ion separation by exploiting the predicted, strong ion thermo-diffusion between ion species of large mass and charge difference. Via detailed analyses of imaging x-ray-spectroscopy data, we extract Ar-atom-fraction radial profiles at different times, and observe both enhancement and depletion compared to the initial 1%-Ar gas fill. The experimental results are interpreted with radiation-hydrodynamic simulations that include recently implemented, first-principles models of interspecies ion diffusion. The experimentally inferred Ar-atom-fraction profiles agree reasonably, but not exactly, with calculated profiles associated with the incoming and rebounding first shock.

  4. Electrochemical selective ion separation in capacitive deionization with sodium manganese oxide.

    PubMed

    Kim, Seonghwan; Yoon, Hansun; Shin, Dongyoon; Lee, Jaehan; Yoon, Jeyong

    2017-11-15

    Electrochemical selective ion separation via capacitive deionization, for example, separation of lithium resource from brine, using lithium ion batteries is proposed and demonstrated to have the potential for separating specific ions selectively from a solution containing diverse ions. This separation method is of great industrial concern because of applicability in various fields such as deionization, water softening, purification, heavy metal removal, and resource recovery. Nevertheless, besid