Determination of Benzene, Toluene, and Xylene by means of an ion mobility spectrometer device using photoionization

NASA Technical Reports Server (NTRS)

Leonhardt, J. W.; Bensch, H.; Berger, D.; Nolting, M.; Baumbach, J. I.

1995-01-01

The continuous monitoring of changes on the quality of ambient air is a field of advantage of ion mobility spectrometry. Benzene, Toluene, and Xylene are substances of special interest because of their toxicity. We present an optimized drift tube for ion mobility spectrometers, which uses photo-ionization tubes to produce the ions to be analyzed. The actual version of this drift tube has a length of 45 mm, an electric field strength established within the drift tube of about 180 V/cm and a shutter-opening-time of 400 mus. With the hydrogen tube used for ionisation a mean flux of 10(exp 12) photons/sq cm s was established for the experiments described. We discuss the results of investigations on Benzene, Toluene, and Xylene in normal used gasoline SUPER. The detection limits obtained with the ion mobility spectrometer developed in co-operation are in the range of 10 ppbv in this case. Normally, charge transfer from Benzene ions to Toluene takes place. Nevertheless the simultaneous determination in mixtures is possible by a data evaluation procedure developed for this case. The interferences found between Xylene and others are rather weak. The ion mobility spectra of different concentrations of gasoline SUPER are attached as an example for the resolution and the detection limit of the instrument developed. Resolution and sensitivity of the system are well demonstrated. A hand-held portable device produced just now is to be tested for special environmental analytical problems in some industrial and scientific laboratories in Germany.

A four dimensional separation method based on continuous heart-cutting gas chromatography with ion mobility and high resolution mass spectrometry.

PubMed

Lipok, Christian; Hippler, Jörg; Schmitz, Oliver J

2018-02-09

A two-dimensional GC (2D-GC) method was developed and coupled to an ion mobility-high resolution mass spectrometer, which enables the separation of complex samples in four dimensions (2D-GC, ion mobilility spectrometry and mass spectrometry). This approach works as a continuous multiheart-cutting GC-system (GC+GC), using a long modulation time of 20s, which allows the complete transfer of most of the first dimension peaks to the second dimension column without fractionation, in comparison to comprehensive two-dimensional gas chromatography (GCxGC). Hence, each compound delivers only one peak in the second dimension, which simplifies the data handling even when ion mobility spectrometry as a third and mass spectrometry as a fourth dimension are introduced. The analysis of a plant extract from Calendula officinales shows the separation power of this four dimensional separation method. The introduction of ion mobility spectrometry provides an additional separation dimension and allows to determine collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 800 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. Copyright © 2017 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Xueyun; Deng, Liulin; Baker, Erin S.

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.

Characterization of applied fields for ion mobility in traveling wave based structures for lossless ion manipulations (SLIM)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamid, Ahmed M.; Prabhakaran Nair Syamala Amma, Aneesh; Garimella, Venkata BS

2018-03-21

Ion mobility (IM) is rapidly gaining attention for the analysis of biomolecules due to the ability to distinguish the shapes of ions. However, conventional constant electric field drift tube IM has limited resolving power, constrained by practical limitations on the path length and maximum applied voltage. The implementation of traveling waves (TW) in IM removes the latter limitation, allowing higher resolution to be achieved using extended path lengths. These can be readily obtainable in structures for lossless ion manipulations (SLIM), which are fabricated from electric fields that are generated by appropriate potentials applied to arrays of electrodes patterned on twomore » parallel surfaces. In this work we have investigated the relationship between the various SLIM variables, such as electrode dimensions, inter-surface gap, and the TW applied voltages, that directly impact the fields experienced by ions. Ion simulation and theoretical calculations have been utilized to understand the dependence of SLIM geometry and effective electric field. The variables explored impact both ion confinement and the observed IM resolution in Structures for Lossless Ion Manipulations (SLIM) modules.« less

Characterization of applied fields for ion mobility separations in traveling wave based structures for lossless ion manipulations (SLIM)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamid, Ahmed M.; Prabhakaran, Aneesh; Garimella, Sandilya V. B.

Ion mobility (IM) is rapidly gaining attention for the analysis of biomolecules due to the ability to distinguish the shapes of ions. However, conventional constant electric field drift tube IM has limited resolving power, constrained by practical limitations on the path length and maximum applied voltage. The implementation of traveling waves (TW) in IM removes the latter limitation, allowing higher resolution to be achieved using extended path lengths. These can be readily obtainable in structures for lossless ion manipulations (SLIM), which are fabricated from electric fields that are generated by appropriate potentials applied to arrays of electrodes patterned on twomore » parallel surfaces. In this work we have investigated the relationship between the various SLIM variables, such as electrode dimensions, inter-surface gap, and the TW applied voltages, that directly impact the fields experienced by ions. Ion simulation and theoretical calculations have been utilized to understand the dependence of SLIM geometry and effective electric field. The variables explored impact both ion confinement and the observed IM resolution in Structures for Lossless Ion Manipulations (SLIM) modules.« less

Development and Evaluation of a Reverse-Entry Ion Source Orbitrap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Poltash, Michael L.; McCabe, Jacob W.; Patrick, John W.; Laganowsky, Arthur; Russell, David H.

2018-05-01

As a step towards development of a high-resolution ion mobility mass spectrometer using the orbitrap mass analyzer platform, we describe herein a novel reverse-entry ion source (REIS) coupled to the higher-energy C-trap dissociation (HCD) cell of an orbitrap mass spectrometer with extended mass range. Development of the REIS is a first step in the development of a drift tube ion mobility-orbitrap MS. The REIS approach retains the functionality of the commercial instrument ion source which permits the uninterrupted use of the instrument during development as well as performance comparisons between the two ion sources. Ubiquitin (8.5 kDa) and lipid binding to the ammonia transport channel (AmtB, 126 kDa) protein complex were used as model soluble and membrane proteins, respectively, to evaluate the performance of the REIS instrument. Mass resolution obtained with the REIS is comparable to that obtained using the commercial ion source. The charge state distributions for ubiquitin and AmtB obtained on the REIS are in agreement with previous studies which suggests that the REIS-orbitrap EMR retains native structure in the gas phase.

Tandem ion mobility spectrometry coupled to laser excitation

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

A Hybrid Constant and Oscillatory Field Ion Mobility Analyzer in Structures for Lossless Ion Manipulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran Nair Syamala Amma, Aneesh; Hamid, Ahme

2018-02-28

Ion mobility (IM) spectrometry is becoming an important approach for analyzing molecular ions in the gas phase with applications that span a multitude of scientific areas. There are a variety of IM-based approaches that utilize either constant or oscillatory electric fields. Here, we explore the combination of constant and oscillatory fields applied in a single device to affect the separation and filtering of ions based on their mobilities. The mobility analyzer allows confining and manipulating ions utilizing a combination of radio frequency (RF), direct current (DC) fields, and traveling waves (TW) in a structures for lossless ion manipulations (SLIM) module.more » In this work, we have investigated theoretically and experimentally the concept for continuous filtering of ions based on their mobilities where ions are mobility separated and selected by a combination of TW and constant fields providing opposing forces on the ions. The SLIM module was composed of two surfaces with mirror-image arrays of electrodes and had two regions where the different TW and opposing DC fields could be applied. By appropriately choosing the DC gradient and TW parameters for the two sections, it is possible to transmit ions of a selected mobility while filtering out others. The filtering capabilities are determined by the applied DC gradient and the TW parameters, such as frequency, amplitude and the TW sequence (i.e., the duty cycle of the traveling wave). The effect of different parameters on the sensitivity and the IM resolution of the device have been investigated.« less

A Hybrid Constant and Oscillatory Field Ion Mobility Analyzer Using Structures for Lossless Ion Manipulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran, Aneesh; Hamid, Ahmed M.; Garimella, Sandilya V. B.

Ion mobility (IM) spectrometry is becoming an important approach for analyzing molecular ions in the gas phase with applications that span a multitude of scientific areas. There are a variety of IM-based approaches that utilize either constant or oscillatory electric fields. Here, we explore the combination of constant and oscillatory fields applied in a single device to affect the separation and filtering of ions based on their mobilities. The mobility analyzer allows confining and manipulating ions utilizing a combination of radio frequency (RF), direct current (DC) fields, and traveling waves (TW) in a structures for lossless ion manipulations (SLIM) module.more » In this work, we have investigated theoretically and experimentally the concept for continuous filtering of ions based on their mobilities where ions are mobility separated and selected by a combination of TW and constant fields providing opposing forces on the ions. The SLIM module was composed of two surfaces with mirror-image arrays of electrodes and had two regions where the different TW and opposing DC fields could be applied. By appropriately choosing the DC gradient and TW parameters for the two sections, it is possible to transmit ions of a selected mobility while filtering out others. The filtering capabilities are determined by the applied DC gradient and the TW parameters, such as frequency, amplitude and the TW sequence (i.e., the duty cycle of the traveling wave). The effect of different parameters on the sensitivity and the IM resolution of the device have been investigated.« less

A compact high-resolution X-ray ion mobility spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinecke, T.; Kirk, A. T.; Heptner, A.

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

Real space mapping of ionic diffusion and electrochemical activity in energy storage and conversion materials

DOEpatents

Kalinin, Sergei V; Balke, Nina; Kumar, Amit; Dudney, Nancy J; Jesse, Stephen

2014-05-06

A method and system for probing mobile ion diffusivity and electrochemical reactivity on a nanometer length scale of a free electrochemically active surface includes a control module that biases the surface of the material. An electrical excitation signal is applied to the material and induces the movement of mobile ions. An SPM probe in contact with the surface of the material detects the displacement of mobile ions at the surface of the material. A detector measures an electromechanical strain response at the surface of the material based on the movement and reactions of the mobile ions. The use of an SPM tip to detect local deformations allows highly reproducible measurements in an ambient environment without visible changes in surface structure. The measurements illustrate effective spatial resolution comparable with defect spacing and well below characteristic grain sizes of the material.

Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies.

PubMed

Robbins, Philip J; Surman, Andrew J; Thiel, Johannes; Long, De-Liang; Cronin, Leroy

2013-03-07

We present the high-resolution (HRES-MS) and ion-mobility (IMS-MS) mass spectrometry studies of icosahedral nanoscale polyoxometalate-based {L(30)}{(Mo)Mo(5)} Keplerate clusters, and demonstrate the use of IMS-MS to resolve and map intact nanoclusters, and its potential for the discovery of new structures, in this case the first gas phase observation of 'proto-clustering' of higher order Keplerate supramolecular aggregates.

Development and Evaluation of a Reverse-Entry Ion Source Orbitrap Mass Spectrometer.

PubMed

Poltash, Michael L; McCabe, Jacob W; Patrick, John W; Laganowsky, Arthur; Russell, David H

2018-05-23

As a step towards development of a high-resolution ion mobility mass spectrometer using the orbitrap mass analyzer platform, we describe herein a novel reverse-entry ion source (REIS) coupled to the higher-energy C-trap dissociation (HCD) cell of an orbitrap mass spectrometer with extended mass range. Development of the REIS is a first step in the development of a drift tube ion mobility-orbitrap MS. The REIS approach retains the functionality of the commercial instrument ion source which permits the uninterrupted use of the instrument during development as well as performance comparisons between the two ion sources. Ubiquitin (8.5 kDa) and lipid binding to the ammonia transport channel (AmtB, 126 kDa) protein complex were used as model soluble and membrane proteins, respectively, to evaluate the performance of the REIS instrument. Mass resolution obtained with the REIS is comparable to that obtained using the commercial ion source. The charge state distributions for ubiquitin and AmtB obtained on the REIS are in agreement with previous studies which suggests that the REIS-orbitrap EMR retains native structure in the gas phase. Graphical Abstract ᅟ.

Simple area determination of strongly overlapping ion mobility peaks.

PubMed

Borovcová, Lucie; Hermannová, Martina; Pauk, Volodymyr; Šimek, Matěj; Havlíček, Vladimír; Lemr, Karel

2017-08-15

Coupling of ion mobility with mass spectrometry has brought new frontiers in separation and quantitation of a wide range of isobaric/isomeric compounds. Ion mobility spectrometry may separate ions possessing the identical molecular formula but having different molecular shapes. The separation space in most commercially available instruments is limited and rarely the mobility resolving power exceeds one hundred. From this perspective, new approaches allowing for extracting individual compound signals out of a more complex mixture are needed. In this work we present a new simple analytical approach based on fitting of arrival time distribution (ATD) profiles by Gaussian functions and generating of ATD functions. These ATD functions well describe even distorted ion mobility peaks of individual compounds and allow for extracting their peaks from mobilograms of mixtures. Contrary to classical integration, our approach works well with irregular overlapping peaks. Using mobilograms of standards to generate ATD functions, poorly separated compounds, e.g. isomers, with identical mass spectra representing a hard to solve task for various chemometric methods can be easily distinguished by our procedure. Alternatively ATD functions can be obtained from ATD profiles of ions unique to individual mixture components (if such ions exist) and mobilograms of standards are not required. On a set of hyaluronan-derived oligosaccharides we demonstrated excellent ATD repeatability enabling the resolution of binary mixtures, including mixtures with minor component level about 5%. Ion mobility quantitative data of isomers were confirmed by high performance liquid chromatography. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garimella, Venkata BS; Hamid, Ahmed M.; Deng, Liulin

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 controllablemore » 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.« less

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

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

High-Definition Differential Ion Mobility Spectrometry with Resolving Power up to 500

PubMed Central

Shvartsburg, Alexandre A.; Seim, Tom A.; Danielson, William F.; Norheim, Randy; Moore, Ronald J.; Anderson, Gordon A.; Smith, Richard D.

2013-01-01

As the resolution of analytical methods improves, further progress tends to be increasingly limited by instrumental parameter instabilities that could be ignored before. This is now the case with differential ion mobility spectrometry (FAIMS), where fluctuations of the voltages and gas pressure have become critical. A new high-definition generator for FAIMS compensation voltage reported here provides a stable and accurate output than can be scanned with negligible steps. This reduces the spectral drift and peak width, thus improving the resolving power (R) and resolution. The gain for multiply-charged peptides that have narrowest peaks is up to ~40%, and R ~ 400 – 500 is achievable using He/N2 or H2/N2 gas mixtures. PMID:23345059

High-Definition Differential Ion Mobility Spectrometry with Resolving Power up to 500

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvartsburg, Alexandre A.; Seim, Thomas A.; Danielson, William F.

2013-01-20

As the resolution of analytical methods improve, further progress tends to be increasingly limited by instrumental parameter instabilities that could be ignored before. This is now the case with differential ion mobility spectrometry (FAIMS), where fluctuations of the voltages and gas pressure have become critical. A new high-definition generator for FAIMS compensation voltage reported here provides a stable and accurate output than can be scanned with negligible steps. This reduces the spectral drift and peak width, thus improving the resolving power (R) and resolution. The gain for multiply-charged peptides that have narrowest peaks is up to ~40%, and R ~more » 400 - 500 is achievable using He/N2 or H2/N2 gas mixtures.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simon, Anne-Laure; Choi, Chang Min; Clavier, Christian

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 collisionmore » 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.« less

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection.

PubMed

Matz, Laura M; Hill, Herbert H; Beegle, Luther W; Kanik, Isik

2002-04-01

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Practical application of in silico fragmentation based residue screening with ion mobility high-resolution mass spectrometry.

PubMed

Kaufmann, Anton; Butcher, Patrick; Maden, Kathry; Walker, Stephan; Widmer, Mirjam

2017-07-15

A screening concept for residues in complex matrices based on liquid chromatography coupled to ion mobility high-resolution mass spectrometry LC/IMS-HRMS is presented. The comprehensive four-dimensional data (chromatographic retention time, drift time, mass-to-charge and ion abundance) obtained in data-independent acquisition (DIA) mode was used for data mining. An in silico fragmenter utilizing a molecular structure database was used for suspect screening, instead of targeted screening with reference substances. The utilized data-independent acquisition mode relies on the MS E concept; where two constantly alternating HRMS scans (low and high fragmentation energy) are acquired. Peak deconvolution and drift time alignment of ions from the low (precursor ion) and high (product ion) energy scan result in relatively clean product ion spectra. A bond dissociation in silico fragmenter (MassFragment) supplied with mol files of compounds of interest was used to explain the observed product ions of each extracted candidate component (chromatographic peak). Two complex matrices (fish and bovine liver extract) were fortified with 98 veterinary drugs. Out of 98 screened compounds 94 could be detected with the in silico based screening approach. The high correlation among drift time and m/z value of equally charged ions was utilized for an orthogonal filtration (ranking). Such an orthogonal ion mobility based filter removes multiply charged ions (e.g. peptides and proteins from the matrix) as well as noise and artefacts. Most significantly, this filtration dramatically reduces false positive findings but hardly increases false negative findings. The proposed screening approach may offer new possibilities for applications where reference compounds are hardly or not at all commercially available. Such areas may be the analysis of metabolites of drugs, pyrrolizidine alkaloids, marine toxins, derivatives of sildenafil or novel designer drugs (new psychoactive substances). Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

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

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.

Extracting biomolecule collision cross sections from the high-resolution FT-ICR mass spectral linewidths.

PubMed

Jiang, Ting; Chen, Yu; Mao, Lu; Marshall, Alan G; Xu, Wei

2016-01-14

It is known that the ion collision cross section (CCS) may be calculated from the linewidth of a Fourier transform ion cyclotron resonance (FT-ICR) mass spectral peak at elevated pressure (e.g., ∼10(-6) Torr). However, the high mass resolution of FT-ICR is sacrificed in those experiments due to high buffer gas pressure. In this study, we describe a linewidth correction method to eliminate the windowing-induced peak broadening effect. Together with the energetic ion-neutral collision model previously developed by our group, this method enables the extraction of CCSs of biomolecules from high-resolution FT-ICR mass spectral linewidths, obtained at a typical operating buffer gas pressure of modern FT-ICR instruments (∼10(-10) Torr). CCS values of peptides including MRFA, angiotensin I, and bradykinin measured by the proposed method agree well with ion mobility measurements, and the unfolding of protein ions (ubiquitin) at higher charge states is also observed.

The predictive power of SIMION/SDS simulation software for modeling ion mobility spectrometry instruments

NASA Astrophysics Data System (ADS)

Lai, Hanh; McJunkin, Timothy R.; Miller, Carla J.; Scott, Jill R.; Almirall, José R.

2008-09-01

The combined use of SIMION 7.0 and the statistical diffusion simulation (SDS) user program in conjunction with SolidWorks® with COSMSOSFloWorks® fluid dynamics software to model a complete, commercial ion mobility spectrometer (IMS) was demonstrated for the first time and compared to experimental results for tests using compounds of immediate interest in the security industry (e.g., 2,4,6-trinitrotoluene, 2,7-dinitrofluorene, and cocaine). The effort of this research was to evaluate the predictive power of SIMION/SDS for application to IMS instruments. The simulation was evaluated against experimental results in three studies: (1) a drift:carrier gas flow rates study assesses the ability of SIMION/SDS to correctly predict the ion drift times; (2) a drift gas composition study evaluates the accuracy in predicting the resolution; (3) a gate width study compares the simulated peak shape and peak intensity with the experimental values. SIMION/SDS successfully predicted the correct drift time, intensity, and resolution trends for the operating parameters studied. Despite the need for estimations and assumptions in the construction of the simulated instrument, SIMION/SDS was able to predict the resolution between two ion species in air within 3% accuracy. The preliminary success of IMS simulations using SIMION/SDS software holds great promise for the design of future instruments with enhanced performance.

The Predictive Power of SIMION/SDS Simulation Software for Modeling Ion Mobility Spectrometry Instruments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanh Lai; Timothy R. McJunkin; Carla J. Miller

2008-09-01

The combined use of SIMION 7.0 and the statistical diffusion simulation (SDS) user program in conjunction with SolidWorks® with COSMSOFloWorks® fluid dynamics software to model a complete, commercial ion mobility spectrometer (IMS) was demonstrated for the first time and compared to experimental results for tests using compounds of immediate interest in the security industry (e.g., 2,4,6-trinitrotoluene and cocaine). The effort of this research was to evaluate the predictive power of SIMION/SDS for application to IMS instruments. The simulation was evaluated against experimental results in three studies: 1) a drift:carrier gas flow rates study assesses the ability of SIMION/SDS to correctlymore » predict the ion drift times; 2) a drift gas composition study evaluates the accuracy in predicting the resolution; and 3) a gate width study compares the simulated peak shape and peak intensity with the experimental values. SIMION/SDS successfully predicted the correct drift time, intensity, and resolution trends for the operating parameters studied. Despite the need for estimations and assumptions in the construction of the simulated instrument, SIMION/SDS was able to predict the resolution between two ion species in air within 3% accuracy. The preliminary success of IMS simulations using SIMION/SDS software holds great promise for the design of future instruments with enhanced performance.« less

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.

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.

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.

The hypertrehalosemic neuropeptides of cicadas are structural isomers-evidence by ion mobility mass spectrometry.

PubMed

König, Simone; Marco, Heather; Gäde, Gerd

2017-11-01

It has been known for more than 20 years that the neurosecretory glands of the cicadas, the corpora cardiaca, synthesize two isobaric peptides with hypertrehalosemic activity. Both decapeptides have exactly the same amino acid sequence (pGlu-Val-Asn-Phe-Ser-Pro-Ser-Trp-Gly-Asn-NH 2 ) and mass but differ in their retention time in reversed-phase liquid chromatography. A synthetic peptide with the same sequence elutes together with the second more hydrophobic peptide peak of the natural cicada extract. It is not clear what modification is causing the described observations. Therefore, in the current study, ion mobility separation in conjunction with high-resolution mass spectrometry was used to investigate this phenomenon as it was sensitive to changes in conformation. It detected different drift times in buffer gas for both the intact peptides and some of their fragment ions. Based on the ion mobility and fragment ion intensity of the corresponding ions, it is concluded that the region Pro 6 -Ser 7 -Trp 8 contains a structural feature differing from the L-amino acids present in the known peptide. Whether the conformer is the result of racemization or other biochemical processes needs to be further investigated.

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

A novel four-dimensional analytical approach for analysis of complex samples.

PubMed

Stephan, Susanne; Jakob, Cornelia; Hippler, Jörg; Schmitz, Oliver J

2016-05-01

A two-dimensional LC (2D-LC) method, based on the work of Erni and Frei in 1978, was developed and coupled to an ion mobility-high-resolution mass spectrometer (IM-MS), which enabled the separation of complex samples in four dimensions (2D-LC, ion mobility spectrometry (IMS), and mass spectrometry (MS)). This approach works as a continuous multiheart-cutting LC system, using a long modulation time of 4 min, which allows the complete transfer of most of the first - dimension peaks to the second - dimension column without fractionation, in comparison to comprehensive two-dimensional liquid chromatography. Hence, each compound delivers only one peak in the second dimension, which simplifies the data handling even when ion mobility spectrometry as a third and mass spectrometry as a fourth dimension are introduced. The analysis of a plant extract from Ginkgo biloba shows the separation power of this four-dimensional separation method with a calculated total peak capacity of more than 8700. Furthermore, the advantage of ion mobility for characterizing unknown compounds by their collision cross section (CCS) and accurate mass in a non-target approach is shown for different matrices like plant extracts and coffee. Graphical abstract Principle of the four-dimensional separation.

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.

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

PubMed

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

2017-07-11

While α-linked amino acids in the l-form are exclusively utilized in mammalian protein building, β-linked and d-form amino acids also have important biological roles. Unfortunately, the structural elucidation and separation of these different amino acid types in peptides has been analytically challenging to date due to the numerous isomers present, limiting our knowledge about their existence and biological roles. Here, we utilized an ultrahigh resolution ion mobility spectrometry platform coupled with mass spectrometry (IMS-MS) to separate amyloid β (Aβ) peptides containing l-aspartic acid, d-aspartic acid, l-isoaspartic acid, and d-isoaspartic acid residues which span α- and β-linked amino acids in both d- and l-forms. The results illustrate how IMS-MS could be used to better understand age-related diseases or protein folding disorders resulting from amino acid modifications.

Conformational ordering of biomolecules in the gas phase: nitrogen collision cross sections measured on a prototype high resolution drift tube ion mobility-mass spectrometer.

PubMed

May, Jody C; Goodwin, Cody R; Lareau, Nichole M; Leaptrot, Katrina L; Morris, Caleb B; Kurulugama, Ruwan T; Mordehai, Alex; Klein, Christian; Barry, William; Darland, Ed; Overney, Gregor; Imatani, Kenneth; Stafford, George C; Fjeldsted, John C; McLean, John A

2014-02-18

Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid "omni-omic" characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field.

Conformational Ordering of Biomolecules in the Gas Phase: Nitrogen Collision Cross Sections Measured on a Prototype High Resolution Drift Tube Ion Mobility-Mass Spectrometer

PubMed Central

2014-01-01

Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid “omni-omic” characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field. PMID:24446877

Liquid chromatography of hydrocarbonaeous quaternary amines on cyclodextrin bonded silica

USGS Publications Warehouse

Abidi, S.L.

1986-01-01

Mixtures of n-alkylbenzyldimethylammonium chloride (ABDAC) were resolved into homologous components by high-performance liquid chromatography (HPLC) with a cyclodextrin-bonded silica stationary phase. With a few exceptions, results from this study are similar to those obtained from traditional reversed-phase HPLC. It was found that the presence of electrolytes in aqueous mobile phases is not a critical factor in determining the success of HPLC separation. Under normal HPLC conditions, a mobile phase consisting of either methanol–water (50:50) or acetonitrile–water (30:70) was employed for obtaining adequate resolution of the quaternary ammonium mixtures. Although the percent organic modifier–water profiles were similar to those in previous studies with these compounds, resolution (R) and selectivity (α) parameters were found to be quite susceptible to changes in the mobile phase solvent composition. The retention behavior of the cationic analytes in the homologous series is consistent with the hydrophobic-interaction concept proposed for the retention mechanism via dominant inclusion complex formation. Several electrolytes were chosen for a study of the counter ion effect on the chromatographic characteristics of ABDAC components. Among the electrolytes examined, the perchlorate ion was found most likely to act as an ion-pairing counter ion for ammonium cations in the HPLC system studied. A correlation study established linear relationships between the chain length of ABDAC and the logarithmic capacity factor (k2). The analytical utility of the HPLC method was demonstrated by the analysis of various unknown mixtures.

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)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Liulin; Garimella, Sandilya V. B.; Hamid, Ahmed M.

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

Continuous scanning of the mobility and size distribution of charged clusters and nanometer particles in atmospheric air and the Balanced Scanning Mobility Analyzer BSMA

NASA Astrophysics Data System (ADS)

Tammet, H.

2006-12-01

Measuring of charged nanometer particles in atmospheric air is a routine task in research on atmospheric electricity, where these particles are called the atmospheric ions. An aspiration condenser is the most popular instrument for measuring atmospheric ions. Continuous scanning of a mobility distribution is possible when the aspiration condenser is connected as an arm of a balanced bridge. Transfer function of an aspiration condenser is calculated according to the measurements of geometric dimensions, air flow rate, driving voltage, and electric current. The most complicated phase of the calibration is the estimation of the inlet loss of ions due to the Brownian deposition. The available models of ion deposition on the protective inlet screen and the inlet control electrofilter have the uncertainty of about 20%. To keep the uncertainty of measurements low the adsorption should not exceed a few tens of percent. The online conversion of the mobility distribution to the size distribution and a correct reduction of inlet losses are possible when air temperature and pressure are measured simultaneously with the mobility distribution. Two instruments called the Balanced Scanning Mobility Analyzers (BSMA) were manufactured and tested in routine atmospheric measurements. The concentration of atmospheric ions of the size of about a few nanometers is very low and a high air flow rate is required to collect enough of ion current. The air flow of 52 l/s exceeds the air flow in usual aerosol instruments by 2-3 orders of magnitude. The high flow rate reduces the time of ion passage to 60 ms and the heating of air in an analyzer to 0.2 K, which suppresses a possible transformation of ions inside the instrument. The mobility range of the BSMA of 0.032-3.2 cm 2 V - 1 s - 1 is logarithmically uniformly divided into 16 fractions. The size distribution is presented by 12 fractions in the diameter range of 0.4-7.5 nm. The measurement noise of a fraction concentration is typically about 5 cm - 3 and the time resolution is about 10 min when measuring simultaneously both positive and negative ions in atmospheric air.

Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry.

PubMed

Sun, Jianghao; Baker, Andrew; Chen, Pei

2011-09-30

An ultra-performance liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry (UPLC/IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine or ajmalicine core structure, plus methylated, oxidized and reduced species, were characterized. Common fragments and mass differences are described. It was shown that the use of IMS could provide another molecular descriptor, i.e. molecular shape by rotationally averaged collision cross-section; this is of great value for identification of constituents when reference materials are usually not available. Using the combination of high resolution (~40000) accurate mass measurement with time-aligned parallel (TAP) fragmentation, MS(E) (where E represents collision energy), ion mobility mass spectrometry (IMS) and UPLC chromatography, a total 55 indole alkaloids were characterized and a few new indole alkaloids are reported for the first time. Published in 2011 by John Wiley & Sons, Ltd.

Classification of ion mobility spectra by functional groups using neural networks

NASA Technical Reports Server (NTRS)

Bell, S.; Nazarov, E.; Wang, Y. F.; Eiceman, G. A.

1999-01-01

Neural networks were trained using whole ion mobility spectra from a standardized database of 3137 spectra for 204 chemicals at various concentrations. Performance of the network was measured by the success of classification into ten chemical classes. Eleven stages for evaluation of spectra and of spectral pre-processing were employed and minimums established for response thresholds and spectral purity. After optimization of the database, network, and pre-processing routines, the fraction of successful classifications by functional group was 0.91 throughout a range of concentrations. Network classification relied on a combination of features, including drift times, number of peaks, relative intensities, and other factors apparently including peak shape. The network was opportunistic, exploiting different features within different chemical classes. Application of neural networks in a two-tier design where chemicals were first identified by class and then individually eliminated all but one false positive out of 161 test spectra. These findings establish that ion mobility spectra, even with low resolution instrumentation, contain sufficient detail to permit the development of automated identification systems.

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

PubMed

Regueiro, Jorge; Giri, Anupam; Wenzl, Thomas

2016-06-21

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

Ion transport in sub-5-nm graphene nanopores.

PubMed

Suk, Myung E; Aluru, N R

2014-02-28

Graphene nanopore is a promising device for single molecule sensing, including DNA bases, as its single atom thickness provides high spatial resolution. To attain high sensitivity, the size of the molecule should be comparable to the pore diameter. However, when the pore diameter approaches the size of the molecule, ion properties and dynamics may deviate from the bulk values and continuum analysis may not be accurate. In this paper, we investigate the static and dynamic properties of ions with and without an external voltage drop in sub-5-nm graphene nanopores using molecular dynamics simulations. Ion concentration in graphene nanopores sharply drops from the bulk concentration when the pore radius is smaller than 0.9 nm. Ion mobility in the pore is also smaller than bulk ion mobility due to the layered liquid structure in the pore-axial direction. Our results show that a continuum analysis can be appropriate when the pore radius is larger than 0.9 nm if pore conductivity is properly defined. Since many applications of graphene nanopores, such as DNA and protein sensing, involve ion transport, the results presented here will be useful not only in understanding the behavior of ion transport but also in designing bio-molecular sensors.

Improvement of a device for detection and characterization of certain atmospheric pollutants. Final report. Perfectionnement d'un appareillage de detection et de caracterisation de certains pollutants atmospheriques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tesseyre, Y.

The study allowed development of an original measuring system for mobility, involving simultaneously a repulsive electrical field and a continuous gas flow. It made it possible to define a model to calculate ionic transparency of grates, taking into account electrical fields below and above them, ion mobility, speed of gas flow and geometric transparency. Calculation of the electrical field proceeded in a plane-plane system, taking into account the space load and diffusion; a graphic method was developed to determine the field, thus avoiding numerical integration of the diffusion equation. The tracings of the mobility spectra obtained in different gases mademore » it possible to determine characteristic discrete mobility values comparable to those observed by other more sophisticated systems for measuring mobilities, such as the flight time systems. Detection of pollutants in weak concentration in dry air was shown. However, the presence of water vapor in the air forms agglomerates around the ions formed, reducing resolution of the system and making it less applicable under normal atmospheric conditions.« less

Threshold for ion movements in wood cell walls below fiber saturation observed by X-ray fluorescence microscopy (XFM)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zelinka, Samuel L.; Gleber, Sophie-Charlotte; Vogt, Stefan

Diffusion of chemicals and ions through the wood cell wall plays an important role in wood damage mechanisms. In the present work, free diffusion of ions through wood secondary walls and middle lamellae has been investigated as a function of moisture content (MC) and anatomical direction. Various ions (K, Cl, Zn, Cu) were injected into selected regions of 2 mu m thick wood sections with a microinjector and then the ion distribution was mapped by means of X-ray fluorescence microscopy with submicron spatial resolution. The MC of the wood was controlled in situ by means of climatic chamber with controlledmore » relative humidity (RH). For all ions investigated, there was a threshold RH below which the concentration profiles did not change. The threshold RH depended upon ionic species, cell wall layer, and wood anatomical orientation. Above the threshold RH, differences in mobility among ions were observed and the mobility depended upon anatomical direction and cell wall layer. These observations support a recently proposed percolation model of electrical conduction in wood. The results contribute to understanding the mechanisms of fungal decay and fastener corrosion that occur below the fiber saturation point.« less

A new high transmission inlet for the Caltech nano-RDMA for size distribution measurements of sub-3 nm ions at ambient concentrations

NASA Astrophysics Data System (ADS)

Franchin, A.; Downard, A. J.; Kangasluoma, J.; Nieminen, T.; Lehtipalo, K.; Steiner, G.; Manninen, H. E.; Petäjä, T.; Flagan, R. C.; Kulmala, M.

2015-06-01

Reliable and reproducible measurements of atmospheric aerosol particle number size distributions below 10 nm require optimized classification instruments with high particle transmission efficiency. Almost all DMAs have an unfavorable potential gradient at the outlet (e.g. long column, Vienna type) or at the inlet (nano-radial DMA). This feature prevents them from achieving a good transmission efficiency for the smallest nanoparticles. We developed a new high transmission inlet for the Caltech nano-radial DMA (nRDMA) that increases the transmission efficiency to 12 % for ions as small as 1.3 nm in mobility equivalent diameter (corresponding to 1.2 × 10-4 m2 V-1 s-1 in electrical mobility). We successfully deployed the nRDMA, equipped with the new inlet, in chamber measurements, using a Particle Size Magnifier (PSM) and a booster Condensation Particle Counter (CPC) as a counter. With this setup, we were able to measure size distributions of ions between 1.3 and 6 nm, corresponding to a mobility range from 1.2 × 10-4 to 5.8 × 10-6 m2 V-1 s-1. The system was modeled, tested in the laboratory and used to measure negative ions at ambient concentrations in the CLOUD 7 measurement campaign at CERN. We achieved a higher size resolution than techniques currently used in field measurements, and maintained a good transmission efficiency at moderate inlet and sheath air flows (2.5 and 30 LPM, respectively). In this paper, by measuring size distribution at high size resolution down to 1.3 nm, we extend the limit of the current technology. The current setup is limited to ion measurements. However, we envision that future research focused on the charging mechanisms could extend the technique to measure neutral aerosol particles as well, so that it will be possible to measure size distributions of ambient aerosols from 1 nm to 1 μm.

A new high-transmission inlet for the Caltech nano-RDMA for size distribution measurements of sub-3 nm ions at ambient concentrations

NASA Astrophysics Data System (ADS)

Franchin, Alessandro; Downard, Andy; Kangasluoma, Juha; Nieminen, Tuomo; Lehtipalo, Katrianne; Steiner, Gerhard; Manninen, Hanna E.; Petäjä, Tuukka; Flagan, Richard C.; Kulmala, Markku

2016-06-01

Reliable and reproducible measurements of atmospheric aerosol particle number size distributions below 10 nm require optimized classification instruments with high particle transmission efficiency. Almost all differential mobility analyzers (DMAs) have an unfavorable potential gradient at the outlet (e.g., long column, Vienna type) or at the inlet (nano-radial DMA), preventing them from achieving a good transmission efficiency for the smallest nanoparticles. We developed a new high-transmission inlet for the Caltech nano-radial DMA (nRDMA) that increases the transmission efficiency to 12 % for ions as small as 1.3 nm in Millikan-Fuchs mobility equivalent diameter, Dp (corresponding to 1.2 × 10-4 m2 V-1 s-1 in electrical mobility). We successfully deployed the nRDMA, equipped with the new inlet, in chamber measurements, using a particle size magnifier (PSM) and as a booster a condensation particle counter (CPC). With this setup, we were able to measure size distributions of ions within a mobility range from 1.2 × 10-4 to 5.8 × 10-6 m2 V-1 s-1. The system was modeled, tested in the laboratory and used to measure negative ions at ambient concentrations in the CLOUD (Cosmics Leaving Outdoor Droplets) 7 measurement campaign at CERN. We achieved a higher size resolution (R = 5.5 at Dp = 1.47 nm) than techniques currently used in field measurements (e.g., Neutral cluster and Air Ion Spectrometer (NAIS), which has a R ˜ 2 at largest sizes, and R ˜ 1.8 at Dp = 1.5 nm) and maintained a good total transmission efficiency (6.3 % at Dp = 1.5 nm) at moderate inlet and sheath airflows (2.5 and 30 L min-1, respectively). In this paper, by measuring size distributions at high size resolution down to 1.3 nm, we extend the limit of the current technology. The current setup is limited to ion measurements. However, we envision that future research focused on the charging mechanisms could extend the technique to measure neutral aerosol particles as well, so that it will be possible to measure size distributions of ambient aerosols from 1 nm to 1 µm.

A chemometric approach for characterization of serum transthyretin in familial amyloidotic polyneuropathy type I (FAP-I) by electrospray ionization-ion mobility mass spectrometry.

PubMed

Pont, Laura; Sanz-Nebot, Victoria; Vilaseca, Marta; Jaumot, Joaquim; Tauler, Roma; Benavente, Fernando

2018-05-01

In this study, we describe a chemometric data analysis approach to assist in the interpretation of the complex datasets from the analysis of high-molecular mass oligomeric proteins by ion mobility mass spectrometry (IM-MS). The homotetrameric protein transthyretin (TTR) is involved in familial amyloidotic polyneuropathy type I (FAP-I). FAP-I is associated with a specific TTR mutant variant (TTR(Met30)) that can be easily detected analyzing the monomeric forms of the mutant protein. However, the mechanism of protein misfolding and aggregation onset, which could be triggered by structural changes in the native tetrameric protein, remains under investigation. Serum TTR from healthy controls and FAP-I patients was purified under non-denaturing conditions by conventional immunoprecipitation in solution and analyzed by IM-MS. IM-MS allowed separation and characterization of several tetrameric, trimeric and dimeric TTR gas ions due to their differential drift time. After an appropriate data pre-processing, multivariate curve resolution alternating least squares (MCR-ALS) was applied to the complex datasets. A group of seven independent components being characterized by their ion mobility profiles and mass spectra were resolved to explain the observed data variance in control and patient samples. Then, principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were considered for exploration and classification. Only four out of the seven resolved components were enough for an accurate differentiation. Furthermore, the specific TTR ions identified in the mass spectra of these components and the resolved ion mobility profiles provided a straightforward insight into the most relevant oligomeric TTR proteoforms for the disease. Copyright © 2018 Elsevier B.V. All rights reserved.

Systems and methods for integrating ion mobility and ion trap mass spectrometers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibrahim, Yehia M.; Garimella, Sandilya; Prost, Spencer A.

Described herein are examples of systems and methods for integrating IMS and MS systems. In certain examples, systems and methods for decoding double multiplexed data are described. The systems and methods can also perform multiple refining procedures in order to minimize the demultiplexing artifacts. The systems and methods can be used, for example, for the analysis of proteomic and petroleum samples, where the integration of IMS and high mass resolution are used for accurate assignment of molecular formulae.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibrahim, Yehia M.; Baker, Erin S.; Danielson, William F.

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 developedmore » 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.« less

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

A strategy for identification and structural characterization of compounds from Gardenia jasminoides by integrating macroporous resin column chromatography and liquid chromatography-tandem mass spectrometry combined with ion-mobility spectrometry.

PubMed

Wang, Lu; Liu, Shu; Zhang, Xueju; Xing, Junpeng; Liu, Zhiqiang; Song, Fengrui

2016-06-24

In this paper, an analysis strategy integrating macroporous resin (AB-8) column chromatography and high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) combined with ion mobility spectrometry (IMS) was proposed and applied for identification and structural characterization of compounds from the fruits of Gardenia jasminoides. The extracts of G. jasminoides were separated by AB-8 resin column chromatography combined with reversed phase liquid chromatography (C18 column) and detected by electrospray ionization tandem mass spectrometry. Additionally, ion mobility spectrometry (IMS) was employed as a supplementary separation technique to discover previously undetected isomers from the fruits of G. jasminoides. A total of 71 compounds, including iridoids, flavonoids, triterpenes, monoterpenoids, carotenoids and phenolic acids were identified by the characteristic high resolution mass spectrometry and the ESI-MS/MS fragmentations. In conclusion, the IMS-MS technique achieved the separation of isomers in crocin-3 and crocin-4 according to their acquired mobility drift times differing from classical analysis by mass spectrometry. The proposed strategy can be used as a highly sensitive and efficient procedure for identification and separation isomeric components in extracts of herbal medicines. Copyright © 2016 Elsevier B.V. All rights reserved.

Application of a chromatography model with linear gradient elution experimental data to the rapid scale-up in ion-exchange process chromatography of proteins.

PubMed

Ishihara, Takashi; Kadoya, Toshihiko; Yamamoto, Shuichi

2007-08-24

We applied the model described in our previous paper to the rapid scale-up in the ion exchange chromatography of proteins, in which linear flow velocity, column length and gradient slope were changed. We carried out linear gradient elution experiments, and obtained data for the peak salt concentration and peak width. From these data, the plate height (HETP) was calculated as a function of the mobile phase velocity and iso-resolution curve (the separation time and elution volume relationship for the same resolution) was calculated. The scale-up chromatography conditions were determined by the iso-resolution curve. The scale-up of the linear gradient elution from 5 to 100mL and 2.5L column sizes was performed both by the separation of beta-lactoglobulin A and beta-lactoglobulin B with anion-exchange chromatography and by the purification of a recombinant protein with cation-exchange chromatography. Resolution, recovery and purity were examined in order to verify the proposed method.

High pressure effects in high-field asymmetric waveform ion mobility spectrometry.

PubMed

Wang, Yonghuan; Wang, Xiaozhi; Li, Lingfen; Chen, Chilai; Xu, Tianbai; Wang, Tao; Luo, Jikui

2016-08-30

High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) is an analytical technique based on the principle of non-linear electric field dependence of coefficient of mobility of ions for separation that was originally conceived in the Soviet Union in the early 1980s. Being well developed over the past decades, FAIMS has become an efficient method for the separation and characterization of gas-phase ions at ambient pressure, often in air, to detect trace amounts of chemical species including explosives, toxic chemicals, chemical warfare agents and other compounds. However the resolution of FAIMS and ion separation capability need to be improved for more applications of the technique. The effects of above-ambient pressure varying from 1 to 3 atm on peak position, resolving power, peak width, and peak intensity are investigated theoretically and experimentally using micro-fabricated planar FAIMS in purified air. Peak positions, varying with pressure in a way as a function of dispersion voltage, could be simplified by expressing both compensation and dispersion fields in Townsend units for E/N, the ratio of electric field intensity (E) to the gas number density (N). It is demonstrated that ion Townsend-scale peak positions remain unchanged for a range of pressures investigated, implying that the higher the pressure is, stronger compensation and separation fields are needed within limits of air breakdown field. Increase in pressure is found to separate ions that could not be distinguished in ambient pressure, which could be interpreted as the differentials of ions' peak compensation voltage expanded wider than the dilation of peak widths leading to resolving power enhancement with pressure. Increase in pressure can also result in an increase in peak intensity. Copyright © 2016 John Wiley & Sons, Ltd.

Biologically-Inspired Peptide Reagents for Enhancing IMS-MS Analysis of Carbohydrates

NASA Astrophysics Data System (ADS)

Bohrer, Brian C.; Clemmer, David E.

2011-09-01

The binding properties of a peptidoglycan recognition protein are translated via combinatorial chemistry into short peptides. Non-adjacent histidine, tyrosine, and arginine residues in the protein's binding cleft that associate specifically with the glycan moiety of a peptidoglycan substrate are incorporated into linear sequences creating a library of 27 candidate tripeptide reagents (three possible residues permutated across three positions). Upon electrospraying the peptide library and carbohydrate mixtures, some noncovalent complexes are observed. The binding efficiencies of the peptides vary according to their amino acid composition as well as the disaccharide linkage and carbohydrate ring-type. In addition to providing a charge-carrier for the carbohydrate, peptide reagents can also be used to differentiate carbohydrate isomers by ion mobility spectrometry. The utility of these peptide reagents as a means of enhancing ion mobility analysis of carbohydrates is illustrated by examining four glucose-containing disaccharide isomers, including a pair that is not resolved by ion mobility alone. The specificity and stoichiometry of the peptide-carbohydrate complexes are also investigated. Trihistidine demonstrates both suitable binding efficiency and successful resolution of disaccharides isomers, suggesting it may be a useful reagent in IMS analyses of carbohydrates.

Critical comparison of mass analyzers for forensic hair analysis by ambient ionization mass spectrometry.

PubMed

Duvivier, Wilco F; van Beek, Teris A; Nielen, Michel W F

2016-11-15

Recently, several direct and/or ambient mass spectrometry (MS) approaches have been suggested for drugs of abuse imaging in hair. The use of mass spectrometers with insufficient selectivity could result in false-positive measurements due to isobaric interferences. Different mass analyzers have been evaluated regarding their selectivity and sensitivity for the detection of Δ9-tetrahydrocannabinol (THC) from intact hair samples using direct analysis in real time (DART) ionization. Four different mass analyzers, namely (1) an orbitrap, (2) a quadrupole orbitrap, (3) a triple quadrupole, and (4) a quadrupole time-of-flight (QTOF), were evaluated. Selectivity and sensitivity were assessed by analyzing secondary THC standard dilutions on stainless steel mesh screens and blank hair samples, and by the analysis of authentic cannabis user hair samples. Additionally, separation of isobaric ions by use of travelling wave ion mobility (TWIM) was investigated. The use of a triple quadrupole instrument resulted in the highest sensitivity; however, transitions used for multiple reaction monitoring were only found to be specific when using high mass resolution product ion measurements. A mass resolution of at least 30,000 FWHM at m/z 315 was necessary to avoid overlap of THC with isobaric ions originating from the hair matrix. Even though selectivity was enhanced by use of TWIM, the QTOF instrument in resolution mode could not indisputably differentiate THC from endogenous isobaric ions in drug user hair samples. Only the high resolution of the (quadrupole) orbitrap instruments and the QTOF instrument in high-resolution mode distinguished THC in hair samples from endogenous isobaric interferences. As expected, enhanced selectivity compromises sensitivity and THC was only detectable in hair from heavy users. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

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

PubMed

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

2012-11-20

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

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry.

PubMed

Haler, Jean R N; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-11-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. Graphical Abstract ᅟ.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Haler, Jean R. N.; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-08-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. [Figure not available: see fulltext.

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

PubMed Central

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

2013-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 thatmore » 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.« less

Long-term sub second-response monitoring of gaseous ammonia in ambient air by positive inhaling ion mobility spectrometry.

PubMed

Huang, Wei; Wang, Weiguo; Chen, Chuang; Li, Mei; Peng, Liying; Li, Hang; Liu, Jiwei; Hou, Keyong; Li, Haiyang

2017-12-01

A real-time dynamic measurements of ammonia (NH 3 ) is crucial for understanding the atmospheric nucleation process. A novel method was developed for on line monitoring at the sub-second time scale for the gaseous ammonia in ambient air for months, based on a positive inhaling ion mobility spectrometry (IMS) with a 63 Ni ion source. The selective detection of NH 3 was achieved using a high resolution IMS with an optimization of the drift tube temperature above 150°C. This method improved the peak-to-peak resolution significantly, thus avoided the interferences of the adjacent peaks to the quantitative analysis of NH 3 . The time resolution of the IMS was less than 0.1s at a data averaging of 10 times. The limit of detection (LOD) achieved at sub-ppb level while a linear response of peak intensity versus concentration of NH 3 in the range of 10-60ppb and 60-400ppb were obtained. The relative standard deviations (RSD), the confidence level and the errors were 1.06%, 95% and ± 0.21ppb by measuring 100ppb NH 3 for 100 times. The effect of ambient humidity could be greatly reduced by using the drift temperature of over 150°C. At last, the application of measuring the NH 3 concentration evolutions of Dalian city was performed from June 19 to December 3 in 2015. The results illustrated a potential method of using IMS for a real-time measuring atmospheric NH 3 at an unprecedented accuracy and sensitivity with long-term stability. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Ion peak narrowing by applying additional AC voltage (ripple voltage) to FAIMS extractor electrode.

PubMed

Pervukhin, Viktor V; Sheven, Dmitriy G

2010-01-01

The use of a non-uniform electric field in a high-field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer increases sensitivity but decreases resolution. The application of an additional AC voltage to the extractor electrode ("ripple" voltage, U(ripple)) can overcome this effect, which decreases the FAIMS peak width. In this approach, the diffusion ion loss remains minimal in the non-uniform electric field in the cylindrical part of the device, and all ion losses under U(ripple) occur in a short portion of their path. Application of the ripple voltage to the extractor electrode is twice as efficient as the applying of U(ripple) along the total length of the device. 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Consequences of transition from liquid chromatography to supercritical fluid chromatography on the overall performance of a chiral zwitterionic ion-exchanger.

PubMed

Wolrab, Denise; Frühauf, Peter; Gerner, Christopher; Kohout, Michal; Lindner, Wolfgang

2017-09-29

Major differences in the chromatographic performance of a zwitterion ion-exchange type (ZWIX) chiral stationary phase (CSP) in supercritical fluid chromatography (SFC) and high-performance liquid chromatography (HPLC) have been observed. To explain these differences, transition from HPLC to SFC conditions has been performed. The amount of a protic organic modifier in supercritical carbon dioxide (scCO 2 ) was stepwise increased and the effect of this change studied using acidic, basic and ampholytic analytes. At the same time, the effect of various basic additives to the mobile phase and transient acidic buffer species, formed by the reaction of scCO 2 with the organic modifier and additives, was assessed. Evidence is provided that a transient acid together with the intrinsic counter-ions present in the ZWIX selector structure drive the elution of analytes even when no buffer is employed. We show that the tested analytes can be enantioseparated under both SFC and HPLC conditions; the best conditions for the resolution of ampholytes are in the so-called enhanced-fluidity mobile phase region. As a consequence, subcritical fluid and enhanced-fluidity mobile phase regions seem to be chromatographic modes with a high potential for operating ZWIX CSPs. Copyright © 2017 Elsevier B.V. All rights reserved.

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

NASA Technical Reports Server (NTRS)

Mercado, AL; Marsden, Paul

1995-01-01

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

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.

Mobilities of uranium and mercury ions in helium

NASA Technical Reports Server (NTRS)

Johnsen, R.; Biondi, M. A.

1972-01-01

The mobilities of mass-identified U(+) and Hg (+) ions in helium were determined in a drift tube-mass spectrometer. For uranium ions, a reduced mobility value is obtained at 305 K and a standard gas density of 2.69 x 10 to the 19th power/cu cm. The mobility of mercury ions is in agreement with two previous determinations. The effect of fast ion injection in drift mobility measurements is discussed, and a technique to circumvent these problems is described. The results are compared with existing theories of ion mobilities.

Development of a Fourier-transform ion cyclotron resonance mass spectrometer-ion mobility spectrometer

NASA Astrophysics Data System (ADS)

Bluhm, Brian K.; Gillig, Kent J.; Russell, David H.

2000-11-01

In an effort to incorporate ion-molecule reaction chemistry with ion mobility measurements we designed and constructed a novel instrument that combines a Fourier-transform ion cyclotron resonance (ICR) mass spectrometer with an ion mobility drift cell and a time-of-flight mass spectrometer. Measured mobilities for Ar+ and CO+ in helium are in excellent agreement with accepted literature values demonstrating that there are no adverse effects from the magnetic field on ion mobility measurements. Drift cell pressure, extracted from the measured mobility of Ar+ in helium, indicate that a pressure of ˜0.25 Torr is achieved in the present configuration. There are significant technological challenges associated with combining ICR and ion mobility that occurred during construction of this instrument, such as differential pumping and aperture alignment are presented.

Characterization of chiral amino acids from different milk origins using ultra-performance liquid chromatography coupled to ion-mobility mass spectrometry

NASA Astrophysics Data System (ADS)

Tian, He; Zheng, Nan; Li, Songli; Zhang, Yangdong; Zhao, Shengguo; Wen, Fang; Wang, Jiaqi

2017-04-01

Milk contains free amino acids (AAs) that play essential roles in maintaining the growth and health of infants, and D-AA isomers are increasingly being recognized as important signalling molecules. However, there are no studies of the different characteristics of chiral AA (C-AA) from different milk origins. Here, UPLC coupled to ion-mobility high-resolution MS (IM-HRMS) was employed to characterize 18 pairs of C-AAs in human, cow, yak, buffalo, goat, and camel milk. The results proved that milk origins can be differentiated based on the D- to L- AA ratio-based projection scores by principal component analysis. The present study gives a deeper understanding of the D- to L- AA ratio underlying the biological functions of different animal milks, and provide a new strategy for the study of AA metabolic pathways.

ETD in a traveling wave ion guide at tuned Z-spray ion source conditions allows for site-specific hydrogen/deuterium exchange measurements.

PubMed

Rand, Kasper D; Pringle, Steven D; Morris, Michael; Engen, John R; Brown, Jeffery M

2011-10-01

The recent application of electron transfer dissociation (ETD) to measure the hydrogen exchange of proteins in solution at single-residue resolution (HX-ETD) paves the way for mass spectrometry-based analyses of biomolecular structure at an unprecedented level of detail. The approach requires that activation of polypeptide ions prior to ETD is minimal so as to prevent undesirable gas-phase randomization of the deuterium label from solution (i.e., hydrogen scrambling). Here we explore the use of ETD in a traveling wave ion guide of a quadrupole-time-of-flight (Q-TOF) mass spectrometer with a "Z-spray" type ion source, to measure the deuterium content of individual residues in peptides. We systematically identify key parameters of the Z-spray ion source that contribute to collisional activation and define conditions that allow ETD experiments to be performed in the traveling wave ion guide without gas-phase hydrogen scrambling. We show that ETD and supplemental collisional activation in a subsequent traveling wave ion guide allows for improved extraction of residue-specific deuterium contents in peptides with low charge. Our results demonstrate the feasibility, and illustrate the advantages of performing HX-ETD experiments on a high-resolution Q-TOF instrument equipped with traveling wave ion guides. Determination of parameters of the Z-spray ion source that contribute to ion heating are similarly pertinent to a growing number of MS applications that also rely on an energetically gentle transfer of ions into the gas-phase, such as the analysis of biomolecular structure by native mass spectrometry in combination with gas-phase ion-ion/ion-neutral reactions or ion mobility spectrometry. © American Society for Mass Spectrometry, 2011

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS.

PubMed

Benigni, Paolo; Marin, Rebecca; Sandoval, Kathia; Gardinali, Piero; Fernandez-Lima, Francisco

2017-03-03

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry-Fourier transform-ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

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.

Cyclohexylamine additives for enhanced peptide separations in reversed phase liquid chromatography.

PubMed

Cole, S R; Dorsey, J G

1997-01-01

While the choice of stationary phase, organic modifier, and gradient strength can have significant effects on biomolecule separations, mobile phase additives can also have a significant effect on the chromatographic selectivity, recovery, efficiency and resolution. Given the importance of stationary phase coverage, the beneficial, silanol-masking properties of amines, and the potential for selectivity modification through ion-pair interactions, cyclohexylamine was examined as a mobile phase additive and compared with triethylamine and trifluoroacetic acid. Greatly improved separation was possible when cyclohexylamine was used as compared with phosphate buffer, and cyclohexylamine did not require purification before use, while triethylamine required distillation before 'clean' chromatograms were obtained.

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Liulin; Ibrahim, Yehia M.; Garimella, Sandilya V. B.

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 ionmore » 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adamov, Alexey; Viidanoja, Jyrki; Kaerpaenoja, Esko

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.

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.

Recent advances in lipid separations and structural elucidation using mass spectrometry combined with ion mobility spectrometry, ion-molecule reactions and fragmentation approaches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Xueyun; Smith, Richard D.; Baker, Erin S.

Lipids are a vital class of molecules that play important and varied roles in biological processes. Fully understanding lipid roles, however, is extremely difficult since the number and diversity of lipid species is immense, with cells expressing hundreds of enzymes that synthesize tens of thousands of different lipids. While recent advances in chromatography and high resolution mass spectrometry have greatly progressed the understanding of lipid species and functions, effectively separating many lipids still remains problematic. Isomeric lipids have made lipid characterization especially difficult and occur due to subclasses having the same chemical composition, or species having multiple acyl chains connectivitiesmore » (sn-1, sn-2, or sn-3), double bond positions and orientations (cis or trans), and functional group stereochemistry (R versus S). Fully understanding the roles of lipids in biological processes therefore requires separating and evaluating how isomers change in biological and environmental samples. To address this challenge, ion mobility spectrometry separations, ion-molecule reactions and fragmentation techniques have increasingly been added to lipid analysis workflows to improve identifications. In this manuscript, we review the current state of these approaches and their capabilities for improving the identification of specific lipid species.« less

Correlation between cation conduction and ionic morphology in a PEO-based single ion conductor

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2011-03-01

We use molecular dynamics simulation to study ion transport and backbone mobility of a PEO-based single ion conductor. Ion mobility depends on the chemical structure and the local environment of the ions, which consequently impact ionic conductivity. We characterize the aggregation state of the ions, and assess the role of ion complexes in ionomer dynamics. In addition to solvated cations and pairs, higher order ion clusters are found. Most of the ion clusters are in string-like structure and cross-link two or more different ionomer chains through ionic binding. Ionic crosslinks decrease mobility at the ionic co-monomer; hence the mobility of the adjacent PEO segment is influenced. Na ions show slow mobility when they are inside large clusters. The hopping timescale for Na varies from 20 ns to 200. A correlation is found between Na mobility and the number of hops from one coordination site to another. Besides ether oxygens, Na ions in the ionomer also use the anion and the edge of the cluster as hopping sites. The string-like structure of clusters provide less stable sites at the two ends thus ions are more mobile in those regions. We observed Grotthus like mechanism in our ionomer, in which the positive charge migrates within the string-like cluster without the cations actually moving.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Comprehensive analysis of pharmaceutical products using simultaneous mixed-mode (ion-exchange/reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Nesterenko, Pavel N; Soisungnoen, Phimpha; Burakham, Rodjana; Srijaranai, Supalax; Paull, Brett

2014-08-01

Liquid chromatographic assays were developed using a mixed-mode column coupled in sequence with a hydrophilic interaction liquid chromatography column to allow the simultaneous comprehensive analysis of inorganic/organic anions and cations, active pharmaceutical ingredients, and excipients (carbohydrates). The approach utilized dual sample injection and valve-mediated column switching and was based upon a single high-performance liquid chromatography gradient pump. The separation consisted of three distinct sequential separation mechanisms, namely, (i) ion-exchange, (ii) mixed-mode interactions under an applied dual gradient (reversed-phase/ion-exchange), and (iii) hydrophilic interaction chromatography. Upon first injection, the Scherzo SS C18 column (Imtakt) provided resolution of inorganic anions and cations under isocratic conditions, followed by a dual organic/salt gradient to elute active pharmaceutical ingredients and their respective organic counterions and potential degradants. At the top of the mixed-mode gradient (high acetonitrile content), the mobile phase flow was switched to a preconditioned hydrophilic interaction liquid chromatography column, and the standard/sample was reinjected for the separation of hydrophilic carbohydrates, some of which are commonly known excipients in drug formulations. The approach afforded reproducible separation and resolution of up to 23 chemically diverse solutes in a single run. The method was applied to investigate the composition of commercial cough syrups (Robitussin®), allowing resolution and determination of inorganic ions, active pharmaceutical ingredients, excipients, and numerous well-resolved unknown peaks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Resolution and Assignment of Differential Ion Mobility Spectra of Sarcosine and Isomers.

PubMed

Berthias, Francis; Maatoug, Belkis; Glish, Gary L; Moussa, Fathi; Maitre, Philippe

2018-04-01

Due to their central role in biochemical processes, fast separation and identification of amino acids (AA) is of importance in many areas of the biomedical field including the diagnosis and monitoring of inborn errors of metabolism and biomarker discovery. Due to the large number of AA together with their isomers and isobars, common methods of AA analysis are tedious and time-consuming because they include a chromatographic separation step requiring pre- or post-column derivatization. Here, we propose a rapid method of separation and identification of sarcosine, a biomarker candidate of prostate cancer, from isomers using differential ion mobility spectrometry (DIMS) interfaced with a tandem mass spectrometer (MS/MS) instrument. Baseline separation of protonated sarcosine from α- and β-alanine isomers can be easily achieved. Identification of DIMS peak is performed using an isomer-specific activation mode where DIMS- and mass-selected ions are irradiated at selected wavenumbers allowing for the specific fragmentation via an infrared multiple photon dissociation (IRMPD) process. Two orthogonal methods to MS/MS are thus added, where the MS/MS(IRMPD) is nothing but an isomer-specific multiple reaction monitoring (MRM) method. The identification relies on the comparison of DIMS-MS/MS(IRMPD) chromatograms recorded at different wavenumbers. Based on the comparison of IR spectra of the three isomers, it is shown that specific depletion of the two protonated α- and β-alanine can be achieved, thus allowing for clear identification of the sarcosine peak. It is also demonstrated that DIMS-MS/MS(IRMPD) spectra in the carboxylic C=O stretching region allow for the resolution of overlapping DIMS peaks. Graphical Abstract ᅟ.

Fast Orthogonal Separation by Superposition of Time of Flight and Field Asymmetric Ion Mobility Spectrometry.

PubMed

Bohnhorst, Alexander; Kirk, Ansgar T; Berger, Marc; Zimmermann, Stefan

2018-01-16

Ion mobility spectrometry is a powerful and low-cost technique for the identification of chemical warfare agents, toxic chemicals, or explosives in air. Drift tube ion mobility spectrometers (DT-IMS) separate ions by the absolute value of their low field ion mobility, while field asymmetric ion mobility spectrometers (FAIMS) separate them by the change of their ion mobility at high fields. However, using one of these devices alone, some common and harmless substances show the same response as the hazardous target substances. In order to increase the selectivity, orthogonal data are required. Thus, in this work, we present for the first time an ambient pressure ion mobility spectrometer which is able to separate ions both by their differential and low field mobility, providing additional information for selectivity enhancement. This novel field asymmetric time of flight ion mobility spectrometer (FAT-IMS) allows high repetition rates and reaches limits of detection in the low ppb range common for DT-IMS. The device consists of a compact 44 mm drift tube with a tritium ionization source and a resolving power of 70. An increased separation of four substances with similar low field ion mobility is shown: phosgene (K 0 = 2.33 cm 2 /(V s)), 1,1,2-trichlorethane (K 0 = 2.31 cm 2 /(V s)), chlorine (K 0 = 2.24 cm 2 /(V s)), and nitrogen dioxide (K 0 = 2.25 cm 2 /(V s)). Furthermore, the behavior and limits of detection for acetonitrile, dimethyl methylphosphonate, diisopropyl methyl phosphonate in positive polarity and carbon dioxide, sulfur dioxide, hydrochloric acid, cyanogen chloride, and hydrogen cyanide in negative polarity are investigated.

Mobilities of ground-state and metastable O/+/, O2/+/, O/2+/, and O2/2+/ ions in helium and neon

NASA Astrophysics Data System (ADS)

Johnsen, R.; Biondi, M. A.; Hayashi, M.

1982-09-01

The ionic mobilities of O(+), O2(+), O(2+), and O2(2+) in helium and neon have been measured using a selected-ion drift apparatus (SIDA). It is found that the mobilities of both O(+) and O2(+) ions in the metastable states (2D or 4Pi u) are measurably smaller than those of the same ions carried out by using known, state-selective ion-molecule reactions. A similar mobility differentiation of ground-state and metastable ions was not observed for the O(2+) and O2(2+) ions.

Normal-inverse bimodule operation Hadamard transform ion mobility spectrometry.

PubMed

Hong, Yan; Huang, Chaoqun; Liu, Sheng; Xia, Lei; Shen, Chengyin; Chu, Yannan

2018-10-31

In order to suppress or eliminate the spurious peaks and improve signal-to-noise ratio (SNR) of Hadamard transform ion mobility spectrometry (HT-IMS), a normal-inverse bimodule operation Hadamard transform - ion mobility spectrometry (NIBOHT-IMS) technique was developed. In this novel technique, a normal and inverse pseudo random binary sequence (PRBS) was produced in sequential order by an ion gate controller and utilized to control the ion gate of IMS, and then the normal HT-IMS mobility spectrum and the inverse HT-IMS mobility spectrum were obtained. A NIBOHT-IMS mobility spectrum was gained by subtracting the inverse HT-IMS mobility spectrum from normal HT-IMS mobility spectrum. Experimental results demonstrate that the NIBOHT-IMS technique can significantly suppress or eliminate the spurious peaks, and enhance the SNR by measuring the reactant ions. Furthermore, the gas CHCl 3 and CH 2 Br 2 were measured for evaluating the capability of detecting real sample. The results show that the NIBOHT-IMS technique is able to eliminate the spurious peaks and improve the SNR notably not only for the detection of larger ion signals but also for the detection of small ion signals. Copyright © 2018 Elsevier B.V. All rights reserved.

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation

NASA Astrophysics Data System (ADS)

Di Giovanni, James P.; Barkley, Robert M.; Jones, David N. M.; Hankin, Joseph A.; Murphy, Robert C.

2018-04-01

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H]- ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H]- and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H2O-CO2]- and [M-H-H2O]- displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H2O]- ion from LTB4 was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H2O]- product ions from LTB4 was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques. [Figure not available: see fulltext.

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation.

PubMed

Di Giovanni, James P; Barkley, Robert M; Jones, David N M; Hankin, Joseph A; Murphy, Robert C

2018-04-23

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H] - ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H] - and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H 2 O-CO 2 ] - and [M-H-H 2 O] - displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H 2 O] - ion from LTB 4 was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H 2 O] - product ions from LTB 4 was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques. Graphical Abstract ᅟ.

Separation and Classification of Lipids Using Differential Ion Mobility Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvartsburg, Alexandre A.; Isaac, Georgis; Leveque, Nathalie

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 ofmore » 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.« less

Identification of novel isomeric pectic oligosaccharides using hydrophilic interaction chromatography coupled to traveling-wave ion mobility mass spectrometry.

PubMed

Leijdekkers, Antonius G M; Huang, Jie-Hong; Bakx, Edwin J; Gruppen, Harry; Schols, Henk A

2015-03-02

Separation and characterization of complex mixtures of pectic oligosaccharides still remains challenging and often requires the use of multiple analytical techniques, especially when isomeric structures are present. In this work, it is demonstrated that the coupling of hydrophilic interaction chromatography (HILIC) to traveling-wave ion mobility mass spectrometry (TWIMMS) enabled the simultaneous separation and characterization of complex mixtures of various isomeric pectic oligosaccharides. Labeling of oligosaccharides with 3-aminoquinoline (3-AQ) improved MS-ionization efficiency of the oligosaccharides and reduced the complexity of the product ion mass spectra, without losing resolution of the HILIC separation. In addition, labeling enabled quantification of oligosaccharides on molar basis using in-line fluorescence detection. Isomeric structures were distinguished using TWIMMS. The 3-AQ-HILIC-TWIMMS method was used to characterize a series of isomeric sugar beet rhamnogalacturonan I derived oligosaccharides carrying a glucuronic acid substituent. Thereby, some novel structural features were identified for the first time: glucuronic acid was attached to O-3 or to O-2 of galacturonic acid residues and a single galacturonic acid residue within an oligomer could contain both an acetyl group and a glucuronic acid substituent. Copyright © 2014 Elsevier Ltd. All rights reserved.

High-performance multiple-reflection time-of-flight mass spectrometers for research with exotic nuclei and for analytical mass spectrometry

NASA Astrophysics Data System (ADS)

Plaß, Wolfgang R.; Dickel, Timo; Ayet San Andres, Samuel; Ebert, Jens; Greiner, Florian; Hornung, Christine; Jesch, Christian; Lang, Johannes; Lippert, Wayne; Majoros, Tamas; Short, Devin; Geissel, Hans; Haettner, Emma; Reiter, Moritz P.; Rink, Ann-Kathrin; Scheidenberger, Christoph; Yavor, Mikhail I.

2015-11-01

A class of multiple-reflection time-of-flight mass spectrometers (MR-TOF-MSs) has been developed for research with exotic nuclei at present and future accelerator facilities such as GSI and FAIR (Darmstadt), and TRIUMF (Vancouver). They can perform highly accurate mass measurements of exotic nuclei, serve as high-resolution, high-capacity mass separators and be employed as diagnostics devices to monitor the production, separation and manipulation of beams of exotic nuclei. In addition, a mobile high-resolution MR-TOF-MS has been developed for in situ applications in analytical mass spectrometry ranging from environmental research to medicine. Recently, the MR-TOF-MS for GSI and FAIR has been further developed. A novel RF quadrupole-based ion beam switchyard has been developed that allows merging and splitting of ion beams as well as transport of ions into different directions. It efficiently connects a test and reference ion source and an auxiliary detector to the system. Due to an increase in the kinetic energy of the ions in the time-of-flight analyzer of the MR-TOF-MS, a given mass resolving power is now achieved in less than half the time-of-flight. Conversely, depending on the time-of-flight, the mass resolving power has been increased by a factor of more than two.

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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.

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.

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

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2010-03-01

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

Online Hydrogen-Deuterium Exchange Traveling Wave Ion Mobility Mass Spectrometry (HDX-IM-MS): a Systematic Evaluation

NASA Astrophysics Data System (ADS)

Cryar, Adam; Groves, Kate; Quaglia, Milena

2017-06-01

Hydrogen-deuterium exchange mass spectrometry (HDX-MS) is an important tool for measuring and monitoring protein structure. A bottom-up approach to HDX-MS provides peptide level deuterium uptake values and a more refined localization of deuterium incorporation compared with global HDX-MS measurements. The degree of localization provided by HDX-MS is proportional to the number of peptides that can be identified and monitored across an exchange experiment. Ion mobility spectrometry (IMS) has been shown to improve MS-based peptide analysis of biological samples through increased separation capacity. The integration of IMS within HDX-MS workflows has been commercialized but presently its adoption has not been widespread. The potential benefits of IMS, therefore, have not yet been fully explored. We herein describe a comprehensive evaluation of traveling wave ion mobility integrated within an online-HDX-MS system and present the first reported example of UDMSE acquisition for HDX analysis. Instrument settings required for optimal peptide identifications are described and the effects of detector saturation due to peak compression are discussed. A model system is utilized to confirm the comparability of HDX-IM-MS and HDX-MS uptake values prior to an evaluation of the benefits of IMS at increasing sample complexity. Interestingly, MS and IM-MS acquisitions were found to identify distinct populations of peptides that were unique to the respective methods, a property that can be utilized to increase the spatial resolution of HDX-MS experiments by >60%. [Figure not available: see fulltext.

Conformational structures of a decapeptide validated by first principles calculations and cold ion spectroscopy.

PubMed

Roy, Tapta Kanchan; Kopysov, Vladimir; Nagornova, Natalia S; Rizzo, Thomas R; Boyarkin, Oleg V; Gerber, R Benny

2015-05-18

Calculated structures of the two most stable conformers of a protonated decapeptide gramicidin S in the gas phase have been validated by comparing the vibrational spectra, calculated from first- principles and measured in a wide spectral range using infrared (IR)-UV double resonance cold ion spectroscopy. All the 522 vibrational modes of each conformer were calculated quantum mechanically and compared with the experiment without any recourse to an empirical scaling. The study demonstrates that first-principles calculations, when accounting for vibrational anharmonicity, can reproduce high-resolution experimental spectra well enough for validating structures of molecules as large as of 200 atoms. The validated accurate structures of the peptide may serve as templates for in silico drug design and absolute calibration of ion mobility measurements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

PubMed

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

FAIMS Operation for Realistic Gas Flow Profile and Asymmetric Waveforms Including Electronic Noise and Ripple

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

The use of Field Asymmetric waveform Ion Mobility Spectrometry (FAIMS) has rapidly grown with the advent of commercial FAIMS systems coupled to mass spectrometry. However, many fundamental aspects of FAIMS remain obscure, hindering its technological improvement and expansion of analytical utility. Recently, we developed a comprehensive numerical simulation approach to FAIMS that can handle any device geometry and operational conditions. The formalism was originally set up in one dimension for a uniform gas flow and limited to ideal asymmetric voltage waveforms. Here we extend the model to account for a realistic gas flow velocity distribution in the analytical gap, axialmore » ion diffusion, and waveform imperfections (e.g. noise and ripple). The non-uniformity of gas flow velocity profile has only a minor effect, slightly improving resolution. However, waveform perturbations are significant even at very low levels, in some cases {approx} 0.01% of nominal voltage. These perturbations always improve resolution and decrease sensitivity. Variation of noise or ripple amplitude produces a trade-off between resolution and sensitivity. This trade-off is physically equivalent to that obtained via adjustment of the gap width and/or asymmetric waveform frequency, but the scaling of low-frequency ripple appears to be a more practical way to control FAIMS resolution.« less

Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poad, Berwyck L. J.; Zheng, Xueyun; Mitchell, Todd W.

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressuremore » trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.« less

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Mowei; Yan, Jing; Romano, Christine A.

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase Mnx from Bacillus sp. PL-12 has been successfully overexpressed in active form, unexpectedly, as a protein complex with a molecular weight of 211 kDa with no homology to known proteins in the database. We have recently used surface induced dissociation (SID) and ion mobility – mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data frommore » the native mass spectrometry experiment led to a plausible model of this unknown multicopper oxidase which has been difficult to study by conventional structural biology methods. However, because each subunit of Mnx binds copper ions as cofactor at varying ratios, there were remaining ambiguities in assigning some of the observed peaks to metal-binding species because of the sample heterogeneity and limited mass resolution. In this study, we performed SID in a modified Fourier transform – ion cyclotron resonance (FT-ICR) mass spectrometer for obtaining the ultimate resolution on the released subcomplexes of Mnx. The high mass accuracy and resolution unveiled unexpected artificial modifications in the protein that have been previously thought to be iron bound species based on lower resolution data. Additionally, most released subcomplexes were isotopically resolved for defining metal binding stoichiometry at each structural level. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes.« less

Mathematical models of continuous flow electrophoresis: Electrophoresis technology

NASA Technical Reports Server (NTRS)

Saville, Dudley A.

1986-01-01

Two aspects of continuous flow electrophoresis were studied: (1) the structure of the flow field in continuous flow devices; and (2) the electrokinetic properties of suspended particles relevant to electrophoretic separations. Mathematical models were developed to describe flow structure and stability, with particular emphasis on effects due to buoyancy. To describe the fractionation of an arbitrary particulate sample by continuous flow electrophoresis, a general mathematical model was constructed. In this model, chamber dimensions, field strength, buffer composition, and other design variables can be altered at will to study their effects on resolution and throughput. All these mathematical models were implemented on a digital computer and the codes are available for general use. Experimental and theoretical work with particulate samples probed how particle mobility is related to buffer composition. It was found that ions on the surface of small particles are mobile, contrary to the widely accepted view. This influences particle mobility and suspension conductivity. A novel technique was used to measure the mobility of particles in concentrated suspensions.

Ion Elevators and Escalators in Multilevel Structures for Lossless Ion Manipulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibrahim, Yehia M.; Hamid, Ahmed M.; Cox, Jonathan T.

2017-01-19

We describe two approaches based upon ion ‘elevator’ and ‘escalator’ components that allow moving ions to different levels in structures for lossless ion manipulations (SLIM). Guided by ion motion simulations we designed elevator and escalator components providing essentially lossless transmission in multi-level designs based upon ion current measurements. The ion elevator design allowed ions to efficiently bridge a 4 mm gap between levels. The component was integrated in a SLIM and coupled to a QTOF mass spectrometer using an ion funnel interface to evaluate the m/z range transmitted as compared to transmission within a level (e.g. in a linear section).more » Mass spectra for singly-charged ions of m/z 600-2700 produced similar mass spectra for both elevator and straight (linear motion) components. In the ion escalator design, traveling waves (TW) were utilized to transport ions efficiently between two SLIM levels. Ion current measurements and ion mobility (IM) spectrometry analysis illustrated that ions can be transported between TW-SLIM levels with no significant loss of either ions or IM resolution. These developments provide a path for the development of multilevel designs providing e.g. much longer IM path lengths, more compact designs, and the implementation of much more complex SLIM devices in which e.g. different levels may operate at different temperatures or with different gases.« less

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

PubMed

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

2017-08-04

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

On the isobaric space of 25-hydroxyvitamin D in human serum: potential for interferences in liquid chromatography/tandem mass spectrometry, systematic errors and accuracy issues.

PubMed

Qi, Yulin; Geib, Timon; Schorr, Pascal; Meier, Florian; Volmer, Dietrich A

2015-01-15

Isobaric interferences in human serum can potentially influence the measured concentration levels of 25-hydroxyvitamin D [25(OH)D], when low resolving power liquid chromatography/tandem mass spectrometry (LC/MS/MS) instruments and non-specific MS/MS product ions are employed for analysis. In this study, we provide a detailed characterization of these interferences and a technical solution to reduce the associated systematic errors. Detailed electrospray ionization Fourier transform ion cyclotron resonance (FTICR) high-resolution mass spectrometry (HRMS) experiments were used to characterize co-extracted isobaric components of 25(OH)D from human serum. Differential ion mobility spectrometry (DMS), as a gas-phase ion filter, was implemented on a triple quadrupole mass spectrometer for separation of the isobars. HRMS revealed the presence of multiple isobaric compounds in extracts of human serum for different sample preparation methods. Several of these isobars had the potential to increase the peak areas measured for 25(OH)D on low-resolution MS instruments. A major isobaric component was identified as pentaerythritol oleate, a technical lubricant, which was probably an artifact from the analytical instrumentation. DMS was able to remove several of these isobars prior to MS/MS, when implemented on the low-resolution triple quadrupole mass spectrometer. It was shown in this proof-of-concept study that DMS-MS has the potential to significantly decrease systematic errors, and thus improve accuracy of vitamin D measurements using LC/MS/MS. Copyright © 2014 John Wiley & Sons, Ltd.

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.

Resolution and Assignment of Differential Ion Mobility Spectra of Sarcosine and Isomers

NASA Astrophysics Data System (ADS)

Berthias, Francis; Maatoug, Belkis; Glish, Gary L.; Moussa, Fathi; Maitre, Philippe

2018-02-01

Due to their central role in biochemical processes, fast separation and identification of amino acids (AA) is of importance in many areas of the biomedical field including the diagnosis and monitoring of inborn errors of metabolism and biomarker discovery. Due to the large number of AA together with their isomers and isobars, common methods of AA analysis are tedious and time-consuming because they include a chromatographic separation step requiring pre- or post-column derivatization. Here, we propose a rapid method of separation and identification of sarcosine, a biomarker candidate of prostate cancer, from isomers using differential ion mobility spectrometry (DIMS) interfaced with a tandem mass spectrometer (MS/MS) instrument. Baseline separation of protonated sarcosine from α- and β-alanine isomers can be easily achieved. Identification of DIMS peak is performed using an isomer-specific activation mode where DIMS- and mass-selected ions are irradiated at selected wavenumbers allowing for the specific fragmentation via an infrared multiple photon dissociation (IRMPD) process. Two orthogonal methods to MS/MS are thus added, where the MS/MS(IRMPD) is nothing but an isomer-specific multiple reaction monitoring (MRM) method. The identification relies on the comparison of DIMS-MS/MS(IRMPD) chromatograms recorded at different wavenumbers. Based on the comparison of IR spectra of the three isomers, it is shown that specific depletion of the two protonated α- and β-alanine can be achieved, thus allowing for clear identification of the sarcosine peak. It is also demonstrated that DIMS-MS/MS(IRMPD) spectra in the carboxylic C=O stretching region allow for the resolution of overlapping DIMS peaks. [Figure not available: see fulltext.

Towards Discovery and Targeted Peptide Biomarker Detection Using nanoESI-TIMS-TOF MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garabedian, Alyssa; Benigni, Paolo; Ramirez, Cesar E.

Abstract. In the present work, the potential of trapped ion mobility spectrometry coupled to TOF mass spectrometry (TIMS-TOF MS) for discovery and targeted monitoring of peptide biomarkers from human-in-mouse xenograft tumor tissue was evaluated. In particular, a TIMS-MS workflow was developed for the detection and quantification of peptide biomarkers using internal heavy analogs, taking advantage of the high mobility resolution (R = 150–250) prior to mass analysis. Five peptide biomarkers were separated, identified, and quantified using offline nanoESI-TIMSCID- TOF MS; the results were in good agreement with measurements using a traditional LC-ESI-MS/MS proteomics workflow. The TIMS-TOF MS analysis permitted peptidemore » biomarker detection based on accurate mobility, mass measurements, and high sequence coverage for concentrations in the 10–200 nM range, while simultaneously achieving discovery measurements« less

Surface Induced Dissociation Coupled with High Resolution Mass Spectrometry Unveils Heterogeneity of a 211 kDa Multicopper Oxidase Protein Complex

NASA Astrophysics Data System (ADS)

Zhou, Mowei; Yan, Jing; Romano, Christine A.; Tebo, Bradley M.; Wysocki, Vicki H.; Paša-Tolić, Ljiljana

2018-01-01

Manganese oxidation is an important biogeochemical process that is largely regulated by bacteria through enzymatic reactions. However, the detailed mechanism is poorly understood due to challenges in isolating and characterizing these unknown enzymes. A manganese oxidase, Mnx, from Bacillus sp. PL-12 has been successfully overexpressed in active form as a protein complex with a molecular mass of 211 kDa. We have recently used surface induced dissociation (SID) and ion mobility-mass spectrometry (IM-MS) to release and detect folded subcomplexes for determining subunit connectivity and quaternary structure. The data from the native mass spectrometry experiments led to a plausible structural model of this multicopper oxidase, which has been difficult to study by conventional structural biology methods. It was also revealed that each Mnx subunit binds a variable number of copper ions. Becasue of the heterogeneity of the protein and limited mass resolution, ambiguities in assigning some of the observed peaks remained as a barrier to fully understanding the role of metals and potential unknown ligands in Mnx. In this study, we performed SID in a modified Fourier transform-ion cyclotron resonance (FTICR) mass spectrometer. The high mass accuracy and resolution offered by FTICR unveiled unexpected artificial modifications on the protein that had been previously thought to be iron bound species based on lower resolution spectra. Additionally, isotopically resolved spectra of the released subcomplexes revealed the metal binding stoichiometry at different structural levels. This method holds great potential for in-depth characterization of metalloproteins and protein-ligand complexes. [Figure not available: see fulltext.

Discriminant analysis of fused positive and negative ion mobility spectra using multivariate self-modeling mixture analysis and neural networks.

PubMed

Chen, Ping; Harrington, Peter B

2008-02-01

A new method coupling multivariate self-modeling mixture analysis and pattern recognition has been developed to identify toxic industrial chemicals using fused positive and negative ion mobility spectra (dual scan spectra). A Smiths lightweight chemical detector (LCD), which can measure positive and negative ion mobility spectra simultaneously, was used to acquire the data. Simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) was used to separate the analytical peaks in the ion mobility spectra from the background reactant ion peaks (RIP). The SIMPLSIMA analytical components of the positive and negative ion peaks were combined together in a butterfly representation (i.e., negative spectra are reported with negative drift times and reflected with respect to the ordinate and juxtaposed with the positive ion mobility spectra). Temperature constrained cascade-correlation neural network (TCCCN) models were built to classify the toxic industrial chemicals. Seven common toxic industrial chemicals were used in this project to evaluate the performance of the algorithm. Ten bootstrapped Latin partitions demonstrated that the classification of neural networks using the SIMPLISMA components was statistically better than neural network models trained with fused ion mobility spectra (IMS).

A Simple Analytical Model for Predicting the Detectable Ion Current in Ion Mobility Spectrometry Using Corona Discharge Ionization Sources

NASA Astrophysics Data System (ADS)

Kirk, Ansgar Thomas; Kobelt, Tim; Spehlbrink, Hauke; Zimmermann, Stefan

2018-05-01

Corona discharge ionization sources are often used in ion mobility spectrometers (IMS) when a non-radioactive ion source with high ion currents is required. Typically, the corona discharge is followed by a reaction region where analyte ions are formed from the reactant ions. In this work, we present a simple yet sufficiently accurate model for predicting the ion current available at the end of this reaction region when operating at reduced pressure as in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) or most IMS-MS instruments. It yields excellent qualitative agreement with measurement results and is even able to calculate the ion current within an error of 15%. Additional interesting findings of this model are the ion current at the end of the reaction region being independent from the ion current generated by the corona discharge and the ion current in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) growing quadratically when scaling down the length of the reaction region. [Figure not available: see fulltext.

A Simple Analytical Model for Predicting the Detectable Ion Current in Ion Mobility Spectrometry Using Corona Discharge Ionization Sources.

PubMed

Kirk, Ansgar Thomas; Kobelt, Tim; Spehlbrink, Hauke; Zimmermann, Stefan

2018-05-08

Corona discharge ionization sources are often used in ion mobility spectrometers (IMS) when a non-radioactive ion source with high ion currents is required. Typically, the corona discharge is followed by a reaction region where analyte ions are formed from the reactant ions. In this work, we present a simple yet sufficiently accurate model for predicting the ion current available at the end of this reaction region when operating at reduced pressure as in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) or most IMS-MS instruments. It yields excellent qualitative agreement with measurement results and is even able to calculate the ion current within an error of 15%. Additional interesting findings of this model are the ion current at the end of the reaction region being independent from the ion current generated by the corona discharge and the ion current in High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) growing quadratically when scaling down the length of the reaction region. Graphical Abstract ᅟ.

Integration of Ion Mobility MSE after Fully Automated, Online, High-Resolution Liquid Extraction Surface Analysis Micro-Liquid Chromatography

PubMed Central

2017-01-01

Direct analysis by mass spectrometry (imaging) has become increasingly deployed in preclinical and clinical research due to its rapid and accurate readouts. However, when it comes to biomarker discovery or histopathological diagnostics, more sensitive and in-depth profiling from localized areas is required. We developed a comprehensive, fully automated online platform for high-resolution liquid extraction surface analysis (HR-LESA) followed by micro–liquid chromatography (LC) separation and a data-independent acquisition strategy for untargeted and low abundant analyte identification directly from tissue sections. Applied to tissue sections of rat pituitary, the platform demonstrated improved spatial resolution, allowing sample areas as small as 400 μm to be studied, a major advantage over conventional LESA. The platform integrates an online buffer exchange and washing step for removal of salts and other endogenous contamination that originates from local tissue extraction. Our carry over–free platform showed high reproducibility, with an interextraction variability below 30%. Another strength of the platform is the additional selectivity provided by a postsampling gas-phase ion mobility separation. This allowed distinguishing coeluted isobaric compounds without requiring additional separation time. Furthermore, we identified untargeted and low-abundance analytes, including neuropeptides deriving from the pro-opiomelanocortin precursor protein and localized a specific area of the pituitary gland (i.e., adenohypophysis) known to secrete neuropeptides and other small metabolites related to development, growth, and metabolism. This platform can thus be applied for the in-depth study of small samples of complex tissues with histologic features of ∼400 μm or more, including potential neuropeptide markers involved in many diseases such as neurodegenerative diseases, obesity, bulimia, and anorexia nervosa. PMID:28945354

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

Perfluorinated acids as ion-pairing agents in the determination of monoamine transmitters and some prominent metabolites in rat brain by high-performance liquid chromatography with amperometric detection.

PubMed

Patthy, M; Gyenge, R

1988-09-30

The behaviour of trifluoroacetate and heptafluorobutyrate as pairing ions for the reversed-phase ion-pair separation of monoamine transmitters and related metabolites was studied. The performance of systems with the perfluorinated acids was compared with that of systems containing sodium octyl sulphonate and was found to be better in terms of peak resolution combined with total analysis time, day-to-day reproducibility and the time required for attaining initial chromatographic equilibrium. Rat brain samples were deproteinized in the acidified mobile phase, injected directly on to a high-performance liquid chromatographic column and quantitated using an amperometric detector. Sample run times were 6-8 min, at a relatively low flow-rate. The detection limits achieved are fairly uncommon with conventional bore columns. The two perfluorinated acids studied differ in the dominant mechanisms of ion-pair formation and show selectivity differences as a result.

Separation and characterization of unknown impurities and isomers in flomoxef sodium by LC-IT-TOF MS and study of their negative-ion fragmentation regularities.

PubMed

Yu, Xu; Wang, Fan; Li, Jiani; Shan, Weiguang; Zhu, Bingqi; Wang, Jian

2017-06-05

Thirteen unknown impurities in flomoxef sodium were separated and characterized by liquid chromatography coupled with high resolution ion trap/time-of-flight mass spectrometry (LC-IT-TOF MS)with positive and negative modes of electrospray ionization method for further improvement of official monographs in pharmacopoeias. The fragmentation patterns of impurities in flomoxef in the negative ion mode were studied in detail, and new negative-ion fragmentation regularities were discovered. Chromatographic separation was performed on a Kromasil C18 column (250mm×4.6mm, 5μm). The mobile phase consisted of (A) ammonium formate aqueous solution (10mM)-methanol (84:16, v/v) and (B) ammonium formate aqueous solution (10mM)-methanol (47:53, v/v). In order to determine the m/z values of the molecular ions and formulas of all detected impurities, full scan LC-MS in both positive and negative ion modes was firstly executed to obtain the m/z value of the molecules. Then LC-MS 2 and LC-MS 3 were carried out on target compounds to obtain as much structural information as possible. Complete fragmentation patterns of impurities were studied and used to obtain information about the structures of these impurities. Structures of thirteen unknown degradation products in flomoxef sodium were deduced based on the high resolution MS n data with both positive and negative modes. The forming mechanisms of degradation products in flomoxef sodium were also studied. Copyright © 2017. Published by Elsevier B.V.

Application of a trap-free two-dimensional liquid chromatography combined with ion trap/time-of-flight mass spectrometry for separation and characterization of impurities and isomers in cefpiramide.

PubMed

Wang, Jian; Xu, Yu; Wen, Chunmei; Wang, Zhijian

2017-11-01

High-resolution mass spectrometry had been routinely used for structure identification of impurity. However, all LC-MS methods were based on a volatile mobile phase, and a non-volatile system is used in the official analytical method of United States Pharmacopoeia for cefpiramide which limited the use of mass spectrometry for structure characterization of the impurities. Here we presented the utilization of a trap-free two-dimensional liquid chromatography coupled to high resolution ion trap/time-of-flight mass spectrometry (2D LC-IT-TOF MS) with positive and negative modes of electrospray ionization for characterization of eight impurities in cefpiramide. Trap-free two-dimensional liquid chromatography and online desalting technique made it possible to characterize the impurity in cefpiramide in the condition of official standard, and the TIC chromatogram of LC-MS was in conformity with the LC chromatogram of the official analytical method in the peak sequence of impurities, which could further improve the method of official monographs in pharmacopoeias. Each peak separated by the non-volatile mobile phase was trapped by a 20 μL quantitative loop then transferred into a system with a volatile mobile phase connected to a MS detector. In the first dimension, the column was Kromasil C 8 analytical column (250 mm × 4.6 mm, 5 μm) with a non-volatile salt mobile phase at the flow rate of 0.8 mL min -1 . In the second dimension, the column was Shimadzu Shim-pack GISS C 18 (50 mm × 2.1 mm, 1.9 μm) with a volatile salt mobile phase at the flow rate of 0.3 mL min -1 . Through the multiple heart-cutting 2D-LC approach and online desalting technique, the problem of incompatibility between non-volatile salt mobile phase and mass spectrometry was solved completely. The fragmentation behavior of cefpiramide and its eight impurities were studied. The structures of eight impurities in cefpiramide drug substance were deduced based on the HPLC-MS n data, in which seven impurities were novel impurities. The forming mechanisms of degradation products in cefpiramide were also studied. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

Bahrami, Hamed; Tabrizchi, Mahmoud

2012-08-15

An ion mobility spectrometer is described which is equipped with two non-radioactive ion sources, namely an atmospheric pressure photoionization and a corona discharge ionization source. The two sources cannot only run individually but are additionally capable of operating simultaneously. For photoionization, a UV lamp was mounted parallel to the axis of the ion mobility cell. The corona discharge electrode was mounted perpendicular to the UV radiation. The total ion current from the photoionization source was verified as a function of lamp current, sample flow rate, and drift field. Simultaneous operation of the two ionization sources was investigated by recording ion mobility spectra of selected samples. The design allows one to observe peaks from either the corona discharge or photoionization individually or simultaneously. This makes it possible to accurately compare peaks in the ion mobility spectra from each individual source. Finally, the instrument's capability for discriminating two peaks appearing in approximately identical drift times using each individual ionization source is demonstrated. Copyright © 2012 Elsevier B.V. All rights reserved.

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).

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE PAGES

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary; ...

2017-09-21

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Insight of endo-1,4-xylanase II from Trichoderma reesei: conserved water-mediated H-bond and ion pairs interactions.

PubMed

Vijayakumar, Balakrishnan; Velmurugan, Devadasan

2013-12-01

Endo-1,4-Xylanase II is an enzyme which degrades the linear polysaccharide beta-1,4-xylan into xylose. This enzyme shows highest enzyme activity around 55 °C, even without being stabilized by the disulphide bridges. A set of nine high resolution crystal structures of Xylanase II (1.11-1.80 Å) from Trichoderma reesei were selected and analyzed in order to identify the invariant water molecules, ion pairs and water-mediated ionic interactions. The crystal structure (PDB-id: 2DFB) solved at highest resolution (1.11 Å) was chosen as the reference and the remaining structures were treated as mobile molecules. These structures were then superimposed with the reference molecule to observe the invariant water molecules using 3-dimensional structural superposition server. A total of 37 water molecules were identified to be invariant molecules in all the crystal structures, of which 26 invariant molecules have hydrogen bond interactions with the back bone of residues and 21 invariant water molecules have interactions with side chain residues. The structural and functional roles of these water molecules and ion pairs have been discussed. The results show that the invariant water molecules and ion pairs may be involved in maintaining the structural architecture, dynamics and function of the Endo-1,4-Xylanase II.

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.

Infrared Spectroscopy of Mobility-Selected H+-Gly-Pro-Gly-Gly (GPGG)

NASA Astrophysics Data System (ADS)

Masson, Antoine; Kamrath, Michael Z.; Perez, Marta A. S.; Glover, Matthew S.; Rothlisberger, U.; Clemmer, David E.; Rizzo, Thomas R.

2015-09-01

We report the first results from a new instrument capable of acquiring infrared spectra of mobility-selected ions. This demonstration involves using ion mobility to first separate the protonated peptide Gly-Pro-Gly-Gly (GPGG) into two conformational families with collisional cross-sections of 93.8 and 96.8 Å2. After separation, each family is independently analyzed by acquiring the infrared predissociation spectrum of the H2-tagged molecules. The ion mobility and spectroscopic data combined with density functional theory (DFT) based molecular dynamics simulations confirm the presence of one major conformer per family, which arises from cis/ trans isomerization about the proline residue. We induce isomerization between the two conformers by using collisional activation in the drift tube and monitor the evolution of the ion distribution with ion mobility and infrared spectroscopy. While the cis-proline species is the preferred gas-phase structure, its relative population is smaller than that of the trans-proline species in the initial ion mobility drift distribution. This suggests that a portion of the trans-proline ion population is kinetically trapped as a higher energy conformer and may retain structural elements from solution.

Electrostatic effects on clustering and ion dynamics in ionomer melts

NASA Astrophysics Data System (ADS)

Ma, Boran; Nguyen, Trung; Pryamitsyn, Victor; Olvera de La Cruz, Monica

An understanding of the relationships between ionomer chain morphology, dynamics and counter-ion mobility is a key factor in the design of ion conducting membranes for battery applications. In this study, we investigate the influence of electrostatic coupling between randomly charged copolymers (ionomers) and counter ions on the structural and dynamic features of a model system of ionomer melts. Using coarse-grained molecular dynamics (CGMD) simulations, we found that variations in electrostatic coupling strength (Γ) remarkably affect the formation of ion-counter ion clusters, ion mobility, and polymer dynamics for a range of charged monomer fractions. Specifically, an increase in Γ leads to larger ionic cluster sizes and reduced polymer and ion mobility. Analysis of the distribution of the radius of gyration of the clusters further reveals that the fractal dimension of the ion clusters is nearly independent from Γ for all the cases studied. Finally, at sufficiently high values of Γ, we observed arrested heterogeneous ions mobility, which is correlated with an increase in ion cluster size. These findings provide insight into the role of electrostatics in governing the nanostructures formed by ionomers.

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.

Atmospheric pressure ion focusing in a high-field asymmetric waveform ion mobility spectrometer

NASA Astrophysics Data System (ADS)

Guevremont, Roger; Purves, Randy W.

1999-02-01

The focusing of ions at atmospheric pressure and room temperature in a high-field asymmetric waveform ion mobility spectrometer (FAIMS) has been investigated. FAIMS operates with the application of a high-voltage, high-frequency asymmetric waveform across parallel plates. This establishes conditions wherein an ion migrates towards one of the plates because of a difference in the ion mobility at the low and high electric field conditions during application of the waveform. The migration can be stopped by applying a dc compensation voltage (CV) which serves to create a "balanced" condition wherein the ion experiences no net transverse motion. This method has also been called "transverse field compensation ion mobility spectrometry" and "field ion spectrometry®." If this experiment is conducted using a device with cylindrical geometry, rather than with flat plates, an ion focusing region can exist in the annular space between the two concentric cylinders. Ion trajectory modeling showed that the behavior of the ions in the cylindrical geometry FAIMS analyzer was unlike any previously described atmospheric pressure ion optics system. The ions appeared to be trapped, or focused by being caught between two opposing forces. Requirements for establishing this focus for a given ion were identified: the applied waveform must be asymmetric, the electric field must be sufficiently high that the mobility of the ion deviates from its low-field value during the high-voltage portion of the asymmetric waveform, and finally, the electric field must be nonuniform in space (e.g., cylindrical or spherical geometry). Experimental observations with a prototype FAIMS device, which was designed to measure the radial distribution of ions in the FAIMS analyzer region, have confirmed the results of ion trajectory modeling.

Chemometric studies for the characterization and differentiation of microorganisms using in situ derivatization and thermal desorption ion mobility spectrometry.

PubMed

Ochoa, Mariela L; Harrington, Peter B

2005-02-01

Whole-cell bacteria were characterized and differentiated by thermal desorption ion mobility spectrometry and chemometric modeling. Principal component analysis was used to evaluate the differences in the ion mobility spectra of whole-cell bacteria and the fatty acid methyl esters (FAMEs) generated in situ after derivatization of the bacterial lipids. Alternating least squares served to extract bacterial peaks from the complex ion mobility spectra of intact microorganisms and, therefore, facilitated the characterization of bacterial strains, species, and Gram type. In situ thermal hydrolysis/methylation with tetramethylammonium hydroxide was necessary for the differentiation of Escherichia coli strains, which otherwise could not be distinguished by spectra acquired with the ITEMISER ion mobility spectrometer. The addition of the methylating agent had no effect on Gram-positive bacteria, and therefore, they could not be differentiated by genera. The classification of E. coli strains was possible by analysis of the IMS spectra from the FAMEs generated in situ. By using the fuzzy multivariate rule-building expert system and cross-validation, a correct classification rate of 96% (22 out of 23 spectra) was obtained. Chemometric modeling on bacterial ion mobility spectra coupled to thermal hydrolysis/methylation proved a simple, rapid (2 min/sample), inexpensive, and sensitive technique to characterize and differentiate intact microorganisms. The ITEMISER ion mobility spectrometer could detect as few as 4 x 10(6) cells/sample.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Transfer printing of thermoreversible ion gels for flexible electronics.

PubMed

Lee, Keun Hyung; Zhang, Sipei; Gu, Yuanyan; Lodge, Timothy P; Frisbie, C Daniel

2013-10-09

Thermally assisted transfer printing was employed to pattern thin films of high capacitance ion gels on polyimide, poly(ethylene terephthalate), and SiO2 substrates. The ion gels consisted of 20 wt % block copolymer poly(styrene-b-ethylene oxide-b-styrene and 80 wt % ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)amide. Patterning resolution was on the order of 10 μm. Importantly, ion gels containing the block polymer with short PS end blocks (3.4 kg/mol) could be transfer-printed because of thermoreversible gelation that enabled intimate gel-substrate contact at 100 °C, while gels with long PS blocks (11 kg/mol) were not printable at the same temperature due to poor wetting contact between the gel and substrates. By using printed ion gels as high-capacitance gate insulators, electrolyte-gated thin-film transistors were fabricated that operated at low voltages (<1 V) with high on/off current ratios (∼10(5)). Statistical analysis of carrier mobility, turn-on voltage, and on/off ratio for an array of printed transistors demonstrated the excellent reproducibility of the printing technique. The results show that transfer printing is an attractive route to pattern high-capacitance ion gels for flexible thin-film devices.

Combining Ion Mobility and Cryogenic Spectroscopy for Structural and Analytical Studies of Biomolecular Ions.

PubMed

Kamrath, Michael Z; Rizzo, Thomas R

2018-05-10

Ion mobility spectrometry (IMS) has become a valuable tool in biophysical and bioanalytical chemistry because of its ability to separate and characterize the structure of gas-phase biomolecular ions on the basis of their collisional cross section (CCS). Its importance has grown with the realization that in many cases, biomolecular ions retain important structural characteristics when produced in the gas phase by electrospray ionization (ESI). While a CCS can help distinguish between structures of radically different types, one cannot expect a single number to differentiate similar conformations of a complex molecule. Molecular spectroscopy has also played an increasingly important role for structural characterization of biomolecular ions. Spectroscopic measurements, particularly when performed at cryogenic temperatures, can be extremely sensitive to small changes in a molecule's conformation and provide tight constraints for calculations of biomolecular structures. However, spectra of complex molecules can be heavily congested due to the presence of multiple stable conformations, each of which can have a distinct spectrum. This congestion can inhibit spectral analysis and complicate the extraction of structural information. Even when a single conformation is present, the conformational search process needed to match a measured spectrum with a computed structure can be overwhelming for peptides of more than a few amino acids, for example. We have recently combined ion mobility spectrometry and cryogenic ion spectroscopy (CIS) to characterize the structures of gas-phase biomolecular ions. In this Account, we illustrate how the coupling of IMS and CIS is by nature synergistic. On the one hand, IMS can be used as a conformational filter to reduce spectral congestion that arises from heterogeneous samples, facilitating structural analysis. On the other hand, highly resolved, cryogenic spectra can serve as a selective detector for IMS that can increase the effective resolution and hence the maximum number of distinct species that can be detected. Taken together, spectra and CCS measurements on the same system facilitates structural analysis and strengthens the conclusions that can be drawn from each type of data. After describing different approaches to combining these two techniques in such a way as to simplify the data obtained from each one separately, we present two examples that illustrate the type of insight gained from using spectra and CCS data together for characterizing gas-phase biomolecular ions. In one example, the CCS is used as a constraint for quantum chemical structure calculations of kinetically trapped species, where a lowest-energy criterion is not applicable. In a second example, we use both the CCS and a cryogenic infrared spectrum as a means to distinguish isomeric glycans.

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

Ion-mobility study of two functionalized pentacene structural isomers using a modified electrospray/triple quadrupole mass spectrometer

NASA Astrophysics Data System (ADS)

Prada, Svitlana V.; Bohme, Diethard K.; Baranov, Vladimir I.

2007-03-01

We report ion-mobility measurements with a modified triple quadrupole mass spectrometer fitted with an ion molecule reactor (IMR) designed to investigate ion molecule reactivity in organic mass spectrometry. Functionalized pentacene ions, which are generally unreactive were chosen for study to decouple drift/diffusion effects from reactivity (including clustering). The IMR is equipped with a variable axial electrostatic drift field (ADF) and is able to trap ions. These capabilities were successfully employed in the measurement of ion mobilities in different modes of IMR operation. Theoretical modeling of the drift dynamics and the special localization of the large ion packet was successfully implemented. The contribution of the quadrupole RF field to the drift dynamics also was taken into consideration.

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

PubMed Central

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

2010-01-01

Ion filters based on planar DMS can be integrated with the inlet configuration of most mass spectrometers, and are able to enhance the quality of mass analysis and quantitative accuracy by reducing chemical noise, and by pre-separating ions of similar mass. This paper is the first in a series of three papers describing the optimization of DMS / MS instrumentation. In this paper the important physical parameters of a planar DMS-MS interface including analyzer geometry, analyzer coupling to a mass spectrometer, and transport gas flow control are considered. The goal is to optimize ion transmission and transport efficiency, provide optimal and adjustable resolution, and produce stable operation under conditions of high sample contamination. We discuss the principles of DMS separations and highlight the theoretical underpinnings. The main differences between planar and cylindrical geometries are presented, including a discussion of the advantages and disadvantages of RF ion focusing. In addition, we present a description of optimization of the frequency and amplitude of the DMS fields for resolution and ion transmission, and a discussion of the influence and importance of ion residence time in DMS. We have constructed a mass spectrometer interface for planar geometries that takes advantage of atmospheric pressure gas dynamic principles, rather than ion focusing, to minimize ion losses from diffusion in the analyzer and to maximize total ion transport into the mass spectrometer. A variety of experimental results has been obtained that illustrate the performance of this type of interface, including tests of resistance to high contamination levels, and the separation of stereoisomers. In a subsequent publication the control of the chemical interactions that drive the separation process of a DMS / MS system will be considered. In a third publication we describe novel electronics designed to provide the high voltages asymmetric waveform fields (SV) required for these devices as well as the effects of different waveforms. PMID:21278836

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.

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.

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

PubMed Central

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

2012-01-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ibrahim, Yehia M.; Garimella, Sandilya V. B.; Prost, Spencer A.

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 usedmore » 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.« less

THE DEPENDENCE OF ION AND ELECTRON MOBILITY UPON MOLECULAR STRUCTURE IN DIELECTRIC LIQUIDS (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adamczewski, I.

1961-09-01

The viscosity coefficient of dielectric liquids was found to be dependent upon molecular structure and temperature. From this a general formula for ion and electron mobility was derived. This formula includes the dependence of mobility upon molecular structure and temperature, thus making it possible to give a theoretical explanation of other published experimental results. In addition, the formula can be used to calculate ion mobility for a number of other liquids at various temperatures. (auth)

Using a portable ion mobility spectrometer to screen dietary supplements for sibutramine.

PubMed

Dunn, Jamie D; Gryniewicz-Ruzicka, Connie M; Kauffman, John F; Westenberger, Benjamin J; Buhse, Lucinda F

2011-02-20

In response to recent incidents of undeclared sibutramine, an appetite suppressant found in dietary supplements, we developed a method to detect sibutramine using hand-held ion mobility spectrometers with an analysis time of 15 s. Ion mobility spectrometry is a high-throughput and sensitive technique that has been used for illicit drug, explosive, volatile organic compound and chemical warfare detection. We evaluated a hand-held ion mobility spectrometer as a tool for the analysis of supplement extracts containing sibutramine. The overall instrumental limit of detection of five portable ion mobility spectrometers was 2 ng of sibutramine HCl. When sample extractions containing 30 ng/μl or greater of sibutramine were analyzed, saturation of the ionization chamber of the spectrometer occurred and the instrument required more than three cleaning cycles to remove the drug. Hence, supplement samples suspected of containing sibutramine should be prepared at concentrations of 2-20 ng/μl. To obtain this target concentration range for products containing unknown amounts of sibutramine, we provided a simple sample preparation procedure, allowing the U.S. Food and Drug Administration or other agencies to screen products using the portable ion mobility spectrometer. Published by Elsevier B.V.

Structural Studies of Fucosylated N-Glycans by Ion Mobility Mass Spectrometry and Collision-Induced Fragmentation of Negative Ions

NASA Astrophysics Data System (ADS)

Harvey, David J.; Struwe, Weston B.

2018-05-01

There is considerable potential for the use of ion mobility mass spectrometry in structural glycobiology due in large part to the gas-phase separation attributes not typically observed by orthogonal methods. Here, we evaluate the capability of traveling wave ion mobility combined with negative ion collision-induced dissociation to provide structural information on N-linked glycans containing multiple fucose residues forming the Lewisx and Lewisy epitopes. These epitopes are involved in processes such as cell-cell recognition and are important as cancer biomarkers. Specific information that could be obtained from the intact N-glycans by negative ion CID included the general topology of the glycan such as the presence or absence of a bisecting GlcNAc residue and the branching pattern of the triantennary glycans. Information on the location of the fucose residues was also readily obtainable from ions specific to each antenna. Some isobaric fragment ions produced prior to ion mobility could subsequently be separated and, in some cases, provided additional valuable structural information that was missing from the CID spectra alone.

Structure of Hybrid Polyhedral Oligomeric Silsesquioxane Polymethacrylate Oligomers Using Ion Mobility Mass Spectrometry and Molecular Mechanics

DTIC Science & Technology

2004-12-01

Jones interaction potential is included45 better results are obtained but this method at times overestimates cross-sections in the intermediate 1500 to...utilized to generate sodiated [(PMA)Cp7T8]xNa+ ions, and their collision cross-sections were measured in helium using ion mobility based methods...were measured in helium using ion mobility based methods. Results for x = 1, 2, and 3 were consistent with only one conformer occurring for the Na+1

Ion mobility mass spectrometry for ion recovery and clean-up of MS and MS/MS spectra obtained from low abundance viral samples

PubMed Central

Harvey, David J.; Crispin, Max; Bonomelli, Camille; Scrivens, Jim H.

2016-01-01

Graphical abstract Many samples of complex mixtures of N-glycans released from small amounts of material, such as glycoproteins from viruses, present problems for mass spectrometric analysis because of the presence of contaminating material that is difficult to remove by conventional methods without involving sample loss. This paper describes the use of ion mobility for extraction of glycan profiles from such samples and for obtaining clean CID spectra when targeted m/z values capture additional ions from those of the target compound. N-Glycans were released enzymatically from within SDS-PAGE gels, from the representative glycoprotein, gp120 of the human immunodeficiency virus, and examined by direct infusion electrospray in negative mode followed by ion mobility with a Waters Synapt G2 mass spectrometer. Clean profiles of singly, doubly and triply charged N-glycans were obtained from samples in cases where the raw electrospray spectra displayed only a few glycan ions as the result of low sample concentration or the presence of contamination. Ion mobility also enabled uncontaminated CID spectra to be obtained from glycans when their molecular ions displayed coincidence with ions from fragments or multiply charged ions with similar m/z values. This technique proved to be invaluable for removing extraneous ions from many CID spectra. The presence of such ions often produces spectra that are difficult to interpret. Most CID spectra, even those from abundant glycan constituents, benefited from such clean-up showing that the extra dimension provided by ion mobility was invaluable for studies of this type. PMID:26204966

Comparison of reactant and analyte ions for ⁶³Nickel, corona discharge, and secondary electrospray ionization sources with ion mobility-mass spectrometry.

PubMed

Crawford, C L; Hill, H H

2013-03-30

(63)Nickel radioactive ionization ((63)Ni) is the most common and widely used ion source for ion mobility spectrometry (IMS). Regulatory, financial, and operational concerns with this source have promoted recent development of non-radioactive sources, such as corona discharge ionization (CD), for stand-alone IMS systems. However, there has been no comparison of the negative ion species produced by all three sources in the literature. This study compares the negative reactant and analyte ions produced by three sources on an ion mobility-mass spectrometer: conventional (63)Ni, CD, and secondary electrospray ionization (SESI). Results showed that (63)Ni and SESI produced the same reactant ion species while CD produced only the nitrate monomer and dimer ions. The analyte ions produced by each ion source were the same except for the CD source which produced a different ion species for the explosive RDX than either the (63)Ni or SESI source. Accurate and reproducible reduced mobility (K0) values, including several values reported here for the first time, were found for each explosive with each ion source. Overall, the SESI source most closely reproduced the reactant ion species and analyte ion species profiles for (63)Ni. This source may serve as a non-radioactive, robust, and flexible alternative for (63)Ni. Copyright © 2013 Elsevier B.V. All rights reserved.

Towards Discovery and Targeted Peptide Biomarker Detection Using nanoESI-TIMS-TOF MS

NASA Astrophysics Data System (ADS)

Garabedian, Alyssa; Benigni, Paolo; Ramirez, Cesar E.; Baker, Erin S.; Liu, Tao; Smith, Richard D.; Fernandez-Lima, Francisco

2018-05-01

In the present work, the potential of trapped ion mobility spectrometry coupled to TOF mass spectrometry (TIMS-TOF MS) for discovery and targeted monitoring of peptide biomarkers from human-in-mouse xenograft tumor tissue was evaluated. In particular, a TIMS-MS workflow was developed for the detection and quantification of peptide biomarkers using internal heavy analogs, taking advantage of the high mobility resolution (R = 150-250) prior to mass analysis. Five peptide biomarkers were separated, identified, and quantified using offline nanoESI-TIMS-CID-TOF MS; the results were in good agreement with measurements using a traditional LC-ESI-MS/MS proteomics workflow. The TIMS-TOF MS analysis permitted peptide biomarker detection based on accurate mobility, mass measurements, and high sequence coverage for concentrations in the 10-200 nM range, while simultaneously achieving discovery measurements of not initially targeted peptides as markers from the same proteins and, eventually, other proteins. [Figure not available: see fulltext.

Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces.

PubMed

Frechero, M A; Rocci, M; Sánchez-Santolino, G; Kumar, Amit; Salafranca, J; Schmidt, Rainer; Díaz-Guillén, M R; Durá, O J; Rivera-Calzada, A; Mishra, R; Jesse, Stephen; Pantelides, S T; Kalinin, Sergei V; Varela, M; Pennycook, S J; Santamaria, J; Leon, C

2015-12-17

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.

Paving the way to nanoionics: Atomic origin of barriers for ionic transport through interfaces

DOE PAGES

Frechero, M. A.; Rocci, M.; Sanchez-Santolino, G.; ...

2015-12-17

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together withmore » a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. In conclusion, besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.« less

Measurement of acetates in air using differential ion mobility spectrometer

NASA Astrophysics Data System (ADS)

Szczurek, Andrzej; Maciejewska, Monika; Zajiczek, Żaneta; Maziejuk, Mirosław

2017-11-01

Volatile organic compounds are one of the most important group of air pollutants. Potential health and environmental problems resulting from their emission prompted the requirement for monitoring these species. It motivates development of new measurement techniques which are fast, cost effective, reliable and field deployable. One of novel approaches is ion mobility spectrometry. It dwells on ion separation in electric field, based on differences in ion mobility. Many variants of this method are developed. In this wok, differential ion mobility spectrometry (DMS) was considered in respect of acetate measurements in air. It was demonstrated that DMS offers linear response to methyl, ethyl, propyl and butyl acetate in concentration range from 0.3 ppm to 7 ppm. Positive ions spectrum has to be utilised for this purpose. We showed that fragments of DMS spectrum which secure linearity are compound-specific. The obtained results are promising from the application point of view.

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.

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

PubMed Central

May, Jody C.; McLean, John A.

2013-01-01

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

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

PubMed

May, Jody C; McLean, John A

2003-06-01

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

Ion Mobility Mass Spectrometry for Extracting Spectra of N-Glycans Directly from Incubation Mixtures Following Glycan Release: Application to Glycans from Engineered Glycoforms of Intact, Folded HIV gp120

NASA Astrophysics Data System (ADS)

Harvey, David J.; Sobott, Frank; Crispin, Max; Wrobel, Antoni; Bonomelli, Camille; Vasiljevic, Snezana; Scanlan, Christopher N.; Scarff, Charlotte A.; Thalassinos, Konstantinos; Scrivens, James H.

2011-03-01

The analysis of glycosylation from native biological sources is often frustrated by the low abundances of available material. Here, ion mobility combined with electrospray ionization mass spectrometry have been used to extract the spectra of N-glycans released with PNGase F from a serial titration of recombinantly expressed envelope glycoprotein, gp120, from the human immunodeficiency virus (HIV). Analysis was also performed on gp120 expressed in the α-mannosidase inhibitor, and in a matched mammalian cell line deficient in GlcNAc transferase I. Without ion mobility separation, ESI spectra frequently contained no observable ions from the glycans whereas ions from other compounds such as detergents and residual buffer salts were abundant. After ion mobility separation on a Waters T-wave ion mobility mass spectrometer, the N-glycans fell into a unique region of the ion mobility/ m/z plot allowing their profiles to be extracted with good signal:noise ratios. This method allowed N-glycan profiles to be extracted from crude incubation mixtures with no clean-up even in the presence of surfactants such as NP40. Furthermore, this technique allowed clear profiles to be obtained from sub-microgram amounts of glycoprotein. Glycan profiles were similar to those generated by MALDI-TOF MS although they were more susceptible to double charging and fragmentation. Structural analysis could be accomplished by MS/MS experiments in either positive or negative ion mode but negative ion mode gave the most informative spectra and provided a reliable approach to the analysis of glycans from small amounts of glycoprotein.

Structural characterization of drug-like compounds by ion mobility mass spectrometry: comparison of theoretical and experimentally derived nitrogen collision cross sections.

PubMed

Campuzano, Iain; Bush, Matthew F; Robinson, Carol V; Beaumont, Claire; Richardson, Keith; Kim, Hyungjun; Kim, Hugh I

2012-01-17

We present the use of drug-like molecules as a traveling wave (T-wave) ion mobility (IM) calibration sample set, covering the m/z range of 122.1-609.3, the nitrogen collision cross-section (Ω(N(2))) range of 124.5-254.3 Å(2) and the helium collision cross-section (Ω(He)) range of 63.0-178.8 Å(2). Absolute Ω(N(2)) and Ω(He) values for the drug-like calibrants and two diastereomers were measured using a drift-tube instrument with radio frequency (RF) ion confinement. T-wave drift-times for the protonated diastereomers betamethasone and dexamethasone are reproducibly different. Calibration of these drift-times yields T-wave Ω(N(2)) values of 189.4 and 190.4 Å(2), respectively. These results demonstrate the ability of T-wave IM spectrometry to differentiate diastereomers differing in Ω(N(2)) value by only 1 Å(2), even though the resolution of these IM experiments were ∼40 (Ω/ΔΩ). Demonstrated through density functional theory optimized geometries and ionic electrostatic surface potential analysis, the small but measurable mobility difference between the two diastereomers is mainly due to short-range van der Waals interactions with the neutral buffer gas and not long-range charge-induced dipole interactions. The experimental RF-confining drift-tube and T-wave Ω(N(2)) values were also evaluated using a nitrogen based trajectory method, optimized for T-wave operating temperature and pressures, incorporating additional scaling factors to the Lennard-Jones potentials. Experimental Ω(He) values were also compared to the original and optimized helium based trajectory methods.

Space charge effect in spectrometers of ion mobility increment with planar drift chamber.

PubMed

Elistratov, A A; Sherbakov, L A

2007-01-01

The effect of space charge on the ion beam in a spectrometer of ion mobility increment with the planar drift chamber has been investigated. A model for the drift of ions under a non-uniform high-frequency electric field(1-3) has been developed recently. We have amplified this model by taking space charge effect into account. The ion peak shape taking into consideration the space charge effect is obtained. The output current saturation effect limiting the rise of the ion peak with increasing ion density at the input of the drift chamber of a spectrometer is observed. We show that the saturation effect is caused by the following phenomenon. The maximum possible output ion density exists, depending on the ion type (constant ion mobility, k(0)) and the time of the motion of ions through the drift chamber. At the same time, the ion density does not depend on the parameters of the drift chamber.

Determination of fluspirilene in human plasma by liquid chromatography-tandem mass spectrometry with electrospray ionisation.

PubMed

Swart, K J; Sutherland, F C; van Essen, G H; Hundt, H K; Hundt, A F

1998-12-18

An ultra-sensitive method for the determination of fluspirilene in plasma was established, using high-performance liquid chromatographic separation with tandem mass spectrometric detection. The samples were extracted with hexane/isoamyl alcohol, separated on a Phenomenex Luna C18 5 mu 150 x 2.1 mm column with a mobile phase consisting of methanol-water-acetic acid (600:400:1) at a flow-rate of 0.3 ml/min. Detection was achieved by a Finnigan Matt mass spectrometer (LCQ) at unit resolution in full scan mode scanning the product ion spectrum from m/z 130-500 and monitoring the transition of the protonated molecular ion at m/z 476.2, to the sum of the largest product ions m/z 371, 342 and 274 (MS-MS). Electrospray ionisation was used for ion production. The mean recovery for fluspirilene was 90% with a lower limit of quantification of 21.50 pg/ml using 1 ml plasma for extraction. This is the first chromatographic method described for the determination of fluspirilene in plasma that is accurate and sensitive enough to be used in pharmacokinetic studies.

Ion profiling in an ambient drift tube-ion mobility spectrometer using a high pixel density linear array detector IonCCD.

PubMed

Davila, Stephen J; Hadjar, Omar; Eiceman, Gary A

2013-07-16

A linear pixel-based detector array, the IonCCD, is characterized for use under ambient conditions with thermal (<1 eV) positive ions derived from purified air and a 10 mCi (63)Ni foil. The IonCCD combined with a drift tube-ion mobility spectrometer permitted the direct detection of gas phase ions at atmospheric pressure and confirmed a limit of detection of 3000 ions/pixel/frame established previously in both the keV (1-2 keV) and the hyper-thermal (10-40 eV) regimes. Results demonstrate the "broad-band" application of the IonCCD over 10(5) orders in ion energy and over 10(10) in operating pressure. The Faraday detector of a drift tube for an ion mobility spectrometer was replaced with the IonCCD providing images of ion profiles over the cross-section of the drift tube. Patterns in the ion profiles were developed in the drift tube cross-section by control of electric fields between wires of Bradbury Nielson and Tyndall Powell shutter designs at distances of 1-8 cm from the detector. Results showed that ion beams formed in wire sets, retained their shape with limited mixing by diffusion and Coulombic repulsion. Beam broadening determined as 95 μm/cm for hydrated protons in air with moisture of ~10 ppmv. These findings suggest a value of the IonCCD in further studies of ion motion and diffusion of thermalized ions, enhancing computational results from simulation programs, and in the design or operation of ion mobility spectrometers.

Sensitivity of GRETINA position resolution to hole mobility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasher, V. S.; Cromaz, M.; Merchan, E.

The sensitivity of the position resolution of the gamma-ray tracking array GRETINA to the hole charge-carrier mobility parameter is investigated. The χ 2 results from a fit of averaged signal (“superpulse”) data exhibit a shallow minimum for hole mobilities 15% lower than the currently adopted values. Calibration data on position resolution is analyzed, together with simulations that isolate the hole mobility dependence of signal decomposition from other effects such as electronics cross-talk. Our results effectively exclude hole mobility as a dominant parameter for improving the position resolution for reconstruction of gamma-ray interaction points in GRETINA.

Sensitivity of GRETINA position resolution to hole mobility

DOE PAGES

Prasher, V. S.; Cromaz, M.; Merchan, E.; ...

2017-02-01

The sensitivity of the position resolution of the gamma-ray tracking array GRETINA to the hole charge-carrier mobility parameter is investigated. The χ 2 results from a fit of averaged signal (“superpulse”) data exhibit a shallow minimum for hole mobilities 15% lower than the currently adopted values. Calibration data on position resolution is analyzed, together with simulations that isolate the hole mobility dependence of signal decomposition from other effects such as electronics cross-talk. Our results effectively exclude hole mobility as a dominant parameter for improving the position resolution for reconstruction of gamma-ray interaction points in GRETINA.

High Mobility SiGe/Si Transistor Structures on Sapphire Substrates Using Ion Implantation

NASA Technical Reports Server (NTRS)

Alterovitz, S. A.; Mueller, C. H.; Croke, E. T.

2003-01-01

High mobility n-type SiGe/Si transistor structures have been fabricated on sapphire substrates by ion implanting phosphorus ions into strained 100 Angstrom thick silicon channels for the first time. The strained Si channels were sandwiched between Si(sub 0.7)Ge(sub 0.3) layers, which, in turn, were deposited on Si(sub 0.7)Ge(sub 0.3) virtual substrates and graded SiGe buffer layers. After the molecular beam epitaxy (MBE) film growth process was completed, ion thick silicon channels implantation and post-annealing were used to introduce donors. The phosphorous ions were preferentially located in the Si channel at a peak concentration of approximately 1x10(exp 18)/cu cm. Room temperature electron mobilities exceeding 750 sq cm/V-sec at carrier densities of 1x10(exp 12)/sq cm were measured. Electron concentration appears to be the key factor that determines mobility, with the highest mobility observed for electron densities in the 1 - 2x10(exp 12)/sq cm range.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowell, Kevin L.; Slysz, Gordon W.; Baker, Erin Shammel

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.

Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage

NASA Astrophysics Data System (ADS)

Perera, Sanjaya D.; Archer, Randall B.; Damin, Craig A.; Mendoza-Cruz, Rubén; Rhodes, Christopher P.

2017-03-01

Rechargeable magnesium batteries provide the potential for lower cost and improved safety compared with lithium-ion batteries, however obtaining cathode materials with highly reversible Mg-ion capacities is hindered by the high polarizability of divalent Mg-ions and slow solid-state Mg-ion diffusion. We report that incorporating poly(ethylene oxide) (PEO) between the layers of hydrated vanadium pentoxide (V2O5) xerogels results in significantly improved reversible Mg-ion capacities. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by PEO incorporation. Vibrational spectroscopy supports that the polymer interacts with the V2O5 lattice. The V2O5-PEO nanocomposite exhibited a 5-fold enhancement in Mg-ion capacity, improved stability, and improved rate capabilities compared with V2O5 xerogels. The Mg-ion diffusion coefficient of the nanocomposite was increased compared with that of V2O5 xerogels which is attributed to enhanced Mg-ion mobility due to the shielding interaction of PEO with the V2O5 lattice. This study shows that beyond only interlayer spacing, the nature of interlayer interactions of Mg-ions with V2O5, PEO, and H2O are key factors that affect Mg-ion charge transport and storage in layered materials. The design of layered materials with controlled interlayer interactions provides a new approach to develop improved cathodes for magnesium batteries.

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.

Using different drift gases to change separation factors (alpha) in ion mobility spectrometry

PubMed

Asbury; Hill

2000-02-01

The use of different drift gases to alter separation factors (alpha) in ion mobility spectrometry has been demonstrated. The mobility of a series of low molecular weight compounds and three small peptides was determined in four different drift gases. The drift gases chosen were helium, argon, nitrogen, and carbon dioxide. These drift gases provide a range of polarizabilities and molecular weights. In all instances, the compounds showed the greatest mobility in helium and the lowest mobility in carbon dioxide; however the percentage change of mobility for each compound was different, effectively changing the alpha value. The alpha value changes were primarily due to differences in drift gas polarizability but were also influenced by the mass of the drift gas. In addition, gas-phase ion radii were calculated in each of the different drift gases. These radii were then plotted against drift gas polarizability producing linear plots with r2 values greater than 0.99. The intercept of these plots provides the gas-phase radius of an ion in a nonpolarizing environment, whereas the slope is indicative of the magnitude of the ion's mobility change related to polarizability. It therefore, should be possible to separate any two compounds that have different slopes with the appropriate drift gas.

Peak capacity and peak capacity per unit time in capillary and microchip zone electrophoresis.

PubMed

Foley, Joe P; Blackney, Donna M; Ennis, Erin J

2017-11-10

The origins of the peak capacity concept are described and the important contributions to the development of that concept in chromatography and electrophoresis are reviewed. Whereas numerous quantitative expressions have been reported for one- and two-dimensional separations, most are focused on chromatographic separations and few, if any, quantitative unbiased expressions have been developed for capillary or microchip zone electrophoresis. Making the common assumption that longitudinal diffusion is the predominant source of zone broadening in capillary electrophoresis, analytical expressions for the peak capacity are derived, first in terms of migration time, diffusion coefficient, migration distance, and desired resolution, and then in terms of the remaining underlying fundamental parameters (electric field, electroosmotic and electrophoretic mobilities) that determine the migration time. The latter expressions clearly illustrate the direct square root dependence of peak capacity on electric field and migration distance and the inverse square root dependence on solute diffusion coefficient. Conditions that result in a high peak capacity will result in a low peak capacity per unit time and vice-versa. For a given symmetrical range of relative electrophoretic mobilities for co- and counter-electroosmotic species (cations and anions), the peak capacity increases with the square root of the electric field even as the temporal window narrows considerably, resulting in a significant reduction in analysis time. Over a broad relative electrophoretic mobility interval [-0.9, 0.9], an approximately two-fold greater amount of peak capacity can be generated for counter-electroosmotic species although it takes about five-fold longer to do so, consistent with the well-known bias in migration time and resolving power for co- and counter-electroosmotic species. The optimum lower bound of the relative electrophoretic mobility interval [μ r,Z , μ r,A ] that provides the maximum peak capacity per unit time is a simple function of the upper bound, but its direct application is limited to samples with analytes whose electrophoretic mobilities can be varied independently of electroosmotic flow. For samples containing both co- and counter-electroosmotic ions whose electrophoretic mobilities cannot be easily manipulated, comparable levels of peak capacity and peak capacity per unit time for all ions can be obtained by adjusting the EOF to devote the same amount of time to the separation of each class of ions; this corresponds to μ r,Z =-0.5. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-03-20

The ion mobility behavior of nineteen chemical warfare agents (7 nerve gases, 5 blister agents, 2 lachrymators, 2 blood agents, 3 choking agents) and related compounds including simulants (8 agents) and organic solvents (39) was comparably investigated by the ion mobility spectrometry instrument utilizing weak electric field linear drift tube with corona discharge ionization, ammonia doping, purified inner air drift flow circulation operated at ambient temperature and pressure. Three alkyl methylphosphonofluoridates, tabun, and four organophosphorus simulants gave the intense characteristic positive monomer-derived ion peaks and small dimer-derived ion peaks, and the later ion peaks were increased with the vapor concentrations. VX, RVX and tabun gave both characteristic positive monomer-derived ions and degradation product ions. Nitrogen mustards gave the intense characteristic positive ion peaks, and in addition distinctive negative ion peak appeared from HN3. Mustard gas, lewisite 1, o-chlorobenzylidenemalononitrile and 2-mercaptoethanol gave the characteristic negative ion peaks. Methylphosphonyl difluoride, 2-chloroacetophenone and 1,4-thioxane gave the characteristic ion peaks both in the positive and negative ion mode. 2-Chloroethylethylsulfide and allylisothiocyanate gave weak ion peaks. The marker ion peaks derived from two blood agents and three choking agents were very close to the reactant ion peak in negative ion mode and the respective reduced ion mobility was fluctuated. The reduced ion mobility of the CWA monomer-derived peaks were positively correlated with molecular masses among structurally similar agents such as G-type nerve gases and organophosphorus simulants; V-type nerve gases and nitrogen mustards. The slope values of the calibration plots of the peak heights of the characteristic marker ions versus the vapor concentrations are related to the detection sensitivity, and within chemical warfare agents examined the slope values for sarin, soman, tabun and nitrogen mustards were higher. Some CWA simulants and organic solvents gave the ion peaks eluting at the similar positions of the CWAs, resulting in false positive alarms. Copyright © 2015 Elsevier B.V. All rights reserved.

Detection of explosives using negative ion mobility spectrometry in air based on dopant-assisted thermal ionization.

PubMed

Shahraki, Hassan; Tabrizchi, Mahmoud; Farrokhpor, Hossein

2018-05-26

The ionization source is an essential component of most explosive detectors based on negative ion mobility spectrometry. Conventional ion sources suffer from such inherent limitations as special safety regulations on radioactive sources or generating interfering ions (for non-radioactive sources) such as corona discharge operating in the air. In this study, a new negative ion source is introduced for ion mobility spectrometry that is based on thermal ionization and operates in the air, applicable to explosives detection. Our system consists of a heating filament powered by an isolated power supply connected to negative high voltage. The ionization is assisted by doping chlorinated compounds in the gas phase using chlorinated hydrocarbons in contact with the heating element to yield Cl - reactant ions. Several chlorinated hydrocarbons are evaluated as the reagent chemicals for providing Cl- reactant ions, of which CCl 4 is identified as the best ionizing reagent. The ion source is evaluated by recording the ion mobility spectra of common explosives, including TNT, RDX, and PETN in the air. A detection limit of 150 pg is obtained for TNT. Compared to other ionization sources, the new source is found to be low-cost, simple, and long-lived, making it suited to portable explosives detection devices. Copyright © 2018 Elsevier B.V. All rights reserved.

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

Ion mobilities in diatomic gases: measurement versus prediction with non-specular scattering models.

PubMed

Larriba, Carlos; Hogan, Christopher J

2013-05-16

Ion/electrical mobility measurements of nanoparticles and polyatomic ions are typically linked to particle/ion physical properties through either application of the Stokes-Millikan relationship or comparison to mobilities predicted from polyatomic models, which assume that gas molecules scatter specularly and elastically from rigid structural models. However, there is a discrepancy between these approaches; when specular, elastic scattering models (i.e., elastic-hard-sphere scattering, EHSS) are applied to polyatomic models of nanometer-scale ions with finite-sized impinging gas molecules, predictions are in substantial disagreement with the Stokes-Millikan equation. To rectify this discrepancy, we developed and tested a new approach for mobility calculations using polyatomic models in which non-specular (diffuse) and inelastic gas-molecule scattering is considered. Two distinct semiempirical models of gas-molecule scattering from particle surfaces were considered. In the first, which has been traditionally invoked in the study of aerosol nanoparticles, 91% of collisions are diffuse and thermally accommodating, and 9% are specular and elastic. In the second, all collisions are considered to be diffuse and accommodating, but the average speed of the gas molecules reemitted from a particle surface is 8% lower than the mean thermal speed at the particle temperature. Both scattering models attempt to mimic exchange between translational, vibrational, and rotational modes of energy during collision, as would be expected during collision between a nonmonoatomic gas molecule and a nonfrozen particle surface. The mobility calculation procedure was applied considering both hard-sphere potentials between gas molecules and the atoms within a particle and the long-range ion-induced dipole (polarization) potential. Predictions were compared to previous measurements in air near room temperature of multiply charged poly(ethylene glycol) (PEG) ions, which range in morphology from compact to highly linear, and singly charged tetraalkylammonium cations. It was found that both non-specular, inelastic scattering rules lead to excellent agreement between predictions and experimental mobility measurements (within 5% of each other) and that polarization potentials must be considered to make correct predictions for high-mobility particles/ions. Conversely, traditional specular, elastic scattering models were found to substantially overestimate the mobilities of both types of ions.

Systematic profiling and comparison of the lipidomes from Panax ginseng, P. quinquefolius, and P. notoginseng by ultrahigh performance supercritical fluid chromatography/high-resolution mass spectrometry and ion mobility-derived collision cross section measurement.

PubMed

Shi, Xiaojian; Yang, Wenzhi; Qiu, Shi; Hou, Jinjun; Wu, Wanying; Guo, Dean

2018-05-04

Lipidomics currently is still confronted with challenges from chromatographic separation and lipids identification. Here we report a lipidomics platform by integrating ultrahigh performance supercritical fluid chromatography/quadrupole time-of-flight mass spectrometry (UHPSFC/QTOF-MS) and collision cross section (CCS) measurement using ion mobility spectroscopy/time-of-flight mass spectrometry (IMS/QTOF-MS), aiming to enhance the profiling performance and identification reliability of lipids. The lipidomes extracted from three congeneric Panax species (P. ginseng, P. quinquefolius, and P. notoginseng) by methyl tert-butyl ether are comprehensively profiled and compared by use of this platform. A potent UHPSFC/QTOF-MS approach was developed on a 1.7-μm particles packed Torus 2-PIC column using CH 3 OH (in CO 2 ) as a modifier and CH 3 OH/0.2 mM ammonium acetate as the makeup liquid, enabling well resolution of six lipid subclasses by both positive and negative MS E modes. In contrast to the reversed-phase chromatography, "normal-phase" like elution order and better resolution of polar lipids and some lipid isomers were achieved by UHPSFC separation. Pattern recognition chemometric analysis of 60 batches of Ginseng samples ultimately unveiled 24 lipid markers, of which triacylglycerols were the most important. Aside from the automated MS database searching against HMDB and LIPID MAPS, the application of CCS retrieval or CCS prediction improved lipid identification by reducing the possible hits. In conclusion, this integral platform can significantly improve the chromatographic separation and the reliability of lipids identification in lipidomics studies. It is the first report that systematically compares the lipidomic difference of three reputable Panax species, providing useful information for their quality control in addition to ginsenoside analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Dependence of ion beam current on position of mobile plate tuner in multi-frequencies microwaves electron cyclotron resonance ion source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurisu, Yosuke; Kiriyama, Ryutaro; Takenaka, Tomoya

2012-02-15

We are constructing a tandem-type electron cyclotron resonance ion source (ECRIS). The first stage of this can supply 2.45 GHz and 11-13 GHz microwaves to plasma chamber individually and simultaneously. We optimize the beam current I{sub FC} by the mobile plate tuner. The I{sub FC} is affected by the position of the mobile plate tuner in the chamber as like a circular cavity resonator. We aim to clarify the relation between the I{sub FC} and the ion saturation current in the ECRIS against the position of the mobile plate tuner. We obtained the result that the variation of the plasmamore » density contributes largely to the variation of the I{sub FC} when we change the position of the mobile plate tuner.« less

Engineering of electronic properties of single layer graphene by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Kumar, Sunil; Kumar, Ashish; Tripathi, Ambuj; Tyagi, Chetna; Avasthi, D. K.

2018-04-01

In this work, swift heavy ion irradiation induced effects on the electrical properties of single layer graphene are reported. The modulation in minimum conductivity point in graphene with in-situ electrical measurement during ion irradiation was studied. It is found that the resistance of graphene layer decreases at lower fluences up to 3 × 1011 ions/cm2, which is accompanied by the five-fold increase in electron and hole mobilities. The ion irradiation induced increase in electron and hole mobilities at lower fluence up to 1 × 1011 ions/cm2 is verified by separate Hall measurements on another irradiated graphene sample at the selected fluence. In contrast to the adverse effects of irradiation on the electrical properties of materials, we have found improvement in electrical mobility after irradiation. The increment in mobility is explained by considering the defect annealing in graphene after irradiation at a lower fluence regime. The modification in carrier density after irradiation is also observed. Based on findings of the present work, we suggest ion beam irradiation as a useful tool for tuning of the electrical properties of graphene.

Hydronium ion motion in nanometer 3-methyl-pentane films

NASA Astrophysics Data System (ADS)

Bell, Richard C.; Wu, Kai; Iedema, Martin J.; Cowin, James P.

2007-07-01

An ion soft-landing approach was applied to study the motion of hydronium (D3O+) and cesium (Cs+) ions from 84to104K in glassy 3-methyl-pentane (3MP) films vapor deposited on Pt(111). Both ions were found to have very similar mobilities in 3MP. The span of ion mobilities probed is from ˜10-18to˜10-13m2V-1s-1. Ion transport in these films was studied as a function of film thickness and electric field strength. The drift velocity was found to be linear with applied field below about 2×108V/m and deviated from linearity above this. To a large extent, D3O+ and Cs+ motion in 3MP was well predicted by a simple continuum-based ion mobility model in films from 25 to 20 000 ML thick (including pronounced perturbations 7 ML from both the vacuum and Pt interfaces). The mobility varied with temperature more slowly than predicted by Stokes' law, which may be due to extended inhomogeneous structures in the 3MP near its glass transition at 77K.

Effect of mobile ions on the electric field needed to orient charged diblock copolymer thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dehghan, Ashkan; Shi, An-Chang; Schick, M.

We examine the behavior of lamellar phases of charged/neutral diblock copolymer thin films containing mobile ions in the presence of an external electric field. We employ self-consistent field theory and focus on the aligning effect of the electric field on the lamellae. Of particular interest are the effects of the mobile ions on the critical field, the value required to reorient the lamellae from the parallel configuration favored by the surface interaction to the perpendicular orientation favored by the field. We find that the critical field depends strongly on whether the neutral or charged species is favored by the substrates.more » In the case in which the neutral species is favored, the addition of charges decreases the critical electric field significantly. The effect is greater when the mobile ions are confined to the charged lamellae. In contrast, when the charged species is favored by the substrate, the addition of mobile ions stabilizes the parallel configuration and thus results in an increase in the critical electric field. The presence of ions in the system introduces a new mixed phase in addition to those reported previously.« less

D-region positive and negative ion concentration and mobilities during the February 1979 eclipse

NASA Astrophysics Data System (ADS)

Conley, T. D.; Narcisi, R. S.; Hegblom, E. R.

1983-07-01

Positive and negative ion concentrations and mobilities have been obtained from an analysis of Gerdien condenser measurements on rocket flights, A10.802-1 and A10.802-2, during and after eclipse totality. The aerodynamic instrument calibration and the data analysis techniques are discussed. The measured concentrations on both flights were about 10,000/cu cm in the altitudes range, 45-80 km. These high concentrations at very low altitudes suggest that a relativistic electron precipitation event was occurring during the measurements. The ion concentration measurements along with electron density measurements made by other groups during the eclipse were used to calculate the negative ion/ electron ratio, and the lumped parameter detachment rate. These results are compared with prior measurements during eclipse and solar proton events and code results. The analysis shows that the present negative ion model is incomplete. The reduced mobilities were also determined. The mobility distributions show that the heavy ions of both the positive and negative species dominate from 45 to 70 km. The data reveal more massive ions at higher altitudes than at low altitudes (1000 vs 300 a.m.u.) as well as possible evidence for multiply charged ions below about 60 km.

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.

Pseudo-Random Sequence Modifications for Ion Mobility Orthogonal Time of Flight Mass Spectrometry

PubMed Central

Clowers, Brian H.; Belov, Mikhail E.; Prior, David C.; Danielson, William F.; Ibrahim, Yehia; Smith, Richard D.

2008-01-01

Due to the inherently low duty cycle of ion mobility spectrometry (IMS) experiments that sample from continuous ion sources, a range of experimental advances have been developed to maximize ion utilization efficiency. The use of ion trapping mechanisms prior to the ion mobility drift tube has demonstrated significant gains over discrete sampling from continuous sources; however, these technologies have traditionally relied upon a signal averaging to attain analytically relevant signal-to-noise ratios (SNR). Multiplexed (MP) techniques based upon the Hadamard transform offer an alternative experimental approach by which ion utilization efficiency can be elevated to ∼ 50 %. Recently, our research group demonstrated a unique multiplexed ion mobility time-of-flight (MP-IMS-TOF) approach that incorporates ion trapping and can extend ion utilization efficiency beyond 50 %. However, the spectral reconstruction of the multiplexed signal using this experiment approach requires the use of sample-specific weighing designs. Though general weighing designs have been shown to significantly enhance ion utilization efficiency using this MP technique, such weighing designs cannot be applied to all samples. By modifying both the ion funnel trap and the pseudo random sequence (PRS) used for the MP experiment we have eliminated the need for complex weighing matrices. For both simple and complex mixtures SNR enhancements of up to 13 were routinely observed as compared to the SA-IMS-TOF experiment. In addition, this new class of PRS provides a two fold enhancement in ion throughput compared to the traditional HT-IMS experiment. PMID:18311942

Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

NASA Astrophysics Data System (ADS)

Freitag, K. M.; Walke, P.; Nilges, T.; Kirchhain, H.; Spranger, R. J.; van Wüllen, L.

2018-02-01

Electrospinning is used to fabricate sodium ion conducting fiber membranes composed of polyethylene oxide (PEO), sodium tetrafluoroborate (NaBF4), and succinonitrile (SN) as plasticizer. As compared to conventionally prepared lithium electrolyte membranes with identical composition (PEO:SN:LiBF4), those membranes exhibit conductivities up to 10-4 S cm-1 at 328 K (activation energy ∼36 kJ mol-1, 36:8:1 membrane), which favors such systems as a solid-state electrolyte alternative for batteries. The conduction mechanism is evaluated and the ion mobility are examined. We identified the segment mobility of the polyethylene oxide as the main driving force for the enhanced ion mobility in the membranes. The introduction of SN has only a minor influence on the conductivity and segment mobility at room temperature, but extents the anion and cation mobility to temperatures below ambient. For the 36:8:1 (PEO:SN:NaBF4) membrane we found the highest ion mobility of all membranes under investigation. A comparison of the present sodium membranes with lithium systems of the same composition shows that the overall performance of the sodium systems is comparable. Taking plasticizer-free sodium membranes into account they perform even better than the lithium containing counterparts, and plasticizer-modified membranes show only half an order of magnitude lower conductivities than comparable lithium ones.

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.

Comparison of pulse glow discharge-ion mobility spectrometry and liquid chromatography with tandem mass spectrometry based on multiplug filtration cleanup for the analysis of tricaine mesylate residues in fish and water.

PubMed

Zou, Nan; Chen, Ronghua; Qin, Yuhong; Song, Shuangyu; Tang, Xinglin; Pan, Canping

2016-09-01

Analytical methods based on multiplug filtration cleanup coupled with pulse glow discharge-ion mobility spectrometry and liquid chromatography tandem mass spectrometry were developed for the analysis of tricaine mesylate residue in fish and fish-raising water samples. A silica fiber holder and an appropriate new interface were designed to make the direct introduction of the fiber into the pulse glow discharge-ion mobility spectrometry introduction mechanism. The multiplug filtration cleanup method with adsorption mixtures was optimized for the determination of tricaine mesylate in fish samples. Good linear relationships were obtained by the two methods. For fish samples, limits of detection were 6 and 0.6 μg/kg by ion mobility spectrometry and liquid chromatography with tandem mass spectrometry, respectively. The matrix effect of the established liquid chromatography tandem mass spectrometry method was negligible for fish samples but that of the ion mobility spectrometry method was not. The two methods were compared. The ion mobility spectrometry system could be used a rapid screening tool on site with the advantage of rapidity, simplicity, and portability, and the liquid chromatography tandem mass spectrometry system could be used for validation in laboratory conditions with the advantage of lower limit of detection, stability, and precision. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thin Layer Chromatographic Resolution of Some β-adrenolytics and a β2-Agonist Using Bovine Serum Albumin as Chiral Additive in Stationary Phase.

PubMed

Malik, Poonam; Bhushan, Ravi

2018-01-01

Direct enantiomeric resolution of commonly used five racemic β-adrenolytics, namely, bisoprolol, atenolol, propranolol, salbutamol and carvedilol has been achieved by thin layer chromatography using bovine serum albumin (BSA) as chiral additive in stationary phase. Successful resolution of the enantiomers of all racemic β-adrenolytics was achieved by use of different composition of simple organic solvents having no buffer or inorganic ions. The effect of variation in pH, temperature, amount of BSA as the additive, and composition of mobile phase on resolution was systematically studied. Spots were visualized in iodine vapors. Native enantiomers for each of the five analytes were isolated and identified and their elution order was determined. The limit of detection was found to be 0.7, 1.2, 0.84, 1.6 and 0.9 μg (per spot) for each enantiomer of bisoprolol, atenolol, propranolol, salbutamol and carvedilol, respectively. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Yingying; Triscari, Joseph M.; Tseng, George C.

Data mining was performed on 28 330 unique peptide tandem mass spectra for which sequences were assigned with high confidence. By dividing the spectra into different sets based on structural features and charge states of the corresponding peptides, chemical interactions involved in promoting specific cleavage patterns in gas-phase peptides were characterized. Pairwise fragmentation maps describing cleavages at all Xxx-Zzz residue combinations for b and y ions reveal that the difference in basicity between Arg and Lys results in different dissociation patterns for singly charged Arg- and Lys-ending tryptic peptides. While one dominant protonation form (proton localized) exists for Arg-ending peptides,more » a heterogeneous population of different protonated forms or more facile interconversion of protonated forms (proton partially mobile) exists for Lys-ending peptides. Cleavage C-terminal to acidic residues dominates spectra from peptides that have a localized proton and cleavage N-terminal to Pro dominates those that have a mobile or partially mobile proton. When Pro is absent from peptides that have a mobile or partially mobile proton, cleavage at each peptide bond becomes much more prominent. Whether the above patterns can be found in b ions, y ions, or both depends on the location of the proton holder(s). Enhanced cleavages C-terminal to branched aliphatic residues (Ile, Val, Leu) are observed in both b and y ions from peptides that have a mobile proton, as well as in y ions from peptides that have a partially mobile proton; enhanced cleavages N-terminal to these residues are observed in b ions from peptides that have a partially mobile proton. Statistical tools have been designed to visualize the fragmentation maps and measure the similarity between them. The pairwise cleavage patterns observed expand our knowledge of peptide gas-phase fragmentation behaviors and should be useful in algorithm development that employs improved models to predict fragment ion intensities.« less

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.

The influence of ion content on mobility and ion aggregation in PEO-based single-ion conductors

NASA Astrophysics Data System (ADS)

Caldwell, David; Maranas, Janna

2013-03-01

PEO-based ionomers reduce concentration polarization in solid polymer electrolytes by binding the anion to the polymer backbone. Ionomers have significant ion aggregation compared to PEO/salt systems, and the influence of these aggregates is unclear. When ion transport is coupled to the segmental dynamics of the polymer, aggregation will always reduce ion motion and conductivity. However, the conductivity of PEO ionomers is not sensitive to the degree of aggregation. We present results of molecular dynamics simulations where ion content is systematically varied. We consider the influence of ion content on ion aggregation, polymer mobility and cation motion.

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

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

NASA Technical Reports Server (NTRS)

Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

1995-01-01

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

Effect of Mobile Phone Usage on Nickel Ions Release and pH of Saliva in Patients Undergoing Fixed Orthodontic Treatment.

PubMed

Nanjannawar, Lalita Girish; Girme, Tejashree Suresh; Agrawal, Jiwanasha Manish; Agrawal, Manish Suresh; Fulari, Sangamesh Gurunath; Shetti, Shraddha Subhash; Kagi, Vishwal Ajith

2017-09-01

Hand held mobile phones are presently the most popular means of communication worldwide and have transformed our lives in many aspects. The widespread use of such devices have resulted in growing concerns regarding harmful effects of radiations emitted by them. This study was designed to evaluate the effects of mobile phone usage on nickel ion release as well as pH of saliva in patients with fixed orthodontic appliances. To assess the level of nickel ions in saliva and pH of saliva in mobile phone users undergoing fixed orthodontic treatment using inductively coupled plasma atomic emission spectrometry. A total of 42 healthy patients with fixed orthodontic appliance in mouth for a duration of six to nine months were selected for the study. They were divided into experimental group (n=21) consisting of mobile phone users and control group (n=21) of non mobile phone users. Saliva samples were collected from both the groups and nickel ion levels were measured using inductively coupled plasma-mass spectroscopy. The pH values were also assessed for both groups using pH meter. Unpaired t-test was used for the data analysis. Statistical analysis revealed that though the pH levels were reduced and the nickel ion levels were higher in the experimental group compared to the control group, the results were non significant. Mobile phone usage may affect the pH of saliva and result in increased release of nickel ions in saliva of patients with fixed orthodontic appliances in the oral cavity.

Stability of proton-bound clusters of alkyl alcohols, aldehydes and ketones in Ion Mobility Spectrometry.

PubMed

Jurado-Campos, Natividad; Garrido-Delgado, Rocío; Martínez-Haya, Bruno; Eiceman, Gary A; Arce, Lourdes

2018-08-01

Significant substances in emerging applications of ion mobility spectrometry such as breath analysis for clinical diagnostics and headspace analysis for food purity include low molar mass alcohols, ketones, aldehydes and esters which produce mobility spectra containing protonated monomers and proton-bound dimers. Spectra for all n- alcohols, aldehydes and ketones from carbon number three to eight exhibited protonated monomers and proton-bound dimers with ion drift times of 6.5-13.3 ms at ambient pressure and from 35° to 80 °C in nitrogen. Only n-alcohols from 1-pentanol to 1-octanol produced proton-bound trimers which were sufficiently stable to be observed at these temperatures and drift times of 12.8-16.3 ms. Polar functional groups were protected in compact structures in ab initio models for proton-bound dimers of alcohols, ketones and aldehydes. Only alcohols formed a V-shaped arrangement for proton-bound trimers strengthening ion stability and lifetime. In contrast, models for proton-bound trimers of aldehydes and ketones showed association of the third neutral through weak, non-specific, long-range interactions consistent with ion dissociation in the ion mobility drift tube before arriving at the detector. Collision cross sections derived from reduced mobility coefficients in nitrogen gas atmosphere support the predicted ion structures and approximate degrees of hydration. Copyright © 2018 Elsevier B.V. All rights reserved.

Complex fluids with mobile charge-regulating macro-ions

NASA Astrophysics Data System (ADS)

Markovich, Tomer; Andelman, David; Podgornik, Rudi

2017-10-01

We generalize the concept of charge regulation of ionic solutions, and apply it to complex fluids with mobile macro-ions having internal non-electrostatic degrees of freedom. The suggested framework provides a convenient tool for investigating systems where mobile macro-ions can self-regulate their charge (e.g., proteins). We show that even within a simplified charge-regulation model, the charge dissociation equilibrium results in different and notable properties. Consequences of the charge regulation include a positional dependence of the effective charge of the macro-ions, a non-monotonic dependence of the effective Debye screening length on the concentration of the monovalent salt, a modification of the electric double-layer structure, and buffering by the macro-ions of the background electrolyte.

BIOCHEMISTRY OF MOBILE ZINC AND NITRIC OXIDE REVEALED BY FLUORESCENT SENSORS

PubMed Central

Pluth, Michael D.; Tomat, Elisa; Lippard, Stephen J.

2010-01-01

Biologically mobile zinc and nitric oxide (NO) are two prominent examples of inorganic compounds involved in numerous signaling pathways in living systems. In the past decade, a synergy of regulation, signaling, and translocation of these two species has emerged in several areas of human physiology, providing additional incentive for developing adequate detection systems for Zn(II) ions and NO in biological specimens. Fluorescent probes for both of these bioinorganic analytes provide excellent tools for their detection, with high spatial and temporal resolution. We review the most widely used fluorescent sensors for biological zinc and nitric oxide, together with promising new developments and unmet needs of contemporary Zn(II) and NO biological imaging. The interplay between zinc and nitric oxide in the nervous, cardiovascular, and immune systems is highlighted to illustrate the contributions of selective fluorescent probes to the study of these two important bioinorganic analytes. PMID:21675918

Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish.

PubMed

Cheng, Heyong; Chen, Xiaopan; Shen, Lihuan; Wang, Yuanchao; Xu, Zigang; Liu, Jinhua

2018-01-05

Most of analytical community is focused on reversed phase high performance liquid chromatography (RP-HPLC) for mercury speciation by employing mobile phases comprising of high salts and moderate amounts of organic solvents. This study aims at rapid mercury speciation analysis by ion-pairing RP-HPLC with inductively coupled plasma mass spectrometry (ICP-MS) detection only using low salts for the sake of green analytical chemistry. Two ion-pairing HPLC methods were developed on individual usage of positively and negatively charged ion-pairing reagents (tetrabutylammonium hydroxide -TBAH and sodium dodecylbenzene sulfonate -SDBS), where sodium 3-mercapto-1-propysulfonate (MPS) and l-cysteine (Cys) were individually added in mobile phases to transform mercury species into negative and positive Hg-complexes for good resolution. Addition of phenylalanine was also utilized for rapid baseline separation in combination of short C 18 guard columns. Optimum mobile phases of 2.0mM SDBS+2.0mM Cys+1.0mM Phe (pH 3.0) and 4.0mM TBAH+2.0mM MPS+2.0mM Phe (pH 6.0) both achieved baseline separation of inorganic mercury (Hg 2+ ), methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) on two consecutive 12.5-mm C 18 columns. The former mobile phase was selected for mercury speciation in freshwater fish because of short separation time (3.0min). Detection limits of 0.015 for Hg 2+ , 0.014 for MeHg, 0.028 for EtHg and 0.042μgL -1 for PhHg were obtained along with satisfactory precisions of peak height and area (1.0-2.8% for 5.0μgL -1 Hg-mixture standard). Good accordance of determined values of MeHg and total mercury in certified reference materials of fish tissue (GBW 10029) and tuna fish (BCR-463) with certified values as well as good recoveries (91-106%) proved good accuracy of the proposed method. An example application to freshwater fish indicated its potential in routine analysis, where MeHg was presented at 3.7-20.3μgkg -1 as the dominate species. Copyright © 2017 Elsevier B.V. All rights reserved.

High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

PubMed

Swearingen, Kristian E; Moritz, Robert L

2012-10-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

49 CFR 175.10 - Exceptions for passengers, crewmembers, and air operators.

Code of Federal Regulations, 2012 CFR

2012-10-01

... words “Battery, wet, with wheelchair.” (17) A lithium ion battery-powered wheelchair or other mobility aid as follows: (i) A wheelchair or other mobility aid equipped with a lithium ion battery, when carried as checked baggage, provided— (A) The lithium ion battery must be of a type that successfully...

49 CFR 175.10 - Exceptions for passengers, crewmembers, and air operators.

Code of Federal Regulations, 2011 CFR

2011-10-01

... words “Battery, wet, with wheelchair.” (17) A lithium ion battery-powered wheelchair or other mobility aid as follows: (i) A wheelchair or other mobility aid equipped with a lithium ion battery, when carried as checked baggage, provided— (A) The lithium ion battery must be of a type that successfully...

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

PubMed

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

2014-04-07

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

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

Pb2+ ions mobility perturbation by iron particles during electrokinetic remediation of contaminated soil.

PubMed

Zulfiqar, Waqas; Iqbal, Muhammad Asad; Butt, Mehwish Khalid

2017-02-01

Electrokinetic (EK) remediation is one of the most useful approaches for de-contamination of soils. However, it is unclear that how and when the electrokinetic remediation gives advantages over other remediation techniques in soil. This study was designed to find the influence of Fe 2+ particles on the mobility of Pb 2+ ions, during electrokinetic remediation, in soil contaminated purposely by lead nitrate Pb(NO 3 ) 2 . Two types of electrokinetic experiments were performed, by using iron and graphite electrodes. The Fe 2+ ions from the iron electrodes, produced due to acidic environment in anode compartment, affected the mobility of lead particles by precipitating as Fe(OH) 2 . Fe 2+ ions enhance the adsorption of lead ions in soil. The results show Fe 2+ ions of lower ionic conductivity decreased mobility of other particles in soil. Electrokinetic remediation for up to 120 h with iron electrodes is shown to be less effective for removal of lead. In contrast, graphite electrodes were 15 times more effective in lead removal from soil. Copyright © 2016 Elsevier Ltd. All rights reserved.

A new Ion Mobility Spectrometer

NASA Astrophysics Data System (ADS)

Butler, M. A.

1998-03-01

A new ion mobility spectrometer (IMS) concept has been demonstrated that traps ions in a potential well and then moves the well down a tube to a detector. The charge remaining in the well is measured as a function of well velocity or electric field that the ion experiences; thus separating the ions by mobility. The potential wave is generated and propagated down the tube by a series of ring electrodes along the tube under real-time computer control via an array of DACs. The operating characteristics of this device have been explored including the effects of ion "lifetime," well shape, and well velocity. The ion "lifetime" results from a radial field at the bottom of the potential well that pushes the ions toward the tube wall. This work was supported by the United States Department of Energy under Contract DE-AC04-94AL85000. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy.

Collision Cross Sections and Ion Mobility Separation of Fragment Ions from Complex N-Glycans.

PubMed

Harvey, David J; Watanabe, Yasunori; Allen, Joel D; Rudd, Pauline; Pagel, Kevin; Crispin, Max; Struwe, Weston B

2018-06-01

Ion mobility mass spectrometry (IM-MS) holds great potential for structural glycobiology, in particular in its ability to resolve glycan isomers. Generally, IM-MS has largely been applied to intact glycoconjugate ions with reports focusing on the separation of different adduct types. Here, we explore IM separation and report the collision cross section (CCS) of complex type N-glycans and their fragments in negative ion mode following collision-induced dissociation (CID). CCSs of isomeric fragment ions were found, in some cases, to reveal structural details that were not present in CID spectra themselves. Many fragment ions were confirmed as possessing multiple structure, details of which could be obtained by comparing their drift time profiles to different glycans. By using fragmentation both before and after mobility separation, information was gathered on the fragmentation pathways producing some of the ions. These results help demonstrate the utility of IM and will contribute to the growing use of IM-MS for glycomics. Graphical Abstract ᅟ.

Collision Cross Sections and Ion Mobility Separation of Fragment Ions from Complex N-Glycans

NASA Astrophysics Data System (ADS)

Harvey, David J.; Watanabe, Yasunori; Allen, Joel D.; Rudd, Pauline; Pagel, Kevin; Crispin, Max; Struwe, Weston B.

2018-04-01

Ion mobility mass spectrometry (IM-MS) holds great potential for structural glycobiology, in particular in its ability to resolve glycan isomers. Generally, IM-MS has largely been applied to intact glycoconjugate ions with reports focusing on the separation of different adduct types. Here, we explore IM separation and report the collision cross section (CCS) of complex type N-glycans and their fragments in negative ion mode following collision-induced dissociation (CID). CCSs of isomeric fragment ions were found, in some cases, to reveal structural details that were not present in CID spectra themselves. Many fragment ions were confirmed as possessing multiple structure, details of which could be obtained by comparing their drift time profiles to different glycans. By using fragmentation both before and after mobility separation, information was gathered on the fragmentation pathways producing some of the ions. These results help demonstrate the utility of IM and will contribute to the growing use of IM-MS for glycomics. [Figure not available: see fulltext.

Determination and identification of malathion, ethion and dichlorovos using ion mobility spectrometry.

PubMed

Jafari, Mohammad T

2006-07-15

Positive ion mobility spectra of different organophosphorus pesticides such as malathion (s-(1,2-dicarb-ethoxyethyl) o,o-dimethyl dithiophosphate), ethion (o,o,o',o'-tetraethyl s,s'-methylene bis(phosphorodithioate)) and dichlorovos (2,2-dichlorovinyl dimethyl phosphate) have been studied in air at ambient pressure using ion mobility spectrometry method with (63)Ni ionization source. The limits of quantification (LOQs) were 1.0 x 10(-9), 1.0 x 10(-9) and 5.0 x 10(-9)g for malathion, ethion and dichlorovos, respectively. The working range of these compounds was about three orders of magnitude and the relative standard deviation (R.S.D.) of repeatability at the 5 microg ml(-1) level were all below 15%. Furthermore, in this study, the influences of IMS cell temperature on the ion mobility spectra of these compounds were investigated.

Solvent-mediated nonelectrostatic ion-ion interactions predicting anomalies in electrophoresis.

PubMed

Goswami, Prakash; Dhar, Jayabrata; Ghosh, Uddipta; Chakraborty, Suman

2017-03-01

We study the effects of solvent-mediated nonelectrostatic ion-ion interactions on electrophoretic mobility of a charged spherical particle. To this end, we consider the case of low surface electrostatic potential resulting in the linearization of the governing equations, which enables us to deduce a closed-form analytical solution to the electrophoretic mobility. We subsequently compare our results to the standard model using Henry's approach and report the changes brought about by the nonelectrostatic potential. The classical approach to determine the electrophoretic mobility underpredicts the particle velocity when compared with experiments. We show that this issue can be resolved by taking into account nonelectrostatic interactions. Our analysis further reveals the phenomenon of electrophoretic mobility reversal that has been experimentally observed in numerous previous studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wireless Content Repurposing Architecture for DC Command and Control

DTIC Science & Technology

2003-09-01

was a natural choice as our primary mobile device for the DC investigators. 28 The Clie uses a Lithium Ion battery , which is the longest...projects the screen of the PDA on a head-mounted display maybe used. Battery life of PDAs is relatively short. This means many Lithium Ion...Mobile Devices Mobile devices such as PDAs, mobile phones, and Smartphones have become tightly interwoven as an important part of everyday lives

Identity confirmation of drugs and explosives in ion mobility spectrometry using a secondary drift gas.

PubMed

Kanu, Abu B; Hill, Herbert H

2007-10-15

This work demonstrated the potential of using a secondary drift gas of differing polarizability from the primary drift gas for confirmation of a positive response for drugs or explosives by ion mobility spectrometry (IMS). The gas phase mobilities of response ions for selected drugs and explosives were measured in four drift gases. The drift gases chosen for this study were air, nitrogen, carbon dioxide and nitrous oxide providing a range of polarizability and molecular weights. Four other drift gases (helium, neon, argon and sulfur hexafluoride) were also investigated but design limitations of the commercial instrument prevented their use for this application. When ion mobility was plotted against drift gas polarizability, the resulting slopes were often unique for individual ions, indicating that selectivity factors between any two analytes varied with the choice of drift gas. In some cases, drugs like THC and heroin, which are unresolved in air or nitrogen, were well resolved in carbon dioxide or nitrous oxide.

Mechanisms Underlying Ionic Mobilities in Nanocomposite Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Hanson, Benjamin; Pryamitsyn, Victor

2014-03-01

Recently, a number of experiments have demonstrated that addition of ceramics with nanoscale dimensions can lead to substantial improvements in the low temperature conductivity of the polymeric materials. However, the origin of such behaviors, and more generally, the manner by which nanoscale fillers impact the ion mobilities remain unresolved. In this communication, we report the results of atomistic molecular dynamics simulations which used multibody polarizable force-fields to study lithium ion diffusivities in an amorphous poly(ethylene-oxide) (PEO) melt containing well-dispersed TiO2 nanoparticles. We observed that the lithium ion diffusivities decrease with increased particle loading. Our analysis suggests that the ion mobilities are correlated to the nanoparticle-induced changes in the polymer segmental dynamics. Interestingly, the changes in polymer segmental dynamics were seen to be related to the nanoparticle's influence on the polymer conformational features. Overall, our results indicate that addition of nanoparticle fillers modify polymer conformations and the polymer segmental dynamics, and thereby influence the ion mobilities of polymer electrolytes.

Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry

USGS Publications Warehouse

Leenheer, J.A.; Rostad, C.E.; Gates, Paul M.; Furlong, E.T.; Ferrer, I.

2001-01-01

Molecular weight distributions of fulvic acid from the Suwannee River, Georgia, were investigated by electrospray ionization/quadrupole mass spectrometry (ESI/QMS), and fragmentation pathways of specific fulvic acid masses were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/MS). ESI/QMS studies of the free acid form of low molecular weight poly(carboxylic acid) standards in 75% methanol/25% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can be used for molecular weight determinations. However, experiments with poly(acrylic acid) mixtures and specific high molecular weight standards found multiply charged negative ions that gave a low bias to molecular mass distributions. The number of negative charges on a molecule is dependent on the distance between charges. ESI/MST/MS of model compounds found characteristic water loss from alcohol dehydration and anhydride formation, as well as CO2 loss from decarboxylation, and CO loss from ester structures. Application of these fragmentation pathways to specific masses of fulvic acid isolated and fragmented by ESI/MST/MS is indicative of specific structures that can serve as a basis for future structural confirmation after these hypothesized structures are synthesized.

Sparse super-resolution reconstructions of video from mobile devices in digital TV broadcast applications

NASA Astrophysics Data System (ADS)

Boon, Choong S.; Guleryuz, Onur G.; Kawahara, Toshiro; Suzuki, Yoshinori

2006-08-01

We consider the mobile service scenario where video programming is broadcast to low-resolution wireless terminals. In such a scenario, broadcasters utilize simultaneous data services and bi-directional communications capabilities of the terminals in order to offer substantially enriched viewing experiences to users by allowing user participation and user tuned content. While users immediately benefit from this service when using their phones in mobile environments, the service is less appealing in stationary environments where a regular television provides competing programming at much higher display resolutions. We propose a fast super-resolution technique that allows the mobile terminals to show a much enhanced version of the broadcast video on nearby high-resolution devices, extending the appeal and usefulness of the broadcast service. The proposed single frame super-resolution algorithm uses recent sparse recovery results to provide high quality and high-resolution video reconstructions based solely on individual decoded frames provided by the low-resolution broadcast.

Graphene Nanoribbons Fabricated by Helium Ion microscope

NASA Astrophysics Data System (ADS)

Pickard, D.; Oezyilmaz, B.; Thong, J.; Loh, K. P.; Viswanathan, V.; Zhongkai, A.; Mathew, S.; Kundu, T.; Park, C.; Yi, Z.; Xu, X.; Zhang, K.; Tat, T. C.; Wang, H.; Venkatesan, T.; Botton, G.; Couillard, M.

2010-03-01

Graphene, a monolayer graphitic lattice of carbon atoms has tremendous promise for a variety of applications on account of the zero mass of electrons, high mobility and the sensitivity of transport to perturbations at the interface. Patterning graphene is an obvious challenge and mesoscopic devices based on graphene require high spatial resolution patterning that will induce as little damage as possible. We use a helium ion microscope with its 0.4nm spot size beam to directly write patterns on free standing graphene films. TEM images of the patterns reveal holes as small as 4 nm and ribbons with line widths as narrow as 3 nm. The images show recovery of the graphene lattice at a distance of about a nm from the patterned edge. The linewidths of the ribbon can be varied considerably in a controllable fashion over ribbon lengths of the order of microns. . .

Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

PubMed

Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

2016-08-17

We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions.

Contribution of Li-ion batteries to the environmental impact of electric vehicles.

PubMed

Notter, Dominic A; Gauch, Marcel; Widmer, Rolf; Wäger, Patrick; Stamp, Anna; Zah, Rainer; Althaus, Hans-Jörg

2010-09-01

Battery-powered electric cars (BEVs) play a key role in future mobility scenarios. However, little is known about the environmental impacts of the production, use and disposal of the lithium ion (Li-ion) battery. This makes it difficult to compare the environmental impacts of BEVs with those of internal combustion engine cars (ICEVs). Consequently, a detailed lifecycle inventory of a Li-ion battery and a rough LCA of BEV based mobility were compiled. The study shows that the environmental burdens of mobility are dominated by the operation phase regardless of whether a gasoline-fueled ICEV or a European electricity fueled BEV is used. The share of the total environmental impact of E-mobility caused by the battery (measured in Ecoindicator 99 points) is 15%. The impact caused by the extraction of lithium for the components of the Li-ion battery is less than 2.3% (Ecoindicator 99 points). The major contributor to the environmental burden caused by the battery is the supply of copper and aluminum for the production of the anode and the cathode, plus the required cables or the battery management system. This study provides a sound basis for more detailed environmental assessments of battery based E-mobility.

Effect of Mobile Phone Usage on Nickel Ions Release and pH of Saliva in Patients Undergoing Fixed Orthodontic Treatment

PubMed Central

Girme, Tejashree Suresh; Agrawal, Jiwanasha Manish; Agrawal, Manish Suresh; Fulari, Sangamesh Gurunath; Shetti, Shraddha Subhash; Kagi, Vishwal Ajith

2017-01-01

Introduction Hand held mobile phones are presently the most popular means of communication worldwide and have transformed our lives in many aspects. The widespread use of such devices have resulted in growing concerns regarding harmful effects of radiations emitted by them. This study was designed to evaluate the effects of mobile phone usage on nickel ion release as well as pH of saliva in patients with fixed orthodontic appliances. Aim To assess the level of nickel ions in saliva and pH of saliva in mobile phone users undergoing fixed orthodontic treatment using inductively coupled plasma atomic emission spectrometry. Materials and Methods A total of 42 healthy patients with fixed orthodontic appliance in mouth for a duration of six to nine months were selected for the study. They were divided into experimental group (n=21) consisting of mobile phone users and control group (n=21) of non mobile phone users. Saliva samples were collected from both the groups and nickel ion levels were measured using inductively coupled plasma-mass spectroscopy. The pH values were also assessed for both groups using pH meter. Unpaired t-test was used for the data analysis. Results Statistical analysis revealed that though the pH levels were reduced and the nickel ion levels were higher in the experimental group compared to the control group, the results were non significant. Conclusion Mobile phone usage may affect the pH of saliva and result in increased release of nickel ions in saliva of patients with fixed orthodontic appliances in the oral cavity. PMID:29207841

Temperature dependent mobility measurements of alkali earth ions in superfluid helium

NASA Astrophysics Data System (ADS)

Putlitz, Gisbert Zu; Baumann, I.; Foerste, M.; Jungmann, K.; Riediger, O.; Tabbert, B.; Wiebe, J.; Zühlke, C.

1998-05-01

Mobility measurements of impurity ions in superfluid helium are reported. Alkali earth ions were produced with a laser sputtering technique and were drawn inside the liquid by an electric field. The experiments were carried out in the temperature region from 1.27 up to 1.66 K. The temperature dependence of the mobility of Be^+-ions (measured here for the first time) differs from that of the other alkali earth ions Mg^+, Ca^+, Sr^+ and Ba^+, but behaves similar to that of He^+ (M. Foerste, H. Günther, O. Riediger, J. Wiebe, G. zu Putlitz, Z. Phys. B) 104, 317 (1997). Theories of Atkins (A. Atkins, Phys. Rev.) 116, 1339 (1959) and Cole (M.W. Cole, R.A. Bachmann Phys. Rev. B) 15, 1388 (1977) predict a different defect structure for He^+ and the alkali earth ions: the helium ion is assumed to form a snowball like structure whereas for the alkali earth ions a bubble structure is assumed. If the temperature dependence is a characteristic feature for the different structures, then it seems likely that the Be^+ ion builds a snowball like structure.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

IMS - MS Data Extractor

DOE Office of Scientific and Technical Information (OSTI.GOV)

2015-10-20

An automated drift time extraction and computed associated collision cross section software tool for small molecule analysis with ion mobility spectrometry-mass spectrometry (IMS-MS). The software automatically extracts drift times and computes associated collision cross sections for small molecules analyzed using ion mobility spectrometry-mass spectrometry (IMS-MS) based on a target list of expected ions provided by the user.

High Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) for Mass Spectrometry-Based Proteomics

PubMed Central

Swearingen, Kristian E.; Moritz, Robert L.

2013-01-01

SUMMARY High field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, we review recent developments in LC-FAIMS-MS and its application to MS-based proteomics. PMID:23194268

Experimental ion mobility measurements in Xe-CO2

NASA Astrophysics Data System (ADS)

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

2017-06-01

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-CO2 mixtures are presented. The results for this mixture show the presence of only one peak for all gas ratios of Xe-CO2, low reduced electric fields, E/N, 10-25 Td (2.4-6.1 kV·cm-1·bar-1), low pressures 6-8 Torr (8-10.6 mbar), at room temperature.

Assessment of Dimeric Metal-Glycan Adducts via Isotopic Labeling and Ion Mobility-Mass Spectrometry.

PubMed

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

2018-05-25

Adduction of multivalent metal ions to glycans has been shown in recent years to produce altered tandem mass spectra with collision-induced dissociation, electron transfer techniques, and photon-based fragmentation approaches. However, these approaches assume the presence of a well-characterized precursor ion population and do not fully account for the possibility of multimeric species for select glycan-metal complexes. With the use of ion mobility separations prior to mass analysis, doubly charged dimers are not necessarily problematic for tandem MS experiments given that monomer and dimer drift times are sufficiently different. However, multistage mass spectrometric experiments performed on glycans adducted to multivalent metals without mobility separation can yield chimeric fragmentation spectra that are essentially a superposition of the fragments from both the monomeric and dimeric adducts. For homodimeric adducts, where the dimer contains two of the same glycan species, this is less of a concern but if heterodimers can form, there exists the potential for erroneous and misleading fragment ions to appear if a heterodimer containing two different isomers is fragmented along with a targeted monomer. We present an assessment of heterodimer formation between a series of six tetrasaccharides, of which three are isomers, adducted with cobalt(II) and a monodeuterated tetrasaccharide. Using ion mobility separations prior to single-stage and tandem mass analysis, the data shown demonstrate that heterodimeric species can indeed form, and that ion mobility separations are highly necessary prior to using tandem techniques on metal-glycan adducts. Graphical Abstract ᅟ.

Determination of ion mobility in EHD flow zone of plasma generator

NASA Astrophysics Data System (ADS)

Sumariyah, Kusminarto, Hermanto, Arief; Nuswantoro, Pekik

2015-12-01

Determination has been carried out for ion mobility in EHD flow zone generated using a pin-concentric multiple ring electrodes and a pin-single ring electrode used as a comparator. The pin needle was made from stainless steel with a tip diameter of 0.18 mm. The concentris multiple ring electrode in form three/two concentric ring electrodes which made of metal material connected to each other. Each ring of three concentric ring electrode has a diameter of 24 mm, 16 mm and 8 mm. And each ring of two concentric ring electrode has a diameter of 24 mm and 16 mm. Single ring electrode has a diameter24 mm. The all ring has same of width and thickness were 2 mm and 3 mm. EHD was generated by using a DC high voltage of 10 kV. Pin functional as an active electrode of corona discharge while the all ring electrodes acted as ions collector and passive electrodes. The experimental results show that the ion current is proportional to V2 according to calculations by Chouelo for hyperbolic-field approach. Ion mobility obtained from the quadratic polynomial fitting of experimental data were current and voltage as well as Choelo formulation. The results showed that the mobility of ions in the EHD flow zones utilizing pin-consentric multiple ring electrode larger than utilizing pin-single ring electrode. Pin-three Consentic ring electrode has the largest of ion mobility

Assessment of Dimeric Metal-Glycan Adducts via Isotopic Labeling and Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

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

2018-05-01

Adduction of multivalent metal ions to glycans has been shown in recent years to produce altered tandem mass spectra with collision-induced dissociation, electron transfer techniques, and photon-based fragmentation approaches. However, these approaches assume the presence of a well-characterized precursor ion population and do not fully account for the possibility of multimeric species for select glycan-metal complexes. With the use of ion mobility separations prior to mass analysis, doubly charged dimers are not necessarily problematic for tandem MS experiments given that monomer and dimer drift times are sufficiently different. However, multistage mass spectrometric experiments performed on glycans adducted to multivalent metals without mobility separation can yield chimeric fragmentation spectra that are essentially a superposition of the fragments from both the monomeric and dimeric adducts. For homodimeric adducts, where the dimer contains two of the same glycan species, this is less of a concern but if heterodimers can form, there exists the potential for erroneous and misleading fragment ions to appear if a heterodimer containing two different isomers is fragmented along with a targeted monomer. We present an assessment of heterodimer formation between a series of six tetrasaccharides, of which three are isomers, adducted with cobalt(II) and a monodeuterated tetrasaccharide. Using ion mobility separations prior to single-stage and tandem mass analysis, the data shown demonstrate that heterodimeric species can indeed form, and that ion mobility separations are highly necessary prior to using tandem techniques on metal-glycan adducts.

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

Grouping of Petroleum Substances as Example UVCBs by Ion Mobility-Mass Spectrometry to Enable Chemical Composition-Based Read-Across.

PubMed

Grimm, Fabian A; Russell, William K; Luo, Yu-Syuan; Iwata, Yasuhiro; Chiu, Weihsueh A; Roy, Tim; Boogaard, Peter J; Ketelslegers, Hans B; Rusyn, Ivan

2017-06-20

Substances of Unknown or Variable composition, Complex reaction products, and Biological materials (UVCBs), including many refined petroleum products, present a major challenge in regulatory submissions under the EU Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) and US High Production Volume regulatory regimes. The inherent complexity of these substances, as well as variability in composition obfuscates detailed chemical characterization of each individual substance and their grouping for human and environmental health evaluation through read-across. In this study, we applied ion mobility mass spectrometry in conjunction with cheminformatics-based data integration and visualization to derive substance-specific signatures based on the distribution and abundance of various heteroatom classes. We used petroleum substances from four petroleum substance manufacturing streams and evaluated their chemical composition similarity based on high-dimensional substance-specific quantitative parameters including m/z distribution, drift time, carbon number range, and associated double bond equivalents and hydrogen-to-carbon ratios. Data integration and visualization revealed group-specific similarities for petroleum substances. Observed differences within a product group were indicative of batch- or manufacturer-dependent variation. We demonstrate how high-resolution analytical chemistry approaches can be used effectively to support categorization of UVCBs based on their heteroatom composition and how such data can be used in regulatory decision-making.

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.

Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

PubMed

Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

2011-12-28

We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase measurements to be correlated to biomolecular structures in solution, low charge state ions should be analyzed. Further, to determine if different solution conditions give rise to ions of different structure, ions of similar charge state should be compared. Non-denatured protein ion densities are found to be in excellent agreement with non-denatured protein ion densities inferred from prior DMA and drift tube measurements made without charge reduction (all ions with densities in the 0.85-1.10 g cm(-3) range), showing that these ions are not strongly influenced by Coulombic stretching nor by analysis method.

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

Davidson, Jacob D.; Goulbourne, N. C.

2011-01-01

Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an optimal electromechanical conversion efficiency for bending actuation is achieved by using an ionic liquid where only a relatively small fraction of the ionic liquid ions exist as free ions. Conversely, if it is desired to increase the overall amount of charge transferred, an ionic liquid with a large fraction of free ions should be used. These theoretical considerations are found to be in good qualitative agreement with recent experimental results.

Ion spectrometric detection technologies for ultra-traces of explosives: a review.

PubMed

Mäkinen, Marko; Nousiainen, Marjaana; Sillanpää, Mika

2011-01-01

In recent years, explosive materials have been widely employed for various military applications and civilian conflicts; their use for hostile purposes has increased considerably. The detection of different kind of explosive agents has become crucially important for protection of human lives, infrastructures, and properties. Moreover, both the environmental aspects such as the risk of soil and water contamination and health risks related to the release of explosive particles need to be taken into account. For these reasons, there is a growing need to develop analyzing methods which are faster and more sensitive for detecting explosives. The detection techniques of the explosive materials should ideally serve fast real-time analysis in high accuracy and resolution from a minimal quantity of explosive without involving complicated sample preparation. The performance of the in-field analysis of extremely hazardous material has to be user-friendly and safe for operators. The two closely related ion spectrometric methods used in explosive analyses include mass spectrometry (MS) and ion mobility spectrometry (IMS). The four requirements-speed, selectivity, sensitivity, and sampling-are fulfilled with both of these methods. Copyright © 2011 Wiley Periodicals, Inc.

Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 3. Relating Solution-Phase to Gas-Phase Structures.

PubMed

Kondalaji, Samaneh Ghassabi; Khakinejad, Mahdiar; Valentine, Stephen J

2018-06-01

Molecular dynamics (MD) simulations have been utilized to study peptide ion conformer establishment during the electrospray process. An explicit water model is used for nanodroplets containing a model peptide and hydronium ions. Simulations are conducted at 300 K for two different peptide ion charge configurations and for droplets containing varying numbers of hydronium ions. For all conditions, modeling has been performed until production of the gas-phase ions and the resultant conformers have been compared to proposed gas-phase structures. The latter species were obtained from previous studies in which in silico candidate structures were filtered according to ion mobility and hydrogen-deuterium exchange (HDX) reactivity matches. Results from the present study present three key findings namely (1) the evidence from ion production modeling supports previous structure refinement studies based on mobility and HDX reactivity matching, (2) the modeling of the electrospray process is significantly improved by utilizing initial droplets existing below but close to the calculated Rayleigh limit, and (3) peptide ions in the nanodroplets sample significantly different conformers than those in the bulk solution due to altered physicochemical properties of the solvent. Graphical Abstract ᅟ.

A Novel Microwave-Induced Plasma Ionization Source for Ion Mobility Spectrometry

NASA Astrophysics Data System (ADS)

Dai, Jianxiong; Zhao, Zhongjun; Liang, Gaoling; Duan, Yixiang

2017-03-01

This work demonstrates the application of a novel microwave induced plasma ionization (MIPI) source to ion mobility spectrometry (IMS). The MIPI source, called Surfatron, is composed of a copper cavity and a hollow quartz discharge tube. The ion mobility spectrum of synthetics air has a main peak with reduced mobility of 2.14 cm2V-1s-1 for positive ion mode and 2.29 cm2V-1s-1 for negative ion mode. The relative standard deviations (RSD) are 0.7% and 1.2% for positive and negative ion mode, respectively. The total ion current measured was more than 3.5 nA, which is much higher than that of the conventional 63Ni source. This indicates that a better signal-to-noise ratio (SNR) can be acquired from the MIPI source. The SNR was 110 in the analysis of 500 pptv methyl tert-butyl ether (MTBE), resulting in the limit of detection (SNR = 3) of 14 pptv. The linear range covers close to 2.5 orders of magnitude in the detection of triethylamine with a concentration range from 500 pptv to 80 ppbv. Finally, this new MIPI-IMS was used to detect some volatile organic compounds, which demonstrated that the MIPI-IMS has great potential in monitoring pollutants in air.

Ion Mobility Spectrometry (IMS) and Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 newmore » 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.« less

LC-IMS-MS Feature Finder: detecting multidimensional liquid chromatography, ion mobility and mass spectrometry features in complex datasets.

PubMed

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

2013-11-01

The addition of ion mobility spectrometry to liquid chromatography-mass spectrometry experiments requires new, or updated, software tools to facilitate data processing. 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. LC-IMS-MS Feature Finder is available as a command-line tool for download at http://omics.pnl.gov/software/LC-IMS-MS_Feature_Finder.php. The Microsoft.NET Framework 4.0 is required to run the software. All other dependencies are included with the software package. Usage of this software is limited to non-profit research to use (see README). rds@pnnl.gov. Supplementary data are available at Bioinformatics online.

Analysis of biogenic amines using corona discharge ion mobility spectrometry.

PubMed

Hashemian, Z; Mardihallaj, A; Khayamian, T

2010-05-15

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

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

NASA Technical Reports Server (NTRS)

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

1999-01-01

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

High-mobility low-temperature ZnO transistors with low-voltage operation

NASA Astrophysics Data System (ADS)

Bong, Hyojin; Lee, Wi Hyoung; Lee, Dong Yun; Kim, Beom Joon; Cho, Jeong Ho; Cho, Kilwon

2010-05-01

Low voltage high mobility n-type thin film transistors (TFTs) based on sol-gel processed zinc oxide (ZnO) were fabricated using a high capacitance ion gel gate dielectric. The ion gel gated solution-processed ZnO TFTs were found to exhibit excellent electrical properties. TFT carrier mobilities were 13 cm2/V s, ON/OFF current ratios were 105, regardless of the sintering temperature used for the preparation of the ZnO thin films. Ion gel gated ZnO TFTs are successfully demonstrated on plastic substrates for the large area flexible electronics.

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.

To What Extent is FAIMS Beneficial in the Analysis of Proteins?

NASA Astrophysics Data System (ADS)

Cooper, Helen J.

2016-04-01

High field asymmetric waveform ion mobility spectrometry (FAIMS), also known as differential ion mobility spectrometry, is emerging as a tool for biomolecular analysis. In this article, the benefits and limitations of FAIMS for protein analysis are discussed. The principles and mechanisms of FAIMS separation of ions are described, and the differences between FAIMS and conventional ion mobility spectrometry are detailed. Protein analysis is considered from both the top-down (intact proteins) and the bottom-up (proteolytic peptides) perspective. The roles of FAIMS in the analysis of complex mixtures of multiple intact proteins and in the analysis of multiple conformers of a single protein are assessed. Similarly, the application of FAIMS in proteomics and targeted analysis of peptides are considered.

Laser-stimulated desorption of organic molecules from surfaces, as a method of increasing the efficiency of ion mobility spectrometry analysis.

PubMed

Akmalov, Artem E; Chistyakov, Alexander A; Kotkovskii, Gennadii E

2017-08-01

Application of laser-induced desorption was investigated as a method of increasing the efficiency of gas phase analyzers on principles of field asymmetric ion mobility spectrometry. Mass spectrometric data of investigations of laser desorption of pentaerythritoltetranitrate molecules and cyclotetramethylenetetranitramine molecules from quartz substrate under vacuum were obtained. Laser sources a Nd 3+ :YAG with nanosecond pulse duration (λ = 532 nm) and a continuous wave diode laser (λ = 440 nm) were used. It was shown that both laser sources have different desorption abilities. This is expressed in various time of appearance of desorbed products that is caused by different heating mechanisms of surface layer. The desorbed quantity under action of both laser sources exceeds the detection threshold for all modern gas phase analyzers. It should be noted that despite the presence of surface dissociation of explosives under laser radiation, the quantity of nondissociated molecules is large enough for detection by ion mobility and field asymmetric ion mobility spectrometers. The optimal parameters of laser radiation for effective removal (evaporation) molecules of low-volatile compounds from surfaces are defined. The conclusion about preferable use of a Nd 3+ :YAG laser for increasing the detection ability of detectors based on ion mobility spectrometry was made.

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

Multifactorial Understanding of Ion Abundance in Tandem Mass Spectrometry Experiments.

PubMed

Fazal, Zeeshan; Southey, Bruce R; Sweedler, Jonathan V; Rodriguez-Zas, Sandra L

2013-01-29

In a bottom-up shotgun approach, the proteins of a mixture are enzymatically digested, separated, and analyzed via tandem mass spectrometry. The mass spectra relating fragment ion intensities (abundance) to the mass-to-charge are used to deduce the amino acid sequence and identify the peptides and proteins. The variables that influence intensity were characterized using a multi-factorial mixed-effects model, a ten-fold cross-validation, and stepwise feature selection on 6,352,528 fragment ions from 61,543 peptide ions. Intensity was higher in fragment ions that did not have neutral mass loss relative to any mass loss or that had a +1 charge state. Peptide ions classified for proton mobility as non-mobile had lowest intensity of all mobility levels. Higher basic residue (arginine, lysine or histidine) counts in the peptide ion and low counts in the fragment ion were associated with lower fragment ion intensities. Higher counts of proline in peptide and fragment ions were associated with lower intensities. These results are consistent with the mobile proton theory. Opposite trends between peptide and fragment ion counts and intensity may be due to the different impact of factor under consideration at different stages of the MS/MS experiment or to the different distribution of observations across peptide and fragment ion levels. Presence of basic residues at all three positions next to the fragmentation site was associated with lower fragment ion intensity. The presence of proline proximal to the fragmentation site enhanced fragmentation and had the opposite trend when located distant from the site. A positive association between fragment ion intensity and presence of sulfur residues (cysteine and methionine) on the vicinity of the fragmentation site was identified. These results highlight the multi-factorial nature of fragment ion intensity and could improve the algorithms for peptide identification and the simulation in tandem mass spectrometry experiments.

Multifactorial Understanding of Ion Abundance in Tandem Mass Spectrometry Experiments

PubMed Central

Fazal, Zeeshan; Southey, Bruce R; Sweedler, Jonathan V.; Rodriguez-Zas, Sandra L.

2013-01-01

In a bottom-up shotgun approach, the proteins of a mixture are enzymatically digested, separated, and analyzed via tandem mass spectrometry. The mass spectra relating fragment ion intensities (abundance) to the mass-to-charge are used to deduce the amino acid sequence and identify the peptides and proteins. The variables that influence intensity were characterized using a multi-factorial mixed-effects model, a ten-fold cross-validation, and stepwise feature selection on 6,352,528 fragment ions from 61,543 peptide ions. Intensity was higher in fragment ions that did not have neutral mass loss relative to any mass loss or that had a +1 charge state. Peptide ions classified for proton mobility as non-mobile had lowest intensity of all mobility levels. Higher basic residue (arginine, lysine or histidine) counts in the peptide ion and low counts in the fragment ion were associated with lower fragment ion intensities. Higher counts of proline in peptide and fragment ions were associated with lower intensities. These results are consistent with the mobile proton theory. Opposite trends between peptide and fragment ion counts and intensity may be due to the different impact of factor under consideration at different stages of the MS/MS experiment or to the different distribution of observations across peptide and fragment ion levels. Presence of basic residues at all three positions next to the fragmentation site was associated with lower fragment ion intensity. The presence of proline proximal to the fragmentation site enhanced fragmentation and had the opposite trend when located distant from the site. A positive association between fragment ion intensity and presence of sulfur residues (cysteine and methionine) on the vicinity of the fragmentation site was identified. These results highlight the multi-factorial nature of fragment ion intensity and could improve the algorithms for peptide identification and the simulation in tandem mass spectrometry experiments. PMID:24031159

Transport coefficients of gaseous ions in an electric field

NASA Technical Reports Server (NTRS)

Whealton, J. H.; Mason, E. A.

1974-01-01

A general theory of ion mobility formulated by Kihara (1953) is extended to ion diffusion and to mixtures of neutral gases. The theory assumes that only binary collisions between ions and neutral particles need to be taken into account and that the velocity distribution function of the neutral particles is Maxwellian. These assumptions make it possible to use a linearized Boltzmann equation. Questions of mobility are considered along with aspects of diffusion and deviations from Fick's law of diffusion.

Solid immersion lenses for enhancing the optical resolution of thermal and electroluminescence mapping of GaN-on-SiC transistors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pomeroy, J. W., E-mail: James.Pomeroy@Bristol.ac.uk; Kuball, M.

2015-10-14

Solid immersion lenses (SILs) are shown to greatly enhance optical spatial resolution when measuring AlGaN/GaN High Electron Mobility Transistors (HEMTs), taking advantage of the high refractive index of the SiC substrates commonly used for these devices. Solid immersion lenses can be applied to techniques such as electroluminescence emission microscopy and Raman thermography, aiding the development device physics models. Focused ion beam milling is used to fabricate solid immersion lenses in SiC substrates with a numerical aperture of 1.3. A lateral spatial resolution of 300 nm is demonstrated at an emission wavelength of 700 nm, and an axial spatial resolution of 1.7 ± 0.3 μm atmore » a laser wavelength of 532 nm is demonstrated; this is an improvement of 2.5× and 5×, respectively, when compared with a conventional 0.5 numerical aperture objective lens without a SIL. These results highlight the benefit of applying the solid immersion lenses technique to the optical characterization of GaN HEMTs. Further improvements may be gained through aberration compensation and increasing the SIL numerical aperture.« less

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

DOEpatents

Tang, Keqi [Richland, WA; Shvartsburg, Alexandre A [Richland, WA; Smith, Richard D [Richland, WA

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.

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.

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

NASA Astrophysics Data System (ADS)

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

1994-03-01

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

The Formation and Thermochemical Properties of Multiligand Complexes

DTIC Science & Technology

1987-08-25

SUBJECT TERMS (Continue on revers, if necessary and identify by block numoer) FIELD GROUP SUB-GROUP Ion-molecule reactions, clusters, multiligand...mercaptans, and phosphonates for which the results may be useful in the development of detection techniques that employ ion mobility analyzers or... field involve the use of ion mobility and mass spectrometers. Detection of a species by such instruments in an atmospheric environment requires that the

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

Hooked differential mobility spectrometry apparatus and method therefore

DOEpatents

Shvartsburg, Alexandre A [Richland, WA; Tang, Keqi [Richland, WA; Ibrahim, Yehia M [Richland, WA; Smith, Richard D [Richland, WA

2009-02-17

Disclosed are a device and method for improved interfacing of differential mobility spectrometry (DMS) or field asymmetric waveform ion mobility spectrometry (FAIMS) analyzers of substantially planar geometry to subsequent or preceding instrument stages. Interfacing is achieved using curved DMS elements, where a thick ion beam emitted by planar DMS analyzers or injected into them for ion filtering is compressed to the gap median by DMS ion focusing effect in a spatially inhomogeneous electric field. Resulting thinner beams are more effectively transmitted through necessarily constrained conductance limit apertures to subsequent instrument stages operated at a pressure lower than DMS, and/or more effectively injected into planar DMS analyzers. The technology is synergetic with slit apertures, slit aperture/ion funnels, and high-pressure ion funnel interfaces known in the art which allow for increasing cross-sectional area of MS inlets. The invention may be used in integrated analytical platforms, including, e.g., DMS/MS, LC/DMS/MS, and DMS/IMS/MS that could replace and/or enhance current LC/MS methods, e.g., for proteomics research.

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.

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

PubMed

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

2016-05-23

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

Improved momentum-transfer theory for ion mobility. 1. Derivation of the fundamental equation.

PubMed

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

2012-11-20

For the first time the fundamental ion mobility equation is derived by a bottom-up procedure, with N real atomic ion-atomic neutral collisions replaced by N repetitions of an average collision. Ion drift velocity is identified as the average of all pre- and postcollision velocities in the field direction. To facilitate velocity averaging, collisions are sorted into classes that "cool" and "heat" the ion. Averaging over scattering angles establishes mass-dependent relationships between pre- and postcollision velocities for the cooling and heating classes, and a combined expression for drift velocity is obtained by weighted addition according to relative frequencies of the cooling and heating encounters. At zero field this expression becomes identical to the fundamental low-field ion mobility equation. The bottom-up derivation identifies the low-field drift velocity as 3/4 of the average precollision ion velocity in the field direction and associates the passage from low-field to high-field conditions with the increasing dominance of "cooling" collisions over "heating" collisions. Most significantly, the analysis provides a direct path for generalization to fields of arbitrary strength.

Aerosol Vacuum-Assisted Plasma Ionization (Aero-VaPI) Coupled to Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Blair, Sandra L.; Ng, Nga L.; Zambrzycki, Stephen C.; Li, Anyin; Fernández, Facundo M.

2018-02-01

In this communication, we report on the real-time analysis of organic aerosol particles by Vacuum-assisted Plasma Ionization-Mass Spectrometry (Aero-VaPI-MS) using a home-built VaPI ion source coupled to a Synapt G2-S HDMS ion mobility-mass spectrometry (IM-MS) system. Standards of organic molecules of interest in prebiotic chemistry were used to generate aerosols. Monocaprin and decanoic acid aerosol particles were successfully detected in both the positive and negative ion modes, respectively. A complex aerosol mixture of different sizes of polymers of L-malic acid was also examined through ion mobility (IM) separations, resulting in the detection of polymers of up to eight monomeric units. This noncommercial plasma ion source is proposed as a low cost alternative to other plasma ionization platforms used for aerosol analysis, and a higher-performance alternative to more traditional aerosol mass spectrometers. VaPI provides robust online ionization of organics in aerosols without extensive ion activation, with the coupling to IM-MS providing higher peak capacity and excellent mass accuracy. [Figure not available: see fulltext.

High magnesium mobility in ternary spinel chalcogenides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan

Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door formore » the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.« less

High magnesium mobility in ternary spinel chalcogenides

DOE PAGES

Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan; ...

2017-11-24

Magnesium batteries appear a viable alternative to overcome the safety and energy density limitations faced by current lithium-ion technology. Furthermore, the development of a competitive magnesium battery is plagued by the existing notion of poor magnesium mobility in solids. We demonstrate by using ab initio calculations, nuclear magnetic resonance, and impedance spectroscopy measurements that substantial magnesium ion mobility can indeed be achieved in close-packed frameworks (~ 0.01-0.1 mS cm -1 at 298 K), specifically in the magnesium scandium selenide spinel. Our theoretical predictions also indicate that high magnesium ion mobility is possible in other chalcogenide spinels, opening the door formore » the realization of other magnesium solid ionic conductors and the eventual development of an all-solid-state magnesium battery.« less

Graphene/Pentacene Barristor with Ion-Gel Gate Dielectric: Flexible Ambipolar Transistor with High Mobility and On/Off Ratio.

PubMed

Oh, Gwangtaek; Kim, Jin-Soo; Jeon, Ji Hoon; Won, EunA; Son, Jong Wan; Lee, Duk Hyun; Kim, Cheol Kyeom; Jang, Jingon; Lee, Takhee; Park, Bae Ho

2015-07-28

High-quality channel layer is required for next-generation flexible electronic devices. Graphene is a good candidate due to its high carrier mobility and unique ambipolar transport characteristics but typically shows a low on/off ratio caused by gapless band structure. Popularly investigated organic semiconductors, such as pentacene, suffer from poor carrier mobility. Here, we propose a graphene/pentacene channel layer with high-k ion-gel gate dielectric. The graphene/pentacene device shows both high on/off ratio and carrier mobility as well as excellent mechanical flexibility. Most importantly, it reveals ambipolar behaviors and related negative differential resistance, which are controlled by external bias. Therefore, our graphene/pentacene barristor with ion-gel gate dielectric can offer various flexible device applications with high performances.

Ion-neutral potential models in atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS.

PubMed

Steiner, Wes E; English, William A; Hill, Herbert H

2006-02-09

The ion mobilities and their respective masses of several classes of amines (primary, secondary, and tertiary) were measured by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS. The experimental data obtained were comparatively analyzed by the one-temperature kinetic theory of Chapman-Enskog. Several theoretical models were used to estimate the collision cross-sections; they include the rigid-sphere, polarization-limit, 12-6-4, and 12-4 potential models. These models were investigated to represent the interaction potentials contained within the collision integral that occurs between the polyatomic ions and the neutral drift gas molecules. The effectiveness of these collision cross-section models on predicting the mobility of these amine ions was explored. Moreover, the effects of drift gas selectivity on the reduced-mass term and in the collision cross-section term was examined. Use of a series of drift gases, namely, helium, neon, argon, nitrogen, and carbon dioxide, made it possible to distinguish between mass effects and polarizability effects. It was found that the modified 12-4 potential that compensates for the center of charge not being at the same location as the centers of mass showed improved agreement over the other collision cross-section models with respect to experimental data.

Utility of Higher Harmonics in Electrospray Ionization Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometry.

PubMed

Dziekonski, Eric T; Johnson, Joshua T; McLuckey, Scott A

2017-04-18

Mass resolution (M/ΔM fwhm) is observed to linearly increase with harmonic order in a Fourier transform electrostatic linear ion trap (ELIT) mass spectrometer. This behavior was predicted by Grosshans and Marshall for frequency-multiple detection in a Fourier transform ion cyclotron resonance mass spectrometer only for situations when the prominent mechanism for signal decay is ion ejection from the trap. As the analyzer pressure in our ELIT chamber is relatively high, such that collisional scattering and collision-induced dissociation are expected to underlie much of the ion loss, we sought to explore the relationship between harmonic order and mass resolution. Mass resolutions of 36 900 (fundamental), 75 850 (2nd harmonic), and 108 200 (3rd harmonic) were obtained for GdO + (avg. m/z 173.919) with a transient length of 300 ms. To demonstrate that the mass resolution was truly increasing with harmonic order, the unresolved isotopes at the fundamental distribution of cytochrome c +8 (m/z ∼ 1549) were nearly baseline, resolved at the third harmonic (mass resolution ≈ 23 000) with a transient length of only 200 ms. This experiment demonstrates that, when the ion density is sufficiently low, ions with frequency differences of less than 4 Hz remain uncoalesced. Higher harmonics can be used to increase the effective mass resolution for a fixed transient length and thereby may enable the resolution of closely spaced masses, determination of a protein ion's charge state, and study of the onset of peak coalescence when the resolution at the fundamental frequency is insufficient.

Internal friction and vulnerability of mixed alkali glasses.

PubMed

Peibst, Robby; Schott, Stephan; Maass, Philipp

2005-09-09

Based on a hopping model we show how the mixed alkali effect in glasses can be understood if only a small fraction c(V) of the available sites for the mobile ions is vacant. In particular, we reproduce the peculiar behavior of the internal friction and the steep fall ("vulnerability") of the mobility of the majority ion upon small replacements by the minority ion. The single and mixed alkali internal friction peaks are caused by ion-vacancy and ion-ion exchange processes. If c(V) is small, they can become comparable in height even at small mixing ratios. The large vulnerability is explained by a trapping of vacancies induced by the minority ions. Reasonable choices of model parameters yield typical behaviors found in experiments.

Time‐of‐flight secondary ion mass spectrometry imaging of biological samples with delayed extraction for high mass and high spatial resolutions

PubMed Central

Vanbellingen, Quentin P.; Elie, Nicolas; Eller, Michael J.; Della‐Negra, Serge; Touboul, David

2015-01-01

Rationale In Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS), pulsed and focused primary ion beams enable mass spectrometry imaging, a method which is particularly useful to map various small molecules such as lipids at the surface of biological samples. When using TOF‐SIMS instruments, the focusing modes of the primary ion beam delivered by liquid metal ion guns can provide either a mass resolution of several thousand or a sub‐µm lateral resolution, but the combination of both is generally not possible. Methods With a TOF‐SIMS setup, a delayed extraction applied to secondary ions has been studied extensively on rat cerebellum sections in order to compensate for the effect of long primary ion bunches. Results The use of a delayed extraction has been proven to be an efficient solution leading to unique features, i.e. a mass resolution up to 10000 at m/z 385.4 combined with a lateral resolution of about 400 nm. Simulations of ion trajectories confirm the experimental determination of optimal delayed extraction and allow understanding of the behavior of ions as a function of their mass‐to‐charge ratio. Conclusions Although the use of a delayed extraction has been well known for many years and is very popular in MALDI, it is much less used in TOF‐SIMS. Its full characterization now enables secondary ion images to be recorded in a single run with a submicron spatial resolution and with a mass resolution of several thousand. This improvement is very useful when analyzing lipids on tissue sections, or rare, precious, or very small size samples. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26395603

[Ion mobility spectrometer (IMS): a novel online monitor of trace volatile organic compounds].

PubMed

Li, Fang; Xie, Zhi-yong; Schmidt, H; Sielemann, S; Baumbach, J I

2002-12-01

The principle, character and developments of the instrument of ion mobility spectrometry are introduced, the applications of IMS to chemical warfare agents, explosives, drugs, environments monitoring and on-site industrial sensing are discussed, and some work on IMS in ISAS is represented.

An Investigation of Traveling-Wave Electrophoresis using a Trigonometric Potential

NASA Astrophysics Data System (ADS)

Vopal, James

Traveling-wave electrophoresis, a technique for microfluidic separations in lab-on-achip devices, is investigated using a trigonometric model that naturally incorporates the spatial periodicity of the device. Traveling-wave electrophoresis can be used to separate high-mobility ions from low-mobility ions in forensic and medical applications, with a separation threshold that can be tuned for specific applications by simply choosing the traveling wave frequency. Our simulations predict plateaus in the average ion velocity verses the mobility, plateaus that correspond to Farey fractions and yield Devil's staircases for non-zero discreteness values. The plateaus indicate that ions with different mobilities can travel with the same average velocity. To determine the conditions for chaos, Lyapunov exponents and contact maps are employed. Through the use of contact maps, the chaotic trajectories are determined to be either narrowband or broadband. Narrowband chaotic trajectories are exhibited in the plateaus of the average velocity, while broadband chaotic trajectories are exhibited where the average velocity varies nonmonotonically with the mobility. Narrowband chaos will be investigated in future work incorporating the role of diffusion. The results of this and future work can be used to develop new tools for electrophoretic separation.

Electrotransfer in Liquid Binary Aluminum Alloys

NASA Astrophysics Data System (ADS)

Tekuchev, V. V.; Kalinkin, D. P.; Ivanova, I. V.

2018-07-01

The mobility of ions in a liquid binary metal system based on aluminum is calculated for the first time in a wide range of concentrations, based on studies of its resistivity and self-diffusion coefficient. It is established that in an Al-Cu system, the ions of aluminum move to the anode, while Al-Mg, Al-Sn, and Al-Sb move to the cathode; i.e., there is inversion of the electrotransfer of aluminum ions. When the concentration of a component is reduced, the mobility of its ions is increased by the module.

Exchange, interpretation, and database-search of ion mobility spectra supported by data format JCAMP-DX

NASA Technical Reports Server (NTRS)

Baumback, J. I.; Davies, A. N.; Vonirmer, A.; Lampen, P. H.

1995-01-01

To assist peak assignment in ion mobility spectrometry it is important to have quality reference data. The reference collection should be stored in a database system which is capable of being searched using spectral or substance information. We propose to build such a database customized for ion mobility spectra. To start off with it is important to quickly reach a critical mass of data in the collection. We wish to obtain as many spectra combined with their IMS parameters as possible. Spectra suppliers will be rewarded for their participation with access to the database. To make the data exchange between users and system administration possible, it is important to define a file format specially made for the requirements of ion mobility spectra. The format should be computer readable and flexible enough for extensive comments to be included. In this document we propose a data exchange format, and we would like you to give comments on it. For the international data exchange it is important, to have a standard data exchange format. We propose to base the definition of this format on the JCAMP-DX protocol, which was developed for the exchange of infrared spectra. This standard made by the Joint Committee on Atomic and Molecular Physical Data is of a flexible design. The aim of this paper is to adopt JCAMP-DX to the special requirements of ion mobility spectra.

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

Design of a retarding potential grid system for a neutral particle analyzer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Titus, J. B., E-mail: jtitus@wisc.edu; Mezonlin, E. D.; Anderson, J. K.

2014-11-15

The ion energy distribution in a magnetically confined plasma can be inferred from charge exchange neutral particles. On the Madison Symmetric Torus (MST), deuterium neutrals are measured by the Florida A and M University compact neutral particle analyzer (CNPA) and the advanced neutral particle analyzer (ANPA). The CNPA energy range covers the bulk deuterium ions to the beginning of the fast ion tail (0.34–5.2 keV) with high-energy resolution (25 channels) while the ANPA covers the vast majority of the fast ion tail distribution (∼10–45 keV) with low energy resolution (10 channels). Though the ANPA has provided insight into fast ionmore » energization in MST plasma, more can be gained by increasing the energy resolution in that energy range. To utilize the energy resolution of the CNPA, fast ions can be retarded by an electric potential well, enabling their detection by the diagnostic. The ion energy distribution can be measured with arbitrary resolution by combining data from many similar MST discharges with different energy ranges on the CNPA, providing further insight into ion energization and fast ion dynamics on MST.« less

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Miniaturized Ion Mobility Spectrometer

NASA Technical Reports Server (NTRS)

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

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.

Note: Buffer gas temperature inhomogeneities and design of drift-tube ion mobility spectrometers: Warnings for real-world applications by non-specialists

NASA Astrophysics Data System (ADS)

Fernandez-Maestre, R.

2017-09-01

Ion mobility spectrometry (IMS) separates gas phase ions moving under an electric field according to their size-to-charge ratio. IMS is the method of choice to detect illegal drugs and explosives in customs and airports making accurate determination of reduced ion mobilities (K0) important for national security. An ion mobility spectrometer with electrospray ionization coupled to a quadrupole mass spectrometer was used to study uncertainties in buffer gas temperatures during mobility experiments. Differences up to 16°C were found in the buffer gas temperatures in different regions of the drift tube and up to 42°C between the buffer gas and the drift tube temperatures. The drift tube temperature is used as an approximation to the buffer gas temperature for the calculation of K0 because the buffer gas temperature is hard to measure. This is leading to uncertainties in the determination of K0 values. Inaccurate determination of K0 values yields false positives that delay the cargo and passengers in customs and airports. Therefore, recommendations are issued for building mobility tubes to assure a homogeneous temperature of the buffer gas. Because the temperature and other instrumental parameters are difficult to measure in IMS, chemical standards should always be used when calculating K0. The difference of 42°C between the drift tube and buffer gas temperatures found in these experiments produces a 10.5% error in the calculation of K0. This large inaccuracy in K0 shows the importance of a correct temperature measurement in IMS.

Influence of variation in mobile phase pH and solute pK(a) with the change of organic modifier fraction on QSRRs of hydrophobicity and RP-HPLC retention of weakly acidic compounds.

PubMed

Han, Shu-ying; Liang, Chao; Zou, Kuan; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin

2012-11-15

The variation in mobile phase pH and ionizable solute dissociation constant (pK(a)) with the change of organic modifier fraction in hydroorganic mobile phase has seemingly been a troublesome problem in studies and applications of reversed phase high performance liquid chromatography (RP-HPLC). Most of the early studies regarding the RP-HPLC of acid-base compounds have to measure the actual pH of the mixed mobile phase rigorously, sometimes bringing difficulties in the practices of liquid chromatographic separation. In this paper, the effect of this variation on the apparent n-octanol/water partition coefficient (K(ow)″) and the related quantitative structure-retention relationship (QSRR) of logK(ow)″ vs. logk(w), the logarithm of retention factor of analytes in neat aqueous mobile phases, was investigated for weakly acidic compounds. This QSRR is commonly used as a classical method for K(ow) measurement by RP-HPLC. The theoretical and experimental derivation revealed that the variation in mobile phase pH and solute pK(a) will not affect the QSRRs of acidic compounds. This conclusion is proved to be suitable for various types of ion-suppressors, i.e., strong acid (perchloric acid), weak acid (acetic acid) and buffer salt (potassium dihydrogen phosphate/phosphoric acid, PBS). The QSRRs of logK(ow)″ vs. logk(w) were modeled by 11 substituted benzoic acids using different types of ion-suppressors in a binary methanol-water mobile phase to confirm our deduction. Although different types of ion-suppressor all can be used as mobile phase pH modifiers, the QSRR model obtained by using perchloric acid as the ion-suppressor was found to have the best result, and the slightly inferior QSRRs were obtained by using acetic acid or PBS as the ion-suppressor. Copyright © 2012 Elsevier B.V. All rights reserved.

Determination of linsidomine in human plasma by tandem LC-MS with ESI.

PubMed

Sutherland, F C; de Jager, A D; Swart, K J; Hundt, H K; Scanes, T; Hundt, A F

2000-04-01

A sensitive method for the determination of linsidomine in plasma was developed, using high-performance liquid chromatographic (HPLC) separation with tandem mass spectrometric detection. Linsidomine was derivatised with propyl chloroformate and extracted with tert-butyl methyl ether/1,2-dichloroethane (55:45, v/v), back-extracted into HCl (0.01 M) followed by alkalinisation and back-extraction into ether; the final ether extract evaporated, reconstituted in mobile phase and then separated on a Phenomenex Luna C18 (2) 5 micron 2.1 x 150 mm column with a mobile phase consisting of methanol water formic acid (98/100%) (400:600:0.05, v/v/v) at a flow-rate of 0.4 ml min(-1). Detection was achieved by a Finnigan MAT mass spectrometer (LCQ) at unit resolution in the selected reaction monitoring (SRM) mode monitoring the transition of the protonated molecular ion m/z 257.0 to the product ion m/z 86.0. The mean recovery for linsidomine was 51% with a lower limit of quantification of 0.70 ng/ml using 1 ml plasma for extraction. This LC-MS/MS method for the determination of linsidomine in human plasma allows for better specificity and a higher sample throughput than the traditional LC-UV methods. It also demonstrates the profound effect that the composition of acidic modifiers and matrix constituents can have on the electrospray ionisation (ESI) of the analyte.

Comprehensive characterization of ethoxyquin transformation products in fish feed by traveling-wave ion mobility spectrometry coupled to quadrupole time-of-flight mass spectrometry.

PubMed

Negreira, Noelia; Regueiro, Jorge; Valdersnes, Stig; Berntssen, Marc H G; Ørnsrud, Robin

2017-05-01

Feed additives are typically used in intensive farming production over long periods, and hence, they can accumulate in farmed animal tissues. Concerns regarding the use of ethoxyquin as an antioxidant feed additive, have recently arisen due to its potential conversion into a series of transformation products (TPs). The aim of this work was to characterize the TPs of ethoxyquin in fish feed by a novel approach based on the use of traveling-wave ion mobility spectrometry (TWIMS) coupled to high-resolution quadrupole time-of-flight mass spectrometry (QTOFMS). First, ethoxyquin was oxidized under controlled conditions and the generated TPs were added to a comprehensive database. Atlantic salmon feeds were then screened for ethoxyquin TPs using both targeted and untargeted approaches. Twenty-seven TPs were tentatively identified during the oxidation experiments, fifteen of them also being present in the feed samples. In addition, ten other potential TPs were detected in fish feed following the untargeted approach. Thirty-one of these TPs have been reported for the first time in this work through the oxidation experiments and the feed samples. Therefore, this study provides valuable information on the oxidative fate of ethoxyquin in feed, which can be used for future evaluations of potential risk related to this additive. Copyright © 2017 Elsevier B.V. All rights reserved.

Retention behavior of long chain quaternary ammonium homologues and related nitroso-alkymethylamines

USGS Publications Warehouse

Abidi, S.L.

1985-01-01

Several chromatographic methods have been utilized to study the retentionbehavior of a homologous series of n-alkylbenzyldimethylammonium chlorides (ABDAC) and the corresponding nitroso-n-alkylmethylamines (NAMA). Linear correlation of the logarithmic capacity factor (k') with the number of carbons in the alkyl chain provides useful information on both gas chromatographic (GC) and high-performance liquid chromatographich (HPLC) retention parameters of unknown components. Under all conditions empolyed, GC methodology has proved effective in achieving complete resolution of the homologous mixture of NMA despite its obvious inadequacy in the separation of E-Z configurational isomers. Conversely, normal-phase HPLC on silica demonstrates that the selectivity (a) value for an E-Z pair is much higher than that for an adjacent homologous pair. In the reversed-phase HPLC study, three different silica-based column systems were examined under various mobile phase conditions. The extent of variation in k' was found to be a function of the organic modifier, counter-ion concentration, eluent pH, nature of counter-ion, and the polarity and type of stationary phase. The k'—[NaClO4] profiles showed similar trends between the ABDAC and the NAMA series, supporting the dipolar electronic structures of the latter compounds. Mobile phase and stationary phase effects on component separation are described. The methodology presented establishes the utility of HPLC separation techniques as versatile analytical tools for practical application.

Recent Advances and Future Challenges in Modified Mycotoxin Analysis: Why HRMS Has Become a Key Instrument in Food Contaminant Research

PubMed Central

Righetti, Laura; Paglia, Giuseppe; Galaverna, Gianni; Dall’Asta, Chiara

2016-01-01

Mycotoxins are secondary metabolites produced by pathogenic fungi in crops worldwide. These compounds can undergo modification in plants, leading to the formation of a large number of possible modified forms, whose toxicological relevance and occurrence in food and feed is still largely unexplored. The analysis of modified mycotoxins by liquid chromatography–mass spectrometry remains a challenge because of their chemical diversity, the large number of isomeric forms, and the lack of analytical standards. Here, the potential benefits of high-resolution and ion mobility mass spectrometry as a tool for separation and structure confirmation of modified mycotoxins have been investigated/reviewed. PMID:27918432

Application of ion mobility-mass spectrometry to microRNA analysis.

PubMed

Takebayashi, Kosuke; Hirose, Kenji; Izumi, Yoshihiro; Bamba, Takeshi; Fukusaki, Eiichiro

2013-03-01

Liquid chromatography/mass spectrometry is widely used for studying sequence determination and modification analysis of small RNAs. However, the efficiency of liquid chromatography-based separation of intact small RNA species is insufficient, since the physiochemical properties among small RNAs are very similar. In this study, we focused on ion mobility-mass spectrometry (IM-MS), which is a gas-phase separation technique coupled with mass spectrometry; we have evaluated the utility of IM-MS for microRNA (miRNA) analysis. A multiply charged deprotonated ion derived from an 18-24-nt-long miRNA was formed by electrospray ionization, and then the time, called the "drift time", taken by each ion to migrate through a buffer gas was measured. Each multivalent ion was temporally separated on the basis of the charge state and structural formation; 3 types of unique mass-mobility correlation patterns (i.e., chainlike-form, hairpin-form, and dimer-form) were present on the two-dimensional mobility-mass spectrum. Moreover, we found that the ion size (sequence length) and the secondary structures of the small RNAs strongly contributed to the IM-MS-based separation, although solvent conditions such as pH had no effect. Therefore, sequence isomers could also be discerned by the selection of each specific charged ion, i.e., the 6(-) charged ion reflected a majority among chainlike-, hairpin-, and other structures. We concluded that the IM-MS provides additional capability for separation; thus, this analytical method will be a powerful tool for comprehensive small RNA analysis. Copyright © 2012. Published by Elsevier B.V.

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.

Coupled mobilization of dissolved organic matter and metals (Cu and Zn) in soil columns

NASA Astrophysics Data System (ADS)

Zhao, Lu Y. L.; Schulin, Rainer; Weng, Liping; Nowack, Bernd

2007-07-01

Dissolved organic carbon (DOC) is a key component involved in metal displacement in soils. In this study, we investigated the concentration profiles of soil-borne DOC, Cu and Zn at various irrigation rates with synthetic rain water under quasi steady-state conditions, using repacked soil columns with a metal-polluted topsoil and two unpolluted subsoils. Soil solution was collected using suction cups installed at centimeter intervals over depth. In the topsoil the concentrations of DOC, dissolved metals (Zn and Cu), major cations (Ca 2+ and Mg 2+) and anions ( NO3- and SO42-) increased with depth. In the subsoil, the Cu and Zn concentrations dropped to background levels within 2 cm. All compounds were much faster mobilized in the first 4 cm than in the rest of the topsoil. DOC and Cu concentrations were higher at higher flow rates for a given depth, whereas the concentrations of the other ions decreased with increasing flow rate. The decomposition of soil organic matter resulted in the formation of DOC, SO42-, and NO3- and was the main driver of the system. Regression analysis indicated that Cu mobilization was governed by DOC, whereas Zn mobilization was primarily determined by Ca and to a lesser extent by DOC. Labile Zn and Cu 2+ concentrations were well predicted by the NICA-Donnan model. The results highlight the value of high-resolution in-situ measurements of DOC and metal mobilization in soil profiles.

Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

PubMed Central

Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

2009-01-01

A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

Proceedings of the AFOSR Special Conference on Prime-Power for High Energy Space Systems, Norfolk, Virginia, 22-25 February 1982. Volume 2

DTIC Science & Technology

1982-02-25

However, because the mobility of the ions is much smaller than the mobility of the electrons (for cesium i = 1/500 Me), and because of ion...space applications of this high temperature in- sulation. Use of glass-alumina insulation for motors in mobile applications would reduce cooling...present and/or mobile only during irradiation. VII-7-7 WS 710 01AS$ AesowRpIOr MEA8IJRtED MOt AN FTER L5 MvV ELECTRON NtADIATION Fig. 7 -- Growth of

Field ion spectrometry: a new technology for cocaine and heroin detection

NASA Astrophysics Data System (ADS)

Carnahan, Byron L.; Day, Stephen; Kouznetsov, Viktor; Tarassov, Alexandre

1997-02-01

Field ion spectrometry, also known as transverse field compensation ion mobility spectrometry, is a new technique for trace gas analysis that can be applied to the detection of cocaine and heroin. Its principle is based on filtering ion species according to the functional dependence of their mobilities with electric field strength. Field ion spectrometry eliminates the gating electrodes needed in conventional IMS to pulse ions into the spectrometer; instead, ions are injected in to the spectrometer and reach the detector continuously, resulting in improved sensitivity. The technique enables analyses that are difficult with conventional constant field strength ion mobility spectrometers. We have shown that a filed ion spectrometer can selectively detect the vapors from cocaine and heroin emitted from both their base and hydrochloride forms. The estimated volumetric limits of detection are in the low pptv range, based on testing with standardized drug vapor generation systems. The spectrometer can detect cocaine base in the vapor phase, at concentrations well below its estimated 100 pptv vapor pressure equivalent at 20 degrees C. This paper describes the underlying principles of field ion spectrometry in relation to narcotic drug detection, and recent results obtained for cocaine and heroin. The work has been sponsored in part by the United States Advanced Research Projects Agency under contract DAAB10-95C-0004, for the DOD Counterdrug Technology Development Program.

Ion manipulations in structures for lossless ion manipulations (SLIM): computational evaluation of a 90° turn and a switch

DOE PAGES

Garimella, Sandilya V. B.; Ibrahim, Yehia. M.; Webb, Ian K.; ...

2015-08-19

The process of redirecting ions through 90° turns and ‘tee’ switches utilizing Structures for Lossless Ion Manipulations (SLIM) was evaluated using theoretical and simulation methods at 4 Torr pressure. SIMION simulations were used to optimize and evaluate conditions for performing turns without loss of signal intensity or ion mobility resolving power. Fundamental considerations indicated that the “race track” effect during ion turns may incur only small losses to the ion mobility resolving power at 4 Torr pressure for the typical plume widths predicted in an optimized SLIM ‘tee’ switch design. The dynamic switching of ions into orthogonal channels was alsomore » evaluated using SIMION ion trajectory simulations, and achieved similar performance. Simulation results were in close agreement with experimental results and were used to refine SLIM designs and applied potentials for their use.« less

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.

Molecular Dynamics Simulations of Ion Transport and Mechanisms in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2015-03-01

Using all atom molecular dynamics and trajectory-extending kinetic Monte Carlo simulations, we study the influence of Al2O3 nanoparticles on the transport properties of Li+ ions in polymer electrolytes consisting of polyethylene oxide (PEO) melt solvated with LiBF4 salt. We observe that the nanoparticles have a strong influence on polymer segmental dynamics which in turn correlates with the mobility of Li+ ions. Explicitly, polymer segmental relaxation times and Li+ ion residence times around polymer were found to increase with the addition of nanoparticles. We also observe that increasing short range repulsive interactions between nanoparticles and polymer membrane leads to increasing polymer dynamics and ion mobility. Overall, our simulation results suggest that nanoparticle induced changes in conformational and dynamic properties of the polymer influences the ion mobilities in polymer electrolytes and suggests possible directions for using such findings to improve the polymer matrix conductivity. The authors acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing computing resources that have contributed to the research.

Magnetic resonance imaging of chemistry.

PubMed

Britton, Melanie M

2010-11-01

Magnetic resonance imaging (MRI) has long been recognized as one of the most important tools in medical diagnosis and research. However, MRI is also well placed to image chemical reactions and processes, determine the concentration of chemical species, and look at how chemistry couples with environmental factors, such as flow and heterogeneous media. This tutorial review will explain how magnetic resonance imaging works, reviewing its application in chemistry and its ability to directly visualise chemical processes. It will give information on what resolution and contrast are possible, and what chemical and physical parameters can be measured. It will provide examples of the use of MRI to study chemical systems, its application in chemical engineering and the identification of contrast agents for non-clinical applications. A number of studies are presented including investigation of chemical conversion and selectivity in fixed-bed reactors, temperature probes for catalyst pellets, ion mobility during tablet dissolution, solvent dynamics and ion transport in Nafion polymers and the formation of chemical waves and patterns.

Comparison of Different Ion Mobility Setups Using Poly (Ethylene Oxide) PEO Polymers: Drift Tube, TIMS, and T-Wave

NASA Astrophysics Data System (ADS)

Haler, Jean R. N.; Massonnet, Philippe; Chirot, Fabien; Kune, Christopher; Comby-Zerbino, Clothilde; Jordens, Jan; Honing, Maarten; Mengerink, Ynze; Far, Johann; Dugourd, Philippe; De Pauw, Edwin

2018-01-01

Over the years, polymer analyses using ion mobility-mass spectrometry (IM-MS) measurements have been performed on different ion mobility spectrometry (IMS) setups. In order to be able to compare literature data taken on different IM(-MS) instruments, ion heating and ion temperature evaluations have already been explored. Nevertheless, extrapolations to other analytes are difficult and thus straightforward same-sample instrument comparisons seem to be the only reliable way to make sure that the different IM(-MS) setups do not greatly change the gas-phase behavior. We used a large range of degrees of polymerization (DP) of poly(ethylene oxide) PEO homopolymers to measure IMS drift times on three different IM-MS setups: a homemade drift tube (DT), a trapped (TIMS), and a traveling wave (T-Wave) IMS setup. The drift time evolutions were followed for increasing polymer DPs (masses) and charge states, and they are found to be comparable and reproducible on the three instruments. [Figure not available: see fulltext.

The Relationship between Bulk and Mobile Forms of Heavy Metals in Soils of Kursk

NASA Astrophysics Data System (ADS)

Nevedrov, N. P.; Protsenko, E. P.; Glebova, I. V.

2018-01-01

The contamination of Kursk urboecotopes by heavy metals (Pb, Cd, Zn, Cu, Ni) is considered. The relationships between the contents of bulk and mobile forms of heavy metal ions have been examined. The results of monitoring studies attest to a tendency for the accumulation of both bulk and mobile forms of heavy metals in the humus-accumulative horizon, except for bulk cadmium and mobile nickel. Linear and nonlinear regression models of the bulk contents of Pb, Cd, Zn, and Ni as dependent on the contents of their mobile forms have been developed. These models allow us to calculate the bulk content of heavy metal ions in the soils of urboecotopes using simpler methods of the extraction and laboratory determination of their mobile forms.

High-resolution, low-delay, and error-resilient medical ultrasound video communication using H.264/AVC over mobile WiMAX networks.

PubMed

Panayides, Andreas; Antoniou, Zinonas C; Mylonas, Yiannos; Pattichis, Marios S; Pitsillides, Andreas; Pattichis, Constantinos S

2013-05-01

In this study, we describe an effective video communication framework for the wireless transmission of H.264/AVC medical ultrasound video over mobile WiMAX networks. Medical ultrasound video is encoded using diagnostically-driven, error resilient encoding, where quantization levels are varied as a function of the diagnostic significance of each image region. We demonstrate how our proposed system allows for the transmission of high-resolution clinical video that is encoded at the clinical acquisition resolution and can then be decoded with low-delay. To validate performance, we perform OPNET simulations of mobile WiMAX Medium Access Control (MAC) and Physical (PHY) layers characteristics that include service prioritization classes, different modulation and coding schemes, fading channels conditions, and mobility. We encode the medical ultrasound videos at the 4CIF (704 × 576) resolution that can accommodate clinical acquisition that is typically performed at lower resolutions. Video quality assessment is based on both clinical (subjective) and objective evaluations.

Mass spectrometry and tandem mass spectrometry of citrus limonoids.

PubMed

Tian, Qingguo; Schwartz, Steven J

2003-10-15

Methods for atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) of citrus limonoid aglycones and electrospray ionization tandem mass spectrometry (ESI-MS/MS) of limonoid glucosides are reported. The fragmentation patterns of four citrus limonoid aglycones (limonin, nomilin, obacunone, and deacetylnomilin) and six limonoid glucosides, that is, limonin 17-beta-D-glucopyranoside (LG), nomilin 17-beta-D-glucopyranoside (NG), nomilinic acid 17-beta-D-glucopyranoside (NAG), deacetyl nomilinic acid 17-beta-D-glucopyranoside (DNAG), obacunone 17-beta-D-glucopyranoside (OG), and obacunoic acid 17-beta-D-glucopyranoside (OAG) were investigated using a quadruple mass spectrometer in low-energy collisionally activated dissociation (CAD). The four limonoid aglycones and four limonoid glucosides (LG, OG, NAG, and DNAG) were purified from citrus seeds; the other two limonoid glucosides (NG and OAG) were tentatively identified in the crude extract of grapefruit seeds by ESI mass spectrometry in both positive and negative ion analysis. Ammonium hydroxide or acetic acid was added to the mobile phase to facilitate ionization. During positive ion APCI analysis of limonoid aglycones, protonated molecular ion, [M + H]+, or adduct ion, [M + NH3 + H]-, was formed as base peaks when ammonium hydroxide was added to the mobile phase. Molecular anions or adduct ions with acetic acid ([M + HOAc - H] and [M + HOAc]-) or a deprotonated molecular ion were produced during negative ion APCI analysis of limonoid aglycones, depending on the mobile-phase modifier used. Positive ion ESI-MS of limonoid glucosides produced adduct ions of [M + H + NH3]+, [M + Na]+, and [M + K]+ when ammonium hydroxide was added to the mobile phase. After collisionally activated dissociation (CAD) of the limonoid aglycone molecular ions in negative ion APCI analysis, fragment ions indicated structural information of the precursor ions, showing the presence of methyl, carboxyl, and oxygenated ring structure. CAD of the adduct ion [M + H + NH3]+ of limonoid glucosides produced the aglycone moiety corresponding to each glucoside. The combination of mass spectrometry and tandem mass spectrometry provides a powerful technique for identification and characterization of citrus limonoids.

Imaging of Endogenous Metabolites of Plant Leaves by Mass Spectrometry Based on Laser Activated Electron Tunneling.

PubMed

Huang, Lulu; Tang, Xuemei; Zhang, Wenyang; Jiang, Ruowei; Chen, Disong; Zhang, Juan; Zhong, Hongying

2016-04-07

A new mass spectrometric imaging approach based on laser activated electron tunneling (LAET) was described and applied to analysis of endogenous metabolites of plant leaves. LAET is an electron-directed soft ionization technique. Compressed thin films of semiconductor nanoparticles of bismuth cobalt zinc oxide were placed on the sample plate for proof-of-principle demonstration because they can not only absorb ultraviolet laser but also have high electron mobility. Upon laser irradiation, electrons are excited from valence bands to conduction bands. With appropriate kinetic energies, photoexcited electrons can tunnel away from the barrier and eventually be captured by charge deficient atoms present in neutral molecules. Resultant unpaired electron subsequently initiates specific chemical bond cleavage and generates ions that can be detected in negative ion mode of the mass spectrometer. LAET avoids the co-crystallization process of routinely used organic matrix materials with analyzes in MALDI (matrix assisted-laser desorption ionization) analysis. Thus uneven distribution of crystals with different sizes and shapes as well as background peaks in the low mass range resulting from matrix molecules is eliminated. Advantages of LAET imaging technique include not only improved spatial resolution but also photoelectron capture dissociation which produces predictable fragment ions.

A High-Pressure Hollow Cathode Discharge Source for Ion Mobility Spectrometers for In-Situ Detection of Organic Molecules on Mars

NASA Technical Reports Server (NTRS)

Beegle, L. W.; Noren, C.; Kanik, I.

2000-01-01

We have designed, constructed and begun testing of a new high-pressure (5-10 Torr) hollow cathode discharge source (HCDS) that can be utilized as an ionizer for ion mobility spectrometers as well as in a wide variety of mass analyzers.

High-resolution high-sensitivity elemental imaging by secondary ion mass spectrometry: from traditional 2D and 3D imaging to correlative microscopy

NASA Astrophysics Data System (ADS)

Wirtz, T.; Philipp, P.; Audinot, J.-N.; Dowsett, D.; Eswara, S.

2015-10-01

Secondary ion mass spectrometry (SIMS) constitutes an extremely sensitive technique for imaging surfaces in 2D and 3D. Apart from its excellent sensitivity and high lateral resolution (50 nm on state-of-the-art SIMS instruments), advantages of SIMS include high dynamic range and the ability to differentiate between isotopes. This paper first reviews the underlying principles of SIMS as well as the performance and applications of 2D and 3D SIMS elemental imaging. The prospects for further improving the capabilities of SIMS imaging are discussed. The lateral resolution in SIMS imaging when using the microprobe mode is limited by (i) the ion probe size, which is dependent on the brightness of the primary ion source, the quality of the optics of the primary ion column and the electric fields in the near sample region used to extract secondary ions; (ii) the sensitivity of the analysis as a reasonable secondary ion signal, which must be detected from very tiny voxel sizes and thus from a very limited number of sputtered atoms; and (iii) the physical dimensions of the collision cascade determining the origin of the sputtered ions with respect to the impact site of the incident primary ion probe. One interesting prospect is the use of SIMS-based correlative microscopy. In this approach SIMS is combined with various high-resolution microscopy techniques, so that elemental/chemical information at the highest sensitivity can be obtained with SIMS, while excellent spatial resolution is provided by overlaying the SIMS images with high-resolution images obtained by these microscopy techniques. Examples of this approach are given by presenting in situ combinations of SIMS with transmission electron microscopy (TEM), helium ion microscopy (HIM) and scanning probe microscopy (SPM).

Comprehensive lipidomic analysis of human plasma using multidimensional liquid- and gas-phase separations: Two-dimensional liquid chromatography-mass spectrometry vs. liquid chromatography-trapped-ion-mobility-mass spectrometry.

PubMed

Baglai, Anna; Gargano, Andrea F G; Jordens, Jan; Mengerink, Ynze; Honing, Maarten; van der Wal, Sjoerd; Schoenmakers, Peter J

2017-12-29

Recent advancements in separation science have resulted in the commercialization of multidimensional separation systems that provide higher peak capacities and, hence, enable a more-detailed characterization of complex mixtures. In particular, two powerful analytical tools are increasingly used by analytical scientists, namely online comprehensive two-dimensional liquid chromatography (LC×LC, having a second-dimension separation in the liquid phase) and liquid chromatography-ion mobility-spectrometry (LC-IMS, second dimension separation in the gas phase). The goal of the current study was a general assessment of the liquid-chromatography-trapped-ion-mobility-mass spectrometry (LC-TIMS-MS) and comprehensive two-dimensional liquid chromatography-mass spectrometry (LC×LC-MS) platforms for untargeted lipid mapping in human plasma. For the first time trapped-ion-mobility spectrometry (TIMS) was employed for the separation of the major lipid classes and ion-mobility-derived collision-cross-section values were determined for a number of lipid standards. The general effects of a number of influencing parameters have been inspected and possible directions for improvements are discussed. We aimed to provide a general indication and practical guidelines for the analyst to choose an efficient multidimensional separation platform according to the particular requirements of the application. Analysis time, orthogonality, peak capacity, and an indicative measure for the resolving power are discussed as main characteristics for multidimensional separation systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of moisture on the field dependence of mobility for gas-phase ions of organophosphorus compounds at atmospheric pressure with field asymmetric ion mobility spectrometry.

PubMed

Krylova, N; Krylov, E; Eiceman, G A; Stone, J A

2003-05-15

The electric field dependence of the mobilities of gas-phase protonated monomers [(MH+(H2O)n] and proton-bound dimers [M2H+(H2O)n] of organophosphorus compounds was determined at E/N values between 0 and 140 Td at ambient pressure in air with moisture between 0.1 and 15 000 ppm. Field dependence was described as alpha (E/N) and was obtained from the measurements of compensation voltage versus field amplitude in a planar high-field asymmetric waveform ion mobility spectrometer. The alpha function for protonated monomers to 140 Td was constant from 0.1 to 10 ppm moisture in air with onset of effect at approximately 50 ppm. The value of alpha increased 2-fold from 100 to 1000 ppm at all E/N values. At moisture values between 1000 and 10 000 ppm, a 2-fold or more increase in alpha (E/N) was observed. In a model proposed here, field dependence for mobility through changes in collision cross sections is governed by the degree of solvation of the protonated molecule by neutral molecules. The process of ion declustering at high E/N values was consistent with the kinetics of ion-neutral collisional periods, and the duty cycle of the waveform applied to the drift tube. Water was the principal neutral above 50 ppm moisture in air, and nitrogen was proposed as the principal neutral below 50 ppm.

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

DOEpatents

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

2015-09-01

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

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Structure of alcohol cluster ions in the gas phase, according to spectrometry and ab initio calculations

NASA Astrophysics Data System (ADS)

Krisilov, A. V.; Lantsuzskaya, E. V.; Levina, A. M.

2017-01-01

Reduced ion mobility and scattering cross sections are calculated from experimentally obtained spectra of the ion mobility of linear aliphatic alcohols with carbon atom numbers from 2 to 9. A linear increase in the scattering cross sections as the molecular weight grows is found. According to the results from experiments and quantum chemical calculations, alcohol cluster ions do not form a compact structure. Neither are dipole moments compensated for during dimerization, in contrast to the aldehydes and ketones described earlier. It was concluded from ab initio calculations that charge delocalization in monomeric and dimeric ions of alcohols increases the dipole moment many times over.

Improving depth resolutions in positron beam spectroscopy by concurrent ion-beam sputtering

NASA Astrophysics Data System (ADS)

John, Marco; Dalla, Ayham; Ibrahim, Alaa M.; Anwand, Wolfgang; Wagner, Andreas; Böttger, Roman; Krause-Rehberg, Reinhard

2018-05-01

The depth resolution of mono-energetic positron annihilation spectroscopy using a positron beam is shown to improve by concurrently removing the sample surface layer during positron beam spectroscopy. During ion-beam sputtering with argon ions, Doppler-broadening spectroscopy is performed with energies ranging from 3 keV to 5 keV allowing for high-resolution defect studies just below the sputtered surface. With this technique, significantly improved depth resolutions could be obtained even at larger depths when compared to standard positron beam experiments which suffer from extended positron implantation profiles at higher positron energies. Our results show that it is possible to investigate layered structures with a thickness of about 4 microns with significantly improved depth resolution. We demonstrated that a purposely generated ion-beam induced defect profile in a silicon sample could be resolved employing the new technique. A depth resolution of less than 100 nm could be reached.

Interpretation of inverted photocurrent transients in organic lead halide perovskite solar cells: proof of the field screening by mobile ions and determination of the space charge layer widths

DOE PAGES

Belisle, Rebecca A.; Nguyen, William H.; Bowring, Andrea R.; ...

2017-01-01

In Methyl Ammonium Lead Iodide (MAPI) perovskite solar cells, screening of the built-in field by mobile ions has been proposed as part of the cause of the large hysteresis observed in the current/voltage scans in many cells. Here, we show that photocurrent transients measured immediately (e.g. 100 μs) after a voltage step can provide direct evidence that this field screening exists. Just after a step to forward bias, the photocurrent transients are reversed in sign (i.e. inverted), and the magnitude of the inverted transients can be used to find an upper bound on the width of the space charge layersmore » adjacent to the electrodes. This in turn provides a lower bound on the mobile charge concentration, which we find to be ≳1 x 10 17 cm -3. Using a new photocurrent transient experiment, we show that the space charge layer thickness remains approximately constant as a function of bias, as expected for mobile ions in a solid electrolyte. We also discuss additional characteristics of the inverted photocurrent transients that imply either an unusually stable deep trapping, or a photo effect on the mobile ion conductivity.« less

Interpretation of inverted photocurrent transients in organic lead halide perovskite solar cells: proof of the field screening by mobile ions and determination of the space charge layer widths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belisle, Rebecca A.; Nguyen, William H.; Bowring, Andrea R.

In Methyl Ammonium Lead Iodide (MAPI) perovskite solar cells, screening of the built-in field by mobile ions has been proposed as part of the cause of the large hysteresis observed in the current/voltage scans in many cells. Here, we show that photocurrent transients measured immediately (e.g. 100 μs) after a voltage step can provide direct evidence that this field screening exists. Just after a step to forward bias, the photocurrent transients are reversed in sign (i.e. inverted), and the magnitude of the inverted transients can be used to find an upper bound on the width of the space charge layersmore » adjacent to the electrodes. This in turn provides a lower bound on the mobile charge concentration, which we find to be ≳1 x 10 17 cm -3. Using a new photocurrent transient experiment, we show that the space charge layer thickness remains approximately constant as a function of bias, as expected for mobile ions in a solid electrolyte. We also discuss additional characteristics of the inverted photocurrent transients that imply either an unusually stable deep trapping, or a photo effect on the mobile ion conductivity.« less

Ion optical design of a collinear laser-negative ion beam apparatus.

PubMed

Diehl, C; Wendt, K; Lindahl, A O; Andersson, P; Hanstorp, D

2011-05-01

An apparatus for photodetachment studies on atomic and molecular negative ions of medium up to heavy mass (M ≃ 500) has been designed and constructed. Laser and ion beams are merged in the apparatus in a collinear geometry and atoms, neutral molecules and negative ions are detected in the forward direction. The ion optical design and the components used to optimize the mass resolution and the transmission through the extended field-free interaction region are described. A 90° sector field magnet with 50 cm bending radius in combination with two slits is used for mass dispersion providing a resolution of M∕ΔM≅800 for molecular ions and M∕ΔM≅400 for atomic ions. The difference in mass resolution for atomic and molecular ions is attributed to different energy distributions of the sputtered ions. With 1 mm slits, transmission from the source through the interaction region to the final ion detector was determined to be about 0.14%.

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.

A micropixelated ion-imaging detector for mass resolution enhancement of a QMS instrument.

PubMed

Syed, Sarfaraz U A H; Eijkel, Gert B; Maher, Simon; Kistemaker, Piet; Taylor, Stephen; Heeren, Ron M A

2015-03-01

An in-vacuum position-sensitive micropixelated detector (Timepix) is used to investigate the time-dependent spatial distribution of different charge state (and hence different mass-to-charge (m/z)) ions exiting an electrospray ionization (ESI)-based quadrupole mass spectrometer (QMS) instrument. Ion images obtained from the Timepix detector provide a detailed insight into the positions of stable and unstable ions of the mass peak as they exit the QMS. With the help of image processing algorithms and by selecting areas on the ion images where more stable ions impact the detector, an improvement in mass resolution by a factor of 5 was obtained for certain operating conditions. Moreover, our experimental approach of mass resolution enhancement was confirmed by in-house-developed novel QMS instrument simulation software. Utilizing the imaging-based mass resolution enhancement approach, the software predicts instrument mass resolution of ∼1,0000 for a single-filter QMS instrument with a 210-mm long mass filter and a low operating frequency (880 kHz) of the radio frequency (RF) voltage.

Formation of iron complexs from trifluoroacetic acid based liquid chromatography mobile phases as interference ions in liquid chromatography/electrospray ionization mass spectrometric analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukla, Anil K.; Zhang, Rui; Orton, Daniel J.

Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are not due to any contamination from solvents and chemicals used for mobile and stationary phases or from the laboratory atmospheric environment. Instead these ions are clusters of trifluoroacetic acid formed in association with acetonitrile, water and iron from the stainless steel union used to connect the column with the electrospray tip and to applymore » high voltage; the molecular formulae are Fe+((OH)(H2O)2)9(CF3COOH)5 and Fe+((OH)(H2O)2)6 (CF3COOH)5.« less

Space charge effect in spectrometers of ion mobility increment with cylindrical drift chamber.

PubMed

Elistratov, A A; Sherbakov, L A

2007-01-01

We have amplified the model for the drift of ions under a non-uniform high-frequency electric field by taking space charge effect into account. By this means, we have investigated the effect of space charge on the dynamics of a single type of ions in a spectrometer of ion mobility increment with a cylindrical drift chamber. The counteraction of the space charge effect and the focusing effect is investigated. The output ion current saturation caused by the effect of the space charge is observed. The shape of the ion peak taking into consideration the space charge effect has been obtained. We show that the effect of the space charge is sufficient for the relative ion density greater than 10 ppt by order of magnitude (for a cylindrical geometry spectrometer with typical parameters).

Measuring the effects of Coulomb repulsion via signal decay in an atmospheric pressure laser ionization ion mobility spectrometer.

PubMed

Ihlenborg, Marvin; Schuster, Ann-Kathrin; Grotemeyer, Juergen; Gunzer, Frank

2018-01-01

Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

LC-IMS-MS Feature Finder

DOE Office of Scientific and Technical Information (OSTI.GOV)

2013-03-07

LC-IMS-MS Feature Finder is a command line software application which searches for possible molecular ion signatures in multidimensional liquid chromatography, ion mobility spectrometry, and mass spectrometry data by clustering deisotoped peaks with similar monoisotopic mass values, charge states, elution times, and drift times. The software application includes an algorithm for detecting multiple conformations and co-eluting species in the ion mobility dimension. LC-IMS-MS Feature Finder is designed to create an output file with detected features that includes associated information about the detected features.

High resolution x-ray absorption and emission spectroscopy of Li x CoO2 single crystals as a function delithiation

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Iwai, C.; Miyoshi, K.; Takeuchi, J.; Mizokawa, T.; Saini, N. L.

2017-03-01

The effect of delithiation in Li x CoO2 is studied by high resolution Co K-edge x-ray absorption and x-ray emission spectroscopy. Polarization dependence of the x-ray absorption spectra on single crystal samples is exploited to reveal information on the anisotropic electronic structure. We find that the electronic structure of Li x CoO2 is significantly affected by delithiation in which the Co ions oxidation state tending to change from 3+  to 4+. The Co intersite (intrasite) 4p-3d hybridization suffers a decrease (increase) by delithiation. The unoccupied 3d t 2g orbitals with a 1g symmetry, containing substantial O 2p character, hybridize isotropically with Co 4p orbitals and likely to have itinerant character unlike anisotropically hybridized 3d e g orbitals. Such a peculiar electronic structure could have significant effect on the mobility of Li in Li x CoO2 cathode and hence the battery characteristics.

An HS-MRM Assay for the Quantification of Host-cell Proteins in Protein Biopharmaceuticals by Liquid Chromatography Ion Mobility QTOF Mass Spectrometry.

PubMed

Doneanu, Catalin; Fang, Jing; Alelyunas, Yun; Yu, Ying Qing; Wrona, Mark; Chen, Weibin

2018-04-17

The analysis of low-level (1-100 ppm) protein impurities (e.g., host-cell proteins (HCPs)) in protein biotherapeutics is a challenging assay requiring high sensitivity and a wide dynamic range. Mass spectrometry-based quantification assays for proteins typically involve protein digestion followed by the selective reaction monitoring/multiple reaction monitoring (SRM/MRM) quantification of peptides using a low-resolution (Rs ~1,000) tandem quadrupole mass spectrometer. One of the limitations of this approach is the interference phenomenon observed when the peptide of interest has the "same" precursor and fragment mass (in terms of m/z values) as other co-eluting peptides present in the sample (within a 1-Da window). To avoid this phenomenon, we propose an alternative mass spectrometric approach, a high selectivity (HS) MRM assay that combines the ion mobility separation of peptide precursors with the high-resolution (Rs ~30,000) MS detection of peptide fragments. We explored the capabilities of this approach to quantify low-abundance peptide standards spiked in a monoclonal antibody (mAb) digest and demonstrated that it has the sensitivity and dynamic range (at least 3 orders of magnitude) typically achieved in HCP analysis. All six peptide standards were detected at concentrations as low as 0.1 nM (1 femtomole loaded on a 2.1-mm ID chromatographic column) in the presence of a high-abundance peptide background (2 µg of a mAb digest loaded on-column). When considering the MW of rabbit phosphorylase (97.2 kDa), from which the spiked peptides were derived, the LOQ of this assay is lower than 50 ppm. Relative standard deviations (RSD) of peak areas (n = 4 replicates) were less than 15% across the entire concentration range investigated (0.1-100 nM or 1-1,000 ppm) in this study.

Deprotonation effect of tetrahydrofuran-2-carbonitrile buffer gas dopant in ion mobility spectrometry.

PubMed

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

2016-06-15

When dopants are introduced into the buffer gas of an ion mobility spectrometer, spectra are simplified due to charge competition. We used electrospray ionization to inject tetrahydrofuran-2-carbonitrile (F, 2-furonitrile or 2-furancarbonitrile) as a buffer gas dopant into an ion mobility spectrometer coupled to a quadrupole mass spectrometer. Density functional theory was used for theoretical calculations of dopant-ion interaction energies and proton affinities, using the hybrid functional X3LYP/6-311++(d,p) with the Gaussian 09 program that accounts for the basis set superposition error; analytes structures and theoretical calculations with Gaussian were used to explain the behavior of the analytes upon interaction with F. When F was used as a dopant at concentrations below 1.5 mmol m(-3) in the buffer gas, ions were not observed for α-amino acids due to charge competition with the dopant; this deprotonation capability arises from the production of a dimer with a high formation energy that stabilized the positive charge and created steric hindrance that deterred the equilibrium with analyte ions. F could not completely strip other compounds of their charge because they either showed steric hindrance at the charge site that deterred the approach of the dopant (2,4-lutidine, and DTBP), formed intramolecular bonds that stabilized the positive charge (atenolol), had high proton affinity (2,4-lutidine, DTBP, valinol and atenolol), or were inherently ionic (tetraalkylammonium ions). This selective deprotonation suggests the use of F to simplify spectra of complex mixtures in ion mobility and mass spectrometry in metabolomics, proteomics and other studies that generate complex spectra with thousands of peaks. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Separation and characterization of allergic polymerized impurities in cephalosporins by 2D-HPSEC×LC-IT-TOF MS.

PubMed

Xu, Yu; Wang, DanDan; Tang, Lan; Wang, Jian

2017-10-25

Eleven unknown allergic impurities in cefodizime, cefmenoxime and cefonicid were separated and characterized by a trap-free two-dimensional high performance size exclusion chromatography (HPSEC) and reversed phase liquid chromatography (RP-HPLC) coupled to high resolution ion trap/time-of-flight mass spectrometry (2D-HPSEC×LC-IT-TOF MS) with positive and negative modes of electrospray ionization method. Separation and characterization the allergic polymerized impurities in β-lactam antibiotics were on the basis of column-switching technique which effectively combined the advantages of HPSEC and the ability of RP-HPLC to identify the special impurities. In the first dimension HPSEC, the column was Xtimate SEC-120 analytical column (7.8mm×30cm, 5μm), and the gradient elution used pH 7.0 buffer-acetonitrile as mobile phase And the second dimension analytical column was ZORBAX SB-C18 (4.6×150mm, 3.5μm) with ammonium formate solution (10mM) and ammonium formate (8mM) in [acetonitrile-water (4:1, v/v)] solution as mobile phase. Structures of eleven unknown impurities were deduced based on the high resolution MS n data with both positive and negative modes, in which nine impurities were polymerized impurities. The forming mechanism of β-lactam antibiotic polymerization in cephalosporins was also studied. The question on incompatibility between non-volatile salt mobile phase and mass spectrometry was solved completely by multidimensional heart-cutting approaches and online demineralization technique, which was worthy of widespread use and application for the advantages of stability and repeatability. Copyright © 2017. Published by Elsevier B.V.

Ammonium Ion Binding to DNA G-Quadruplexes: Do Electrospray Mass Spectra Faithfully Reflect the Solution-Phase Species?

NASA Astrophysics Data System (ADS)

Balthasart, Françoise; Plavec, Janez; Gabelica, Valérie

2013-01-01

G-quadruplex nucleic acids can bind ammonium ions in solution, and these complexes can be detected by electrospray mass spectrometry (ESI-MS). However, because ammonium ions are volatile, the extent to which ESI-MS quantitatively could provide an accurate reflection of such solution-phase equilibria is unclear. Here we studied five G-quadruplexes having known solution-phase structure and ammonium ion binding constants: the bimolecular G-quadruplexes (dG4T4G4)2, (dG4T3G4)2, and (dG3T4G4)2, and the intramolecular G-quadruplexes dG4(T4G4)3 and dG2T2G2TGTG2T2G2 (thrombin binding aptamer). We found that not all mass spectrometers are equally suited to reflect the solution phase species. Ion activation can occur in the electrospray source, or in a high-pressure traveling wave ion mobility cell. When the softest instrumental conditions are used, ammonium ions bound between G-quartets, but also additional ammonium ions bound at specific sites outside the external G-quartets, can be observed. However, even specifically bound ammonium ions are in some instances too labile to be fully retained in the gas phase structures, and although the ammonium ion distribution observed by ESI-MS shows biases at specific stoichiometries, the relative abundances in solution are not always faithfully reflected. Ion mobility spectrometry results show that all inter-quartet ammonium ions are necessary to preserve the G-quadruplex fold in the gas phase. Ion mobility experiments, therefore, help assign the number of inner ammonium ions in the solution phase structure.[Figure not available: see fulltext.

A critical review of ion mobility spectrometry for the detection of explosives and explosive related compounds.

PubMed

Ewing, R G; Atkinson, D A; Eiceman, G A; Ewing, G J

2001-05-10

Ion mobility spectrometry has become the most successful and widely used technology for the detection of trace levels of nitro-organic explosives on handbags and carry on-luggage in airports throughout the US. The low detection limits are provided by the efficient ionization process, namely, atmospheric pressure chemical ionization (APCI) reactions in negative polarity. An additional level of confidence in a measurement is imparted by characterization of ions for mobilities in weak electric fields of a drift tube at ambient pressure. Findings from over 30 years of investigations into IMS response to these explosives have been collected and assessed to allow a comprehensive view of the APCI reactions characteristic of nitro-organic explosives. Also, the drift tube conditions needed to obtain particular mobility spectra have been summarized. During the past decade, improvements have occurred in IMS on the understanding of reagent gas chemistries, the influence of temperature on ion stability, and sampling methods. In addition, commercial instruments have been refined to provide fast and reliable measurements for on-site detection of explosives. The gas phase ion chemistry of most explosives is mediated by the fragile CONO(2) bonds or the acidity of protons. Thus, M(-) or M.Cl(-) species are found with only a few explosives and loss of NO(2), NO(3) and proton abstraction reactions are common and complicating pathways. However, once ions are formed, they appear to have stabilities on time scales equal to or longer than ion drift times from 5-20 ms. As such, peak shapes in IMS are suitable for high selectivity and sensitivity.

High-resolution grazing-incidence grating spectrometer for temperature measurements of low-Z ions emitting in the 100-300 Å spectral banda)

NASA Astrophysics Data System (ADS)

Widmann, K.; Beiersdorfer, P.; Magee, E. W.; Boyle, D. P.; Kaita, R.; Majeski, R.

2014-11-01

We have constructed a high-resolution grazing-incidence spectrometer designed for measuring the ion temperature of low-Z elements, such as Li+ or Li2 +, which radiate near 199 Å and 135 Å, respectively. Based on measurements at the Livermore Electron Beam Ion Trap we have shown that the instrumental resolution is better than 48 mÅ at the 200 Å setting and better than 40 mÅ for the 135-Å range. Such a high spectral resolution corresponds to an instrumental limit for line-width based temperature measurements of about 45 eV for the 199 Å Li+ and 65 eV for the 135 Å Li2 + lines. Recently obtained survey spectra from the Lithium Tokamak Experiment at the Princeton Plasma Physics Laboratory show the presence of these lithium emission lines and the expected core ion temperature of approximately 70 eV is sufficiently high to demonstrate the feasibility of utilizing our high-resolution spectrometer as an ion-temperature diagnostic.

Profiling the indole alkaloids in yohimbe bark with ultra-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry

USDA-ARS?s Scientific Manuscript database

An ultra-high performance liquid chromatography-ion mobility- quadrupole time-of-flight mass spectrometry (UHPLC-IM-QTOF-MS) method was developed for profiling the indole alkaloids in yohimbe bark. Many indole alkaloids with the yohimbine core structure, plus methylated, oxidized, and reduced speci...

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

1995-01-01

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

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

NASA Technical Reports Server (NTRS)

Baumbach, J. I.; Vonirmer, A.

1995-01-01

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

Measurement of drug facilitated sexual assault agents in simulated sweat by ion mobility spectrometry.

PubMed

Demoranville, Leonard T; Verkouteren, Jennifer R

2013-03-15

Ion mobility spectrometry has found widespread use for the detection of explosives and illicit drugs. The technique offers rapid results with high sensitivity and little sample preparation. As such, it is well suited for field deployed screening settings. Here the response of ion mobility spectrometers for three drug-facilitated sexual assault (DFSA) agents - flunitrazepam, ketamine, and MDMA - and related metabolites has been studied in the presence of a simulated sweat. While all three DFSA agents present certain challenges for qualitative identification, IMS can provide useful information to guide the early treatment and investigation of sexual assault cases. Used as a presumptive test, the identification of DFSA agents would later require confirmatory analysis by other techniques. Published by Elsevier B.V.

Experimental ion mobility measurements in Xe-CF4 mixtures

NASA Astrophysics Data System (ADS)

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

2018-04-01

In this paper we present the results of the ion mobility measurements made in gaseous mixtures of xenon with carbon tetrafluoride (Xe-CF4) for pressures ranging from 6 to 10 Torr (8-10.6 mbar) and for low reduced electric fields in the 10 to 25 Td range (2.4-6.1 kVṡcm‑1ṡbar‑1), at room temperature. The time-of-arrival spectra revealed one or two peaks depending on the gas relative abundances, which were attributed to CF3+ and to Xe2+ ions. However, for Xe concentrations above 60%, only one peak remains (Xe2+). The reduced mobilities obtained from the peak centroid of the time-of-arrival spectra are presented for Xe concentrations in the 5%-95% range.

Detection of methamphetamine in the presence of nicotine using in situ chemical derivatization and ion mobility spectrometry.

PubMed

Ochoa, Mariela L; Harrington, Peter B

2004-02-15

The detection of methamphetamine in the presence of nicotine has been successfully accomplished using in situ chemical derivatization with propyl chloroformate as the derivatization reagent and ion mobility spectrometry (IMS). The rapid detection of methamphetamine is important for forensic scientists in order to establish a chain of evidence and link criminals to the crime scene. Nicotine is pervasive in clandestine drug laboratories from cigarette smoke residue. It has been demonstrated that nicotine obscures the methamphetamine peaks in ion mobility spectrometers due to their similar charge affinities and ion mobilities, which makes their detection a challenging task. As a consequence, false positive or negative responses may arise. In situ chemical derivatization poses as a sensitive, accurate, and reproducible alternative to remove the nicotine background when detecting nanogram amounts of methamphetamine. The derivatization agent was coated onto the sample disk, and the derivatization product corresponding to propyl methamphetamine carbamate was detected. In the present study, in situ chemical derivatization was demonstrated to be a feasible method to detect methamphetamine hydrochloride as the carbamate derivative, which was baseline-resolved from the nicotine peak. Alternating least squares (ALS) was used to model the datasets. A mixture containing both compounds revealed reduced mobilities of 1.61 cm(2)/V.s and 1.54 cm(2)/V.s for methamphetamine and nicotine, respectively. The reduced mobility of propyl methamphetamine carbamate was found at 1.35 cm(2)/V.s.

A complementary mobile phase approach based on the peak count concept oriented to the full resolution of complex mixtures.

PubMed

Ortín, A; Torres-Lapasió, J R; García-Álvarez-Coque, M C

2011-08-26

Situations of minimal resolution are often found in liquid chromatography, when samples that contain a large number of compounds, or highly similar in terms of structure and/or polarity, are analysed. This makes full resolution with a single separation condition (e.g., mobile phase, gradient or column) unfeasible. In this work, the optimisation of the resolution of such samples in reversed-phase liquid chromatography is approached using two or more isocratic mobile phases with a complementary resolution behaviour (complementary mobile phases, CMPs). Each mobile phase is dedicated to the separation of a group of compounds. The CMPs are selected in such a way that, when the separation is considered globally, all the compounds in the sample are satisfactorily resolved. The search of optimal CMPs can be carried out through a comprehensive examination of the mobile phases in a selected domain. The computation time of this search has been reported to be substantially reduced by application of a genetic algorithm with local search (LOGA). A much simpler approach is here described, which is accessible to non-experts in programming, and offers solutions of the same quality as LOGA, with a similar computation time. The approach makes a sequential search of CMPs based on the peak count concept, which is the number of peaks exceeding a pre-established resolution threshold. The new approach is described using as test sample a mixture of 30 probe compounds, 23 of them with an ionisable character, and the pH and organic solvent contents as experimental factors. Copyright © 2011 Elsevier B.V. All rights reserved.

Simultaneous Determination of Formoterol Fumarate and Budesonide Epimers in Metered Dose Inhaler Using Ion-Pair Chromatography.

PubMed

Salem, Y A; Shaldam, M A; El-Sherbiny, D T; El-Wasseef, D R; El-Ashry, S M

2017-11-01

A simple, accurate and valid ion-pairing chromatographic method was developed for the simultaneous determination of formoterol fumarate (FF) and budesonide (BUD) epimers in metered dose inhaler. The separation was performed on C-18 column using mobile phase consisting of acetonitrile:0.05 M sodium acetate buffer (40:60% v/v) containing 0.03% sodium dodecyl sulfate adjusted to pH 3.1 using increasing volumes of either TEA or orthophosphoric acid isocratically eluted at 1.0 mL/min. Quantitation was achieved with UV detection at 214 nm. The retention times were 3.22, 6.41 and 6.91 min for formoterol fumarate, budesonide epimers B and A, respectively. The linearity range was 0.05-5.0 μg/mL for formoterol fumarate and 0.5-50.0 μg/mL for budesonide. The method was validated for, linearity; lower limit of quantification, lower limit of detection accuracy and precision. The proposed method is rapid (7 min), reproducible (RSD < 2.0%) and achieves satisfactory resolution between FF and BUD B (resolution factor = 12.07). The mean recoveries of the analytes in metered dose inhaler (99.97 and 99.83% for FF and BUD, respectively) were satisfactory. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

A novel ToF-SIMS operation mode for sub 100 nm lateral resolution: Application and performance.

PubMed

Kubicek, Markus; Holzlechner, Gerald; Opitz, Alexander K; Larisegger, Silvia; Hutter, Herbert; Fleig, Jürgen

2014-01-15

A novel operation mode for time of flight-secondary ion mass spectrometry (ToF-SIMS) is described for a TOF.SIMS 5 instrument with a Bi-ion gun. It features sub 100 nm lateral resolution, adjustable primary ion currents and the possibility to measure with high lateral resolution as well as high mass resolution. The adjustment and performance of the novel operation mode are described and compared to established ToF-SIMS operation modes. Several examples of application featuring novel scientific results show the capabilities of the operation mode in terms of lateral resolution, accuracy of isotope analysis of oxygen, and combination of high lateral and mass resolution. The relationship between high lateral resolution and operation of SIMS in static mode is discussed.

Development and Application of a Soil Moisture Downscaling Method for Mobility Assessment

DTIC Science & Technology

2011-05-01

instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send...REPORT Development and Application of a Soil Moisture Downscaling Method for Mobility Assessment 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Soil...cells). Thus, a method is required to downscale intermediate-resolution patterns to finer resolutions. Fortunately, fine-resolution variations in

Identification of Lasso Peptide Topologies Using Native Nanoelectrospray Ionization-Trapped Ion Mobility Spectrometry-Mass Spectrometry.

PubMed

Dit Fouque, Kevin Jeanne; Moreno, Javier; Hegemann, Julian D; Zirah, Séverine; Rebuffat, Sylvie; Fernandez-Lima, Francisco

2018-04-17

Lasso peptides are a fascinating class of bioactive ribosomal natural products characterized by a mechanically interlocked topology. In contrast to their branched-cyclic forms, lasso peptides have higher stability and have become a scaffold for drug development. However, the identification and separation of lasso peptides from their unthreaded topoisomers (branched-cyclic peptides) is analytically challenging since the higher stability is based solely on differences in their tertiary structures. In the present work, a fast and effective workflow is proposed for the separation and identification of lasso from branched cyclic peptides based on differences in their mobility space under native nanoelectrospray ionization-trapped ion mobility spectrometry-mass spectrometry (nESI-TIMS-MS). The high mobility resolving power ( R) of TIMS resulted in the separation of lasso and branched-cyclic topoisomers ( R up to 250, 150 needed on average). The advantages of alkali metalation reagents (e.g., Na, K, and Cs salts) as a way to increase the analytical power of TIMS is demonstrated for topoisomers with similar mobilities as protonated species, efficiently turning the metal ion adduction into additional separation dimensions.

Voltage sweep ion mobility spectrometry.

PubMed

Davis, Eric J; Williams, Michael D; Siems, William F; Hill, Herbert H

2011-02-15

Ion mobility spectrometry (IMS) is a rapid, gas-phase separation technique that exhibits excellent separation of ions as a standalone instrument. However, IMS cannot achieve optimal separation power with both small and large ions simultaneously. Similar to the general elution problem in chromatography, fast ions are well resolved using a low electric field (50-150 V/cm), whereas slow drifting molecules are best separated using a higher electric field (250-500 V/cm). While using a low electric field, IMS systems tend to suffer from low ion transmission and low signal-to-noise ratios. Through the use a novel voltage algorithm, some of these effects can be alleviated. The electric field was swept from low to high while monitoring a specific drift time, and the resulting data were processed to create a 'voltage-sweep' spectrum. If an optimal drift time is calculated for each voltage and scanned simultaneously, a spectrum may be obtained with optimal separation throughout the mobility range. This increased the resolving power up to the theoretical maximum for every peak in the spectrum and extended the peak capacity of the IMS system, while maintaining accurate drift time measurements. These advantages may be extended to any IMS, requiring only a change in software.

Effects of the Discharge Parameters on the Efficiency and Stability of Ambient Metastable-Induced Desorption Ionization

NASA Astrophysics Data System (ADS)

Zhang, Xiaotian; Chen, Chilai; Liu, Youjiang; Wang, Hongwei; Zhang, Lehua; Kong, Deyi; Mario, Chavarria

2015-12-01

Ionization efficiency is an important factor for ion sources in mass spectrometry and ion mobility spectrometry. Using helium as the discharge gas, acetone as the sample, and high-field asymmetric ion mobility spectrometry (FAIMS) as the ion detection method, this work investigates in detail the effects of discharge parameters on the efficiency of ambient metastable-induced desorption ionization (AMDI) at atmospheric pressure. The results indicate that the discharge power and gas flow rate are both significantly correlated with the ionization efficiency. Specifically, an increase in the applied discharge power leads to a rapid increase in the ionization efficiency, which gradually reaches equilibrium due to ion saturation. Moreover, when the discharge voltage is fixed at 2.1 kV, a maximum efficiency can be achieved at the flow rate of 9.0 m/s. This study provides a foundation for the design and application of AMDI for on-line detection with mass spectrometry and ion mobility spectrometry. supported by National Natural Science Foundation of China (No. 61374016), the Changzhou Science and Technology Support Program, China (No. CE20120081) and the External Cooperation Program of Chinese Academy of Sciences (No. GJHZ1218)

New high-resolution electrostatic ion mass analyzer using time of flight

NASA Technical Reports Server (NTRS)

Hamilton, D. C.; Gloeckler, G.; Ipavich, F. M.; Lundgren, R. A.; Sheldon, R. B.

1990-01-01

The design of a high-resolution ion-mass analyzer is described, which is based on an accurate measurement of the time of flight (TOF) of ions within a region configured to produce a harmonic potential. In this device, the TOF, which is independent of ion energy, is determined from a start pulse from secondary electrons produced when the ion passes through a thin carbon foil at the entrance of the TOF region and at a stop pulse from the ion striking a microchannel plate upon exciting the region. A laboratory prototype instrument called 'VMASS' was built and was tested at the Goddard Space Flight Center electrostatic accelerator, showing a good mass resolution of the instrument. Sensors of the VMASS type will form part of the WIND Solar Wind and Suprathermal Ion experiment, the Soho mission, and the Advanced Composition Explorer.

Corona discharge ionization of paracetamol molecule: Peak assignment

NASA Astrophysics Data System (ADS)

Bahrami, H.; Farrokhpour, H.

2015-01-01

Ionization of paracetamol was investigated using ion mobility spectrometry equipped with a corona discharge ionization source. The measurements were performed in the positive ion mode and three peaks were observed in the ion mobility spectrum. Experimental evidence and theoretical calculations were used to correlate the peaks to related ionic species of paracetamol. Two peaks were attributed to protonated isomers of paracetamol and the other peak was attributed to paracetamol fragment ions formed by dissociation of the N-C bond after protonation of the nitrogen atom. It was observed that three sites of paracetamol compete for protonation and their relative intensities, depending on the sample concentration. The ratio of ion products could be predicted from the internal proton affinity of the protonation sites at each concentration.

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.

The mixed alkali effect in ionically conducting glasses revisited: a study by molecular dynamics simulation.

PubMed

Habasaki, Junko; Ngai, Kia L

2007-09-07

When more than two kinds of mobile ions are mixed in ionic conducting glasses and crystals, there is a non-linear decrease of the transport coefficients of either type of ion. This phenomenon is known as the mixed mobile ion effect or Mixed Alkali Effect (MAE), and remains an unsolved problem. We use molecular dynamics simulation to study the complex ion dynamics in ionically conducting glasses including the MAE. In the mixed alkali lithium-potassium silicate glasses and related systems, a distinct part of the van Hove functions reveals that jumps from one kind of site to another are suppressed. Although, consensus for the existence of preferential jump paths for each kind of mobile ions seems to have been reached amongst researchers, the role of network formers and the number of unoccupied ion sites remain controversial in explaining the MAE. In principle, these factors when incorporated into a theory can generate the MAE, but in reality they are not essential for a viable explanation of the ion dynamics and the MAE. Instead, dynamical heterogeneity and "cooperativity blockage" originating from ion-ion interaction and correlation are fundamental for the observed ion dynamics and the MAE. Suppression of long range motion with increased back-correlated motions is shown to be a cause of the large decrease of the diffusivity especially in dilute foreign alkali regions. Support for our conclusion also comes from the fact that these features of ion dynamics are common to other ionic conductors, which have no glassy networks, and yet they all exhibit the MAE.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waltman, Melanie J.

2010-05-01

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

Human Mobility Monitoring in Very Low Resolution Visual Sensor Network

PubMed Central

Bo Bo, Nyan; Deboeverie, Francis; Eldib, Mohamed; Guan, Junzhi; Xie, Xingzhe; Niño, Jorge; Van Haerenborgh, Dirk; Slembrouck, Maarten; Van de Velde, Samuel; Steendam, Heidi; Veelaert, Peter; Kleihorst, Richard; Aghajan, Hamid; Philips, Wilfried

2014-01-01

This paper proposes an automated system for monitoring mobility patterns using a network of very low resolution visual sensors (30 × 30 pixels). The use of very low resolution sensors reduces privacy concern, cost, computation requirement and power consumption. The core of our proposed system is a robust people tracker that uses low resolution videos provided by the visual sensor network. The distributed processing architecture of our tracking system allows all image processing tasks to be done on the digital signal controller in each visual sensor. In this paper, we experimentally show that reliable tracking of people is possible using very low resolution imagery. We also compare the performance of our tracker against a state-of-the-art tracking method and show that our method outperforms. Moreover, the mobility statistics of tracks such as total distance traveled and average speed derived from trajectories are compared with those derived from ground truth given by Ultra-Wide Band sensors. The results of this comparison show that the trajectories from our system are accurate enough to obtain useful mobility statistics. PMID:25375754

High Resolution Observations of Escaping Ions in the Martian Magnetotail

NASA Astrophysics Data System (ADS)

Halekas, J. S.; Raman, C.; Brain, D.; DiBraccio, G. A.; Harada, Y.; McFadden, J. P.; Mitchell, D. L.; Connerney, J. E. P.; Jakosky, B. M.

2016-12-01

Ions escape from the Martian upper atmosphere via a number of channels, including the central plasmasheet of the magnetotail. Mars Express observations show that the heavy ions O+ and O2+ escaping through the central tail often have approximately the same energy, suggesting acceleration in a quasi-static electric field, which has been interpreted as a Hall electric field. The Solar Wind Ion Analyzer (SWIA) on MAVEN was designed to measure the upstream solar wind. However, during orbit segments with appropriate spacecraft attitude, SWIA can also make high resolution measurements of escaping ions in the tail. During the prime mission, these observations were only returned sporadically, during periods of intense escaping fluxes that fortuitously triggered a mode switch. Now, in the extended mission, we return high resolution observations from SWIA routinely. Some of these high resolution measurements reveal slight differences in both the direction and energy of escaping O+ and O2+ ions, which may help determine the acceleration process(es). We investigate the location and solar wind conditions for which the escaping ions separate in energy and angle and the systematics of their energies and flow vectors, and discuss the implications for ion acceleration and the overall picture of Martian atmospheric escape.

Stimulated Motion Suppression (STMS): a New Approach to Break the Resolution Barrier for Ion Trap Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhou, Xiaoyu; Liu, Xinwei; Chiang, Spencer; Cao, Wenbo; Li, Ming; Ouyang, Zheng

2018-05-01

Ion trap is an excellent platform to perform tandem mass spectrometry (MS/MS), but has an intrinsic drawback in resolving power. Using ion resonant ejection as an example, the resolution degradation can be largely attributed to the broadening of the resonant frequency band (RFB) between ion motion and driving alternative-current (AC). To solve this problem, stimulated motion suppression (STMS) was developed. The key idea of STMS is the use of two suppression alternative-current (SAC) signals, which both have reversed initial phases to the main AC. The SACs can block the unexpected sideband ion resonances (or ejections), therefore playing a key role in sharpening the RFB. The proof-of-concept has been demonstrated through ion trajectory simulations and validated experimentally. STMS provides a new and versatile means for the improvement of the ion trap resolution, which for a long time has reached the bottleneck through conventional methods, e.g., increasing the radio-frequency (RF) voltage and decreasing the mass scan rate. At the end, it is worth noting that the idea of STMS is very general and principally can be applied in any RF device for the purposes of high-resolution mass analysis and ion isolation.

Combining Structural Probes in the Gas Phase - Ion Mobility- Resolved Action-FRET

NASA Astrophysics Data System (ADS)

Daly, Steven; MacAleese, Luke; Dugourd, Philippe; Chirot, Fabien

2018-01-01

In the context of native mass spectrometry, the development of gas-phase structural probes sensitive to the different levels of structuration of biomolecular assemblies is necessary to push forward conformational studies. In this paper, we provide the first example of the combination of ion mobility (IM) and Förster resonance energy transfer (FRET) measurements within the same experimental setup. The possibility to obtain mass- and mobility-resolved FRET measurements is demonstrated on a model peptide and applied to monitor the collision-induced unfolding of ubiquitin. [Figure not available: see fulltext.

Fast detection of toxic industrial compounds by laser ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Oberhuettinger, Carola; Langmeier, Andreas; Oberpriller, Helmut; Kessler, Matthias; Goebel, Johann; Mueller, Gerhard

2009-05-01

Trace detection of toxic industrial compounds has been investigated with the help of a laser ion mobility spectrometer (LIMS). The LIMS was equipped with a tuneable UV laser source for enabling two-photon ionization of the analyte gases and an ion drift tube for the measurement of the ion mobility. Different aromatic and aliphatic hydrocarbons as well as amines were investigated. We find that the first class of molecules can be well ionized due to the delocalization of their valence electron shells and the second due to the presence of non-bonding electrons in lone-pair orbitals. Selectivity of detection is attained on the basis of molecule-specific photo-ionization and drift time spectra. Ion currents were found to scale linearly with the substance concentration over several orders of magnitude down to the detection limits in the ppt range. As besides toxic industrial compounds, similar electron configurations also occur in illicit drugs, toxins and pharmaceutical substances, LIMS can be applied in a variety of fields ranging from environmental analysis, air pollution monitoring, drug detection and chemical process monitoring.

Neural network recognition of chemical class information in mobility spectra obtained at high temperatures

NASA Technical Reports Server (NTRS)

Bell, S.; Nazarov, E.; Wang, Y. F.; Rodriguez, J. E.; Eiceman, G. A.

2000-01-01

A minimal neural network was applied to a large library of high-temperature mobility spectra drawn from 16 chemical classes including 154 substances with 2000 spectra at various concentrations. A genetic algorithm was used to create a representative subset of points from the mobility spectrum as input to a cascade-type back-propagation network. This network demonstrated that significant information specific to chemical class was located in the spectral region near the reactant ions. This network failed to generalize the solution to unfamiliar compounds necessitating the use of complete spectra in network processing. An extended back-propagation network classified unfamiliar chemicals by functional group with a mean for average values of 0.83 without sulfides and 0.79 with sulfides. Further experiments confirmed that chemical class information was resident in the spectral region near the reactant ions. Deconvolution of spectra demonstrated the presence of ions, merged with the reactant ion peaks that originated from introduced samples. The ability of the neural network to generalize the solution to unfamiliar compounds suggests that these ions are distinct and class specific.

Design of a TW-SLIM Module for Dual Polarity Confinement, Transport, and Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garimella, Sandilya V. B.; Webb, Ian K.; Prabhakaran, Aneesh

2017-05-30

Here we describe instrumental approaches for performing dual polarity ion confinement, transport, ion mobility separations and reactions in Structures for Lossless Ion Manipulations (SLIM). Previous means of ion confinement in SLIM based upon rf- generated pseudopotentials and dc fields for lateral confinement cannot trap ions of opposite polarity simultaneously. Here we explore alternative approaches to provide lateral confinement of both ion polarities. Traveling wave ion mobility (IM) separations experienced by both polarities in such SLIM cause ions of both polarities migrate in the same directions and exhibit similar separations. The ion motion (and relative motion of the two polarities) undermore » both surfing and IM separation conditions are discussed. Strategies to separate the two populations to minimize reactive losses during transport are presented. A theoretical treatment of the time scales over which two populations (injected into a dc field-free region of the dual polarity SLIM device) interact is considered, and SLIM designs for allowing ion/ion interactions and other manipulations with dual polarities at 4 torr are presented.« less

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burrows, T.A.; Thoma, P.J.

Two types of ion-mobility detectors were evaluated in both laboratory and field tests. Laboratory test results show that these detectors are highly sensitive to dynamite and pistol powder and have good false-alarm agent rejection. Field tests of these two detectors revealed that they would detect dynamite and Ball-C-Propellent in free air. However, neither of the ion-mobility detectors would detect these explosives if the explosives were concealed.

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

PubMed

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

2015-11-01

In this work a rapid and simple method for creatinine determination in urine and plasma samples based on aqueous derivatization of creatinine and complete vaporization of sample (as low as 10 µL), followed by ion mobility spectrometry analysis has been proposed. The effect of four important parameters (extraction temperature, total volume of solution, desorption temperature and extraction time) on ion mobility signal has been studied. Under the optimized conditions, the quantitative response of ion mobility spectrometry for creatinine was linear in the range of 0-500 mg L(-1) with a detection limit of 0.6 mg L(-1) in urine and 0-250 mg L(-1) with a detection limit of 2.6 mg L(-1) in plasma sample. The limit of quantitation of creatinine was 2.1 mg L(-1) and 8.7 mg L(-1) in urine and plasma samples, respectively. The relative standard deviation of the method was found to be 13%. The method was successfully applied to the analysis of creatinine in biological samples, showing recoveries from 92% to 104% in urine and 101-110% in plasma samples. Copyright © 2015 Elsevier B.V. All rights reserved.

High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal.

PubMed

Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Haskey, S R; Kaplan, D H

2016-11-01

A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. The unique combination of experimentally measured main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling

NASA Astrophysics Data System (ADS)

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

2016-03-01

Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H]2- ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H]3- ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H]2- ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H]3- ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

Rapid analysis of pesticide residues in drinking water samples by dispersive solid-phase extraction based on multiwalled carbon nanotubes and pulse glow discharge ion source ion mobility spectrometry.

PubMed

Zou, Nan; Gu, Kejia; Liu, Shaowen; Hou, Yanbing; Zhang, Jialei; Xu, Xiang; Li, Xuesheng; Pan, Canping

2016-03-01

An analytical method based on dispersive solid-phase extraction with a multiwalled carbon nanotubes sorbent coupled with positive pulse glow discharge ion mobility spectrometry was developed for analysis of 30 pesticide residues in drinking water samples. Reduced ion mobilities and the mass-mobility correlation of 30 pesticides were measured. The pesticides were divided into five groups to verify the separation capability of pulse glow discharge in mobility spectrometry. The extraction conditions such as desorption solvent, ionic strength, conditions of adsorption and desorption, the amounts of multiwalled carbon nanotubes, and solution pH were optimized. The enrichment factors of pesticides were 5.4- to 48.7-fold (theoretical enrichment factor was 50-fold). The detection limits of pesticides were 0.01∼0.77 μg/kg. The linear range was 0.005-0.2 mg/L for pesticide standard solutions, with determination coefficients from 0.9616 to 0.9999. The method was applied for the analysis of practical and spiked drinking water samples. All results were confirmed by high-performance liquid chromatography with tandem mass spectrometry. The proposed method was proven to be a commendably rapid screening qualitative and semiquantitative technique for the analysis of pesticide residues in drinking water samples on site. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Child-Langmuir law applicability for a cathode sheath description of glow discharge in hydrogen

NASA Astrophysics Data System (ADS)

Lisovskiy, V. A.; Artushenko, K. P.; Yegorenkov, V. D.

2016-08-01

The present paper reveals that the Child-Langmuir law version with the constant ion mobility has to be applied for the cathode sheath description of the glow discharge in hydrogen. Using the analytical model we demonstrate that even in a high electric field the constant mobility law version rather than that for the constant ion mean free path has to hold in the case of impeded charge exchange and the dominant effect of polarization forces on the ion motion through the cathode sheath.

SiC detectors to monitor ionizing radiations emitted from nuclear events and plasmas

NASA Astrophysics Data System (ADS)

Torrisi, L.; Cannavò, A.

2016-09-01

Silicon Carbide (SiC) semiconductor detectors are increasingly employed in Nuclear Physics for their advantages with respect to traditional silicon (Si). Such detectors show an energy resolution, charge mobility, response velocity and detection efficiency similar to Si detectors. However, the higher band gap (3.26 eV), the lower leakage current (∼10 pA) maintained also at room temperature, the higher radiation hardness and the higher density with respect to Si represent some indisputable advantages characterizing such detectors. The devices can be employed at high temperatures, at high absorbed doses and in the case of high visible light intensities, for example, in plasma, for limited exposition times without damage. Generally SiC Schottky diodes are employed in reverse polarization with an active region depth of the order of 100 µm, purity below 1014 cm-3 and an active area lower than 1 cm2. Measurements in the regime of proportionality with the radiation energy released in the active region and measurements in time-of-flight configuration are employed for nuclear emission events produced at both low and high fluences. Alpha spectra demonstrated an energy resolution of about 1.3% at 5.8 MeV. Radiation emission from laser-generated plasma can be monitored in terms of detected photons, electrons and ions, using the laser pulse as a start signal and the radiation detection as a stop signal, enabling to measure the ion velocity by knowing the target-detector flight distance. SiC spectra acquired in the Messina University laboratories using radioactive ion sources and at the PALS laboratory facility in Prague (Czech Republic) are presented. A preliminary study of the use of SiC detectors, embedded in a water equivalent polymer, as a dosimeter is presented and discussed.

Mixed mode HILIC/anion exchange separations on latex coated silica monoliths.

PubMed

Ibrahim, Mohammed E A; Lucy, Charles A

2012-10-15

Bare silica monoliths do not possess anion exchange sites hence they show low retention for anions. Moreover, bare silica monoliths show low retention in hydrophilic interaction liquid chromatography (HILIC). Coating the silica surface with cationic nanoparticles e.g. AS9-SC (latex A), AS12A (latex B) and DNApac (latex C) increases the thickness of the water layer on the Onyx silica monolith 8-10 times enabling HILIC retention when a high % acetonitrile (ACN) mobile phase is used. The formed water layer by itself is not sufficient to perform good separation of the studied anions (acetate, formate, nitrate, bromate, thiocyanate and iodide). On the other hand, the latex nanoparticles introduce positively charged sites, making anion exchange chromatography possible, with the anion exchange capacity varying with the latex adsorbed (44.1 ± 0.2, 4.4 ± 0.1 and 14.0 ± 0.7 μeq/column for latex A, B and C, respectively). Latex A nanoparticles which provided the highest ion exchange capacity separated all tested anions with reasonable resolution. Fast separation (2.5 min) of acetate, formate, nitrate, bromate, thiocyanate and iodide was performed using the latex A coated silica monolith. The obtained efficiencies are 13,000-50,000 plates/m at 3 mL/min with a minimum resolution of 0.85. Retention is mixed mode under HILIC conditions with HILIC dominating for the kosmotropic anions and ion exchange dominating for the chaotropic anions. The two different brands of silica monoliths (Merck Chromolith and Phenomenex Onyx) coated with the same latex A nanoparticles displayed similar water layer volumes, ion exchange capacity and selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.

Detection of designer drugs in human hair by ion mobility spectrometry (IMS).

PubMed

Keller, T; Miki, A; Regenscheit, P; Dirnhofer, R; Schneider, A; Tsuchihashi, H

1998-06-08

Since its inception in the early 1970s under the name plasma chromatography, ion mobility spectrometry (IMS) has undergone great changes. It is now utilized more and more in forensic science laboratories where it is used to detect explosives and environmental pollutants [1-4] as well as its use in detecting drugs of abuse [5-8]. Although IMS is known for nearly 30 years now [9], relatively few cases of the application of ion mobility spectrometry to the analysis of human hair have been reported [10-12]. The authors report a new and quick method to rapidly screen and determine MDMA ('ecstasy', 'Adam') and MDEA ('Eve') in human hair. The proposed method using trihexylamine as internal standard resulted in a rapid procedure useful in screening human hair specimens for designer drugs.

THOR Ion Mass Spectrometer (IMS)

NASA Astrophysics Data System (ADS)

Retinò, Alessandro

2017-04-01

Turbulence Heating ObserveR (THOR) is the first mission ever flown in space dedicated to plasma turbulence. The Ion Mass Spectrometer (IMS) onboard THOR will provide the first high-time resolution measurements of mass-resolved ions in near-Earth space, focusing on hot ions in the foreshock, shock and magnetosheath turbulent regions. These measurements are required to study how kinetic-scale turbulent fluctuations heat and accelerate different ion species. IMS will measure the full three-dimensional distribution functions of main ion species (H+, He++, O+) in the energy range 10 eV/q to 30 keV/q with energy resolution DE/E down to 10% and angular resolution down to 11.25˚ . The time resolution will be 150 ms for O+, 300 ms for He++ and ˜ 1s for O+, which correspond to ion scales in the the foreshock, shock and magnetosheath regions. Such high time resolution is achieved by mounting four identical IMS units phased by 90˚ in the spacecraft spin plane. Each IMS unit combines a top-hat electrostatic analyzer with deflectors at the entrance together with a time-of-flight section to perform mass selection. Adequate mass-per-charge resolution (M/q)/(ΔM/q) (≥ 8 for He++ and ≥ 3 for O+) is obtained through a 6 cm long Time-of-Flight (TOF) section. IMS electronics includes a fast sweeping high voltage board that is required to make measurements at high cadence. Ion detection includes Micro Channel Plates (MCPs) combined with Application-Specific Integrated Circuits (ASICs) for charge amplification and discrimination and a discrete Time-to-Amplitude Converter (TAC) to determine the ion time of flight. A processor board will be used to for ion events formatting and will interface with the Particle Processing Unit (PPU), which will perform data processing for THOR particle detectors. The IMS instrument is being designed and will be built and calibrated by an international consortium of scientific institutes from France, USA, Germany and Japan and Switzerland.

Fourier transform ion cyclotron resonance mass resolution and dynamic range limits calculated by computer modeling of ion cloud motion.

PubMed

Vladimirov, Gleb; Hendrickson, Christopher L; Blakney, Greg T; Marshall, Alan G; Heeren, Ron M A; Nikolaev, Eugene N

2012-02-01

Particle-in-Cell (PIC) ion trajectory calculations provide the most realistic simulation of Fourier transform ion cyclotron resonance (FT-ICR) experiments by efficient and accurate calculation of the forces acting on each ion in an ensemble (cloud), including Coulomb interactions (space charge), the electric field of the ICR trap electrodes, image charges on the trap electrodes, the magnetic field, and collisions with neutral gas molecules. It has been shown recently that ion cloud collective behavior is required to generate an FT-ICR signal and that two main phenomena influence mass resolution and dynamic range. The first is formation of an ellipsoidal ion cloud (termed "condensation") at a critical ion number (density), which facilitates signal generation in an FT-ICR cell of arbitrary geometry because the condensed cloud behaves as a quasi-ion. The second phenomenon is peak coalescence. Ion resonances that are closely spaced in m/z coalesce into one resonance if the ion number (density) exceeds a threshold that depends on magnetic field strength, ion cyclotron radius, ion masses and mass difference, and ion initial spatial distribution. These two phenomena decrease dynamic range by rapid cloud dephasing at small ion density and by cloud coalescence at high ion density. Here, we use PIC simulations to quantitate the dependence of coalescence on each critical parameter. Transitions between independent and coalesced motion were observed in a series of the experiments that systematically varied ion number, magnetic field strength, ion radius, ion m/z, ion m/z difference, and ion initial spatial distribution (the present simulations begin from elliptically-shaped ion clouds with constant ion density distribution). Our simulations show that mass resolution is constant at a given magnetic field strength with increasing ion number until a critical value (N) is reached. N dependence on magnetic field strength, cyclotron radius, ion mass, and difference between ion masses was determined for two ion ensembles of different m/z, equal abundance, and equal cyclotron radius. We find that N and dynamic range depend quadratically on magnetic field strength in the range 1-21 Tesla. Dependences on cyclotron radius and Δm/z are linear. N depends on m/z as (m/z)(-2). Empirical expressions for mass resolution as a function of each of the experimental parameters are presented. Here, we provide the first exposition of the origin and extent of trade-off between FT-ICR MS dynamic range and mass resolution (defined not as line width, but as the separation between the most closely resolved masses). © American Society for Mass Spectrometry, 2011

Integrated Chemical and Microorganism Monitoring of Air Using Gas Chromatography/Ion Mobility Spectometry: Toward an Expanded-Use Volatile Organic Analyzer (VOA)

NASA Technical Reports Server (NTRS)

Eiceman, G. A.

1999-01-01

The work described in this research program originated with the choice by NASA of an ion mobility spectrometer for air quality monitoring on-board the international spacestation. Though the gas chromatograph-ion mobility spectrometer analyzer known as VOA met or exceeded expectations, limitations in the basic understanding of response and the utilization of foundational principles into usable technology was considered unacceptable. In this research program, a comprehensive model for the origins of mobility spectra was proposed, tested and verified. The principles considered responsible for the appearance of mobility spectra have now been elucidated through this project. This understanding has been applied in automated identification of mobility spectra using neural networks and routine procedures for this now exist. Finally, the limitation on linear range has been shown to be a technical limitation and not a fundamental limitation so that a hardware component was crafted to extend the linear range of a mobility spectrometer by 10X. This project has led to one Ph.D. dissertation and one MS thesis. In addition, over ten public presentations at professional meetings and six journal publications have resulted from this program of research. The findings are so plentiful that total analysis of the findings may require four to six years or more. The findings confirm that the decision to use VOA was sound and that the chemical and physical principles of mobility spectrometry are both understandable and predictable.

Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

PubMed

Kiss, András; Smith, Donald F; Jungmann, Julia H; Heeren, Ron M A

2013-12-30

Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high-speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with polyatomic primary ion sources, are required to exploit the full potential of microscope mode mass spectrometry imaging, i.e. to efficiently push the limits of ultra-high spatial resolution, sample throughput and sensitivity. In this work, a C60 primary source was combined with a commercial mass microscope for microscope mode secondary ion mass spectrometry imaging. The detector setup is a pixelated detector from the Medipix/Timepix family with high-voltage post-acceleration capabilities. The system's mass spectral and imaging performance is tested with various benchmark samples and thin tissue sections. The high secondary ion yield (with respect to 'traditional' monatomic primary ion sources) of the C60 primary ion source and the increased sensitivity of the high voltage detector setup improve microscope mode secondary ion mass spectrometry imaging. The analysis time and the signal-to-noise ratio are improved compared with other microscope mode imaging systems, all at high spatial resolution. We have demonstrated the unique capabilities of a C60 ion microscope with a Timepix detector for high spatial resolution microscope mode secondary ion mass spectrometry imaging. Copyright © 2013 John Wiley & Sons, Ltd.

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

Contaminant screening of wastewater with HPLC-IM-qTOF-MS and LC+LC-IM-qTOF-MS using a CCS database.

PubMed

Stephan, Susanne; Hippler, Joerg; Köhler, Timo; Deeb, Ahmad A; Schmidt, Torsten C; Schmitz, Oliver J

2016-09-01

Non-target analysis has become an important tool in the field of water analysis since a broad variety of pollutants from different sources are released to the water cycle. For identification of compounds in such complex samples, liquid chromatography coupled to high resolution mass spectrometry are often used. The introduction of ion mobility spectrometry provides an additional separation dimension and allows determining collision cross sections (CCS) of the analytes as a further physicochemical constant supporting the identification. A CCS database with more than 500 standard substances including drug-like compounds and pesticides was used for CCS data base search in this work. A non-target analysis of a wastewater sample was initially performed with high performance liquid chromatography (HPLC) coupled to an ion mobility-quadrupole-time of flight mass spectrometer (IM-qTOF-MS). A database search including exact mass (±5 ppm) and CCS (±1 %) delivered 22 different compounds. Furthermore, the same sample was analyzed with a two-dimensional LC method, called LC+LC, developed in our group for the coupling to IM-qTOF-MS. This four dimensional separation platform revealed 53 different compounds, identified over exact mass and CCS, in the examined wastewater sample. It is demonstrated that the CCS database can also help to distinguish between isobaric structures exemplified for cyclophosphamide and ifosfamide. Graphical Abstract Scheme of sample analysis and database screening.

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Structure and mechanisms underlying ion transport in ternary polymer electrolytes containing ionic liquids

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

We use all atom molecular dynamics simulations to investigate the influence of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) ionic liquid on the structure and transport properties of poly(ethylene oxide) (PEO) polymer electrolytes doped with LiPF6 salt. We observe enhanced diffusivities of the Li+, PF6-, and BMIM+ ions with increasing loading of the ionic liquid. Interplay between the different ion-ion and ion-polymer interactions is seen to lead to a destabilization of the Li-PF6 coordination and increase in the strength of association between the Li+ cations and the polymer backbone. As a consequence, the polymer segmental relaxation times are shown to be only moderately affected by the addition of ionic liquids. The ionic-liquid induced changes in the mobilities of Li+ ions are seen to be correlated to polymer segmental relaxation times. However, the mobilities of BMIM+ ions are seen to be more strongly correlated to the BMIM-PF6 ion-pair relaxation times.

Comparison of single-ion molecular dynamics in common solvents

NASA Astrophysics Data System (ADS)

Muralidharan, A.; Pratt, L. R.; Chaudhari, M. I.; Rempe, S. B.

2018-06-01

Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li+ and PF6- ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. We provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF6-), velocity relaxations are all similar: negative tail relaxations for the VACF and a clear second relaxation for γ (t ), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li+ ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ (t ). But the corresponding analysis of the solventberg Li+(H2O)4 does conform to the standard picture set by all the PF6- results.

JLTV - Briefings to Industry, Ground Vehicle Power and Mobility (GVPM)

DTIC Science & Technology

2009-05-27

lithium ion battery cathodes, separators, and electrolytes. This effort shall also access the...manufacturability of the improved designs using the new materials. PAYOFF: Improved lithium ion battery power density Improved lithium ion battery energy...negative electrodes in lithium-ion batteries. PAYOFF: Better understanding of lithium - ion battery charging limitations Improved safety for

High resolution measurements of nightside ion troughs at Venus - Evidence of electrodynamic perturbations

NASA Technical Reports Server (NTRS)

Taylor, H. A., Jr.; Grebowsky, J. M.; Mayr, H. G.; Niemann, H. B.; Brace, L. H.; Cloutier, P. A.; Daniell, R. E., Jr.; Coulson, J. T.

1982-01-01

The Bennett rf ion mass spectrometer of the Pioneer Venus Orbiter was expressly designed to provide variable temporal resolution for measurements of thermal ion composition and density. The Explore-Adapt mode is used to obtain priority for measuring the most prominent ion species; in the 2/16 configuration, the two dominant ions within the available range of 16 species are selectively sampled at the highest rate of 0.2 sec/sample. The high-resolution measurements are combined with independent observations from the magnetic field, neutral mass spectrometer, and electron temperature experiments in investigating sharply structured troughs in the low-altitude nightside ion concentrations. The results suggest a close correlation between the structure in the ion distributions and the structured configuration of the magnetic field that is draped about the planet. In the regions of the ion depletions, sharp fluctuations in electron temperature and anomalous increases in the density of neutral gases suggest that the ion depletion may be associated with dynamic perturbation in the ion and neutral flows and/or local joule heating.

High-resolution grazing-incidence grating spectrometer for temperature measurements of low-Z ions emitting in the 100–300 Å spectral band

DOE PAGES

Widmann, K.; Beiersdorfer, P.; Magee, E. W.; ...

2014-09-19

In this paper, we have constructed a high-resolution grazing-incidence spectrometer designed for measuring the ion temperature of low-Z elements, such as Li + or Li 2 +, which radiate near 199 Å and 135 Å, respectively. Based on measurements at the Livermore Electron Beam Ion Trap we have shown that the instrumental resolution is better than 48 mÅ at the 200 Å setting and better than 40 mÅ for the 135-Å range. Such a high spectral resolution corresponds to an instrumental limit for line-width based temperature measurements of about 45 eV for the 199 Å Li+ and 65 eV formore » the 135 Å Li 2 + lines. Finally, recently obtained survey spectra from the Lithium Tokamak Experiment at the Princeton Plasma Physics Laboratory show the presence of these lithium emission lines and the expected core ion temperature of approximately 70 eV is sufficiently high to demonstrate the feasibility of utilizing our high-resolution spectrometer as an ion-temperature diagnostic.« less

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

PubMed Central

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

2014-01-01

An ion mobility/time-of-flight mass spectrometer (IMS/TOF MS) platform that allows for resonant excitation collision induced dissociation (CID) is presented. Highly efficient, mass-resolved fragmentation without additional excitation of product ions was accomplished and over-fragmentation common in beam-type CID experiments was alleviated. A quadrupole ion guide was modified to apply a dipolar AC signal across a pair of rods for resonant excitation. The method was characterized with singly protonated methionine enkephalin and triply protonated peptide angiotensin I, yielding maximum CID efficiencies of 44% and 84%, respectively. The Mathieu qx,y parameter was set at 0.707 for these experiments to maximize pseudopotential well depths and CID efficiencies. Resonant excitation CID was compared to beam-type CID for the peptide mixture. The ability to apply resonant waveforms in mobility-resolved windows is demonstrated with a peptide mixture yielding fragmentation over a range of mass-to-charge (m/z) ratios within a single IMS-MS analysis. PMID:24470195

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

Corona discharge ionization of paracetamol molecule: peak assignment.

PubMed

Bahrami, H; Farrokhpour, H

2015-01-25

Ionization of paracetamol was investigated using ion mobility spectrometry equipped with a corona discharge ionization source. The measurements were performed in the positive ion mode and three peaks were observed in the ion mobility spectrum. Experimental evidence and theoretical calculations were used to correlate the peaks to related ionic species of paracetamol. Two peaks were attributed to protonated isomers of paracetamol and the other peak was attributed to paracetamol fragment ions formed by dissociation of the N-C bond after protonation of the nitrogen atom. It was observed that three sites of paracetamol compete for protonation and their relative intensities, depending on the sample concentration. The ratio of ion products could be predicted from the internal proton affinity of the protonation sites at each concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal

DOE PAGES

Grierson, B. A.; Burrell, K. H.; Chrystal, C.; ...

2016-09-12

A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. Furthermore, the unique combination of experimentally measuredmore » main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.« less

Interpenetrating polymer network ion exchange membranes and method for preparing same

DOEpatents

Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

1989-01-01

Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY – HIGH RESOLUTION MASS SPECTROMETRY

PubMed Central

Nikcevic, Irena; Wyrzykiewicz, Tadeusz K.; Limbach, Patrick A.

2010-01-01

Summary An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described. Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3′-terminal phosphate monoester and 3′-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N3 (2-cyanoethyl) adducts of the full length product. When compared with low resolution LC-MS, ~60% more impurities can be identified when charge state and isotopic distribution information is available and used for impurity profiling. PMID:21811394

Transition metal impurities in the solid electrolyte LLZO (Li7La3Zr2O12) : Transport rates and their impact on Li-ion mobility

NASA Astrophysics Data System (ADS)

Yang, Sheng; Siegel, Donald

LLZO has many properties of an ideal solid electrolyte in lithium-ion batteries since it could enable the use of high voltage electrodes and hence enhance the energy density of lithium ion batteries. With supervalent cation doping such as Al3+, Ga3+ on the Li-site, the room temperature ionic conductivity of the cubic LLZO can accomplish high ionic conductivity up to 1mS/cm. However, some experiments suggest that mutual diffusion layers were formed between LLZO and cathode where transition metal (TM) diffused into LLZO, which could possibly lead to large interfacial resistance. In this study, we quantified the performance of LLZO after doping with cobalt, manganese, iron and nickel. In particular, we used molecular dynamics simulations with empirical Morse-type potentials to investigate the TM transport rates and their impact on Li-ion mobility. Our work indicates that TM impurities diffuse slower than Li-ion and they will result in a decrease in the Li-ion mobility by blocking Li-ion pathways. Our work shines light on the origin of interfacial resistance between LLZO and different cathodes. This work was supported by U.S. Department Energy's U.S.- China Clean Energy Research Center Clean Vehicles Consortium (CERC CVC), Grant No. DE-PI0000012.

Shot-noise-limited monitoring and phase locking of the motion of a single trapped ion.

PubMed

Bushev, P; Hétet, G; Slodička, L; Rotter, D; Wilson, M A; Schmidt-Kaler, F; Eschner, J; Blatt, R

2013-03-29

We perform a high-resolution real-time readout of the motion of a single trapped and laser-cooled Ba+ ion. By using an interferometric setup, we demonstrate a shot-noise-limited measurement of thermal oscillations with a resolution of 4 times the standard quantum limit. We apply the real-time monitoring for phase control of the ion motion through a feedback loop, suppressing the photon recoil-induced phase diffusion. Because of the spectral narrowing in the phase-locked mode, the coherent ion oscillation is measured with a resolution of about 0.3 times the standard quantum limit.

Linking molecular models with ion mobility experiments. Illustration with a rigid nucleic acid structure

PubMed Central

D'Atri, Valentina; Porrini, Massimiliano; Rosu, Frédéric; Gabelica, Valérie

2015-01-01

Ion mobility spectrometry experiments allow the mass spectrometrist to determine an ion's rotationally averaged collision cross section ΩEXP. Molecular modelling is used to visualize what ion three-dimensional structure(s) is(are) compatible with the experiment. The collision cross sections of candidate molecular models have to be calculated, and the resulting ΩCALC are compared with the experimental data. Researchers who want to apply this strategy to a new type of molecule face many questions: (1) What experimental error is associated with ΩEXP determination, and how to estimate it (in particular when using a calibration for traveling wave ion guides)? (2) How to generate plausible 3D models in the gas phase? (3) Different collision cross section calculation models exist, which have been developed for other analytes than mine. Which one(s) can I apply to my systems? To apply ion mobility spectrometry to nucleic acid structural characterization, we explored each of these questions using a rigid structure which we know is preserved in the gas phase: the tetramolecular G-quadruplex [dTGGGGT]4, and we will present these detailed investigation in this tutorial. © 2015 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26259654

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

PubMed

Lee, Jihyeon; Park, Sehwan; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sung-Suk; Kim, Jeongkwon

2014-03-01

Corona discharge ionization combined with ion mobility spectrometry-mass spectrometry (IMS-MS) was utilized to investigate five common explosives: cyclonite (RDX), trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), cyclotetramethylenetetranitramine (HMX), and 2,4-dinitrotoluene (DNT). The MS scan and the selected ion IMS analyses confirmed the identities of the existing ion species and their drift times. The ions observed were RDX·NO3(-), TNT(-), PETN·NO3(-), HMX·NO3(-), and DNT(-), with average drift times of 6.93 ms, 10.20 ms, 9.15 ms, 12.24 ms, 11.30 ms, and 8.89 ms, respectively. The reduced ion mobility values, determined from a standard curve calculated by linear regression of (normalized drift times)(-1) versus literature K0 values, were 2.09, 1.38, 1.55, 1.15, 1.25, and 1.60 cm(2) V(-1) s(-1), respectively. The detection limits were found to be 0.1 ng for RDX, 10 ng for TNT, 0.5 ng for PETN, 5.0 ng for HMX, and 10 ng for DNT. Simplified chromatograms were observed when nitrogen, as opposed to air, was used as the drift gas, but the detection limits were approximately 10 times worse (i.e., less sensitivity of detection). © 2013 Elsevier B.V. All rights reserved.

The use of dopants in high field asymmetric waveform spectrometry.

PubMed

Ross, Stuart K; McDonald, Gwenda; Marchant, Sarah

2008-05-01

Ion mobility spectrometry (IMS) is proven core technology for the gas-phase detection of chemical warfare (CW) agents. One disadvantage of IMS technology is that ions of similar mobility cannot readily be resolved, resulting in false alarm responses and a loss of user confidence. High field asymmetric waveform spectrometry (HiFAWS) is an emerging technology for the gas-phase detection of CW agents. Of particular interest is the potential of a HiFAWS-based platform to reduce the number of false alarms by resolving ions that cannot be discriminated using IMS. It has been demonstrated that a water clustering/declustering mechanism can be a dominant process in HiFAWS. Ions that cannot be discriminated in IMS because they possess the same low field mobility value can be resolved using HiFAWS due to differences in the extent of low field ion solvation and high field ion desolvation. When operating in complex environments such as those potentially experienced in military and security arenas, IMS systems commonly employ internal dopants to reduce the number of background responses. It is possible that HiFAWS systems may also require the use of internal dopants for the same reason. It has been demonstrated that dopants employed for use in IMS may not be suitable for use in HiFAWS.

Influence of ion sterics on diffusiophoresis and electrophoresis in concentrated electrolytes

NASA Astrophysics Data System (ADS)

Stout, Robert F.; Khair, Aditya S.

2017-01-01

We quantify the diffusiophoresis and electrophoresis of a uniformly charged, spherical colloid in a binary electrolyte using modified Poisson-Nernst-Planck equations that account for steric repulsion between finite sized ions. Specifically, we utilize the Bikerman (Bik) lattice gas model and the Carnahan-Starling (CS) and Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equations of state for monodisperse and polydisperse, respectively, hard spheres. We compute the phoretic mobility for weak applied fields using an asymptotic approach for thin diffuse layers, where ion steric effects are expected to be most prevalent. The thin diffuse layer limit requires λD/R →0 , where λD is the Debye screening length and R is the particle radius; this limit is readily attained for micron-sized colloids in concentrated electrolytic solutions. It is well known that the classic Poisson-Boltzmann (PB) model for pointlike, noninteracting ions leads to a prediction of a maximum in both the diffusiophoretic and electrophoretic mobilities with increasing particle zeta potential (at fixed λD/R ). In contrast, we find that ion sterics essentially eliminate this maximum (for reasonably attainable zeta potentials) and increase the mobility relative to PB. Next, we consider the more experimentally relevant case of a particle with a constant surface charge density and vary the electrolyte concentration, neglecting charge regulation on surface active sites. Rather surprisingly, there is little difference between the predictions of the four models (PB, Bik, CS, and BMCSL) for electrophoretic mobility in concentrated solutions, at reasonable surface charge densities (˜1 -10 μ C /cm2 ). This is because as the concentration increases, the zeta potential is reduced (to below the thermal voltage for concentrations above about 1 M) and therefore the diffuse layer structure is largely unaffected by ion sterics. For gradients of symmetric electrolytes (equal diffusivities, charge, and size) diffusiophoresis is also essentially unaffected by ion sterics, with a mobility that approaches zero with increasing concentration, just as in electrophoresis. For gradients of asymmetric electrolytes, the difference in diffusivities of the cation and anions leads to an induced electric field that acts on the charged particle. Importantly, we show that ion sterics leads to an excess contribution to the induced electric field, which increases rapidly with concentration. This increase overwhelms the accompanying decrease in zeta potential. The result is the diffusiophoretic mobility increases with concentration, rather than approaching zero. Therefore, diffusiophoresis could be an appealing alternative transport mechanism to electrophoresis in concentrated electrolyte solutions.

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.

High-resolution fluence verification for treatment plan specific QA in ion beam radiotherapy

NASA Astrophysics Data System (ADS)

Martišíková, Mária; Brons, Stephan; Hesse, Bernd M.; Jäkel, Oliver

2013-03-01

Ion beam radiotherapy exploits the finite range of ion beams and the increased dose deposition of ions toward the end of their range in material. This results in high dose conformation to the target region, which can be further increased using scanning ion beams. The standard method for patient-plan verification in ion beam therapy is ionization chamber dosimetry. The spatial resolution of this method is given by the distance between the chambers (typically 1 cm). However, steep dose gradients created by scanning ion beams call for more information and improved spatial resolution. Here we propose a clinically applicable method, supplementary to standard patient-plan verification. It is based on ion fluence measurements in the entrance region with high spatial resolution in the plane perpendicular to the beam, separately for each energy slice. In this paper the usability of the RID256 L amorphous silicon flat-panel detector for the measurements proposed is demonstrated for carbon ion beams. The detector provides sufficient spatial resolution for this kind of measurement (pixel pitch 0.8 mm). The experiments were performed at the Heidelberg Ion-Beam Therapy Center in Germany. This facility is equipped with a synchrotron capable of accelerating ions from protons up to oxygen to energies between 48 and 430 MeV u-1. Beam application is based on beam scanning technology. The measured signal corresponding to single energy slices was translated to ion fluence on a pixel-by-pixel basis, using calibration, which is dependent on energy and ion type. To quantify the agreement of the fluence distributions measured with those planned, a gamma-index criterion was used. In the patient field investigated excellent agreement was found between the two distributions. At least 95% of the slices contained more than 96% of points agreeing with our criteria. Due to the high spatial resolution, this method is especially valuable for measurements of strongly inhomogeneous fluence distributions like those in intensity-modulated treatment plans or plans including dose painting. Since no water phantom is needed to perform measurements, the flat-panel detector investigated has high potential for use with gantries. Before the method can be used in the clinical routine, it has to be sufficiently tested for each detector-facility combination.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berl, M., E-mail: mberl@phys.ethz.ch; Tiemann, L.; Dietsche, W.

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,more » thus minimizing the probability for electrical shorts or leakage and permitting simple contacting schemes.« less

Ion mobility-mass spectrometry as a tool to investigate protein-ligand interactions.

PubMed

Göth, Melanie; Pagel, Kevin

2017-07-01

Ion mobility-mass spectrometry (IM-MS) is a powerful tool for the simultaneous analysis of mass, charge, size, and shape of ionic species. It allows the characterization of even low-abundant species in complex samples and is therefore particularly suitable for the analysis of proteins and their assemblies. In the last few years even complex and intractable species have been investigated successfully with IM-MS and the number of publications in this field is steadily growing. This trend article highlights recent advances in which IM-MS was used to study protein-ligand complexes and in particular focuses on the catch and release (CaR) strategy and collision-induced unfolding (CIU). Graphical Abstract Native mass spectrometry and ion mobility-mass spectrometry are versatile tools to follow the stoichiometry, energetics, and structural impact of protein-ligand binding.

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.

Collision induced unfolding of isolated proteins in the gas phase: past, present, and future.

PubMed

Dixit, Sugyan M; Polasky, Daniel A; Ruotolo, Brandon T

2018-02-01

Rapidly characterizing the three-dimensional structures of proteins and the multimeric machines they form remains one of the great challenges facing modern biological and medical sciences. Ion mobility-mass spectrometry based techniques are playing an expanding role in characterizing these functional complexes, especially in drug discovery and development workflows. Despite this expansion, ion mobility-mass spectrometry faces many challenges, especially in the context of detecting small differences in protein tertiary structure that bear functional consequences. Collision induced unfolding is an ion mobility-mass spectrometry method that enables the rapid differentiation of subtly-different protein isoforms based on their unfolding patterns and stabilities. In this review, we summarize the modern implementation of such gas-phase unfolding experiments and provide an overview of recent developments in both methods and applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Micro faraday-element array detector for ion mobility spectroscopy

DOEpatents

Gresham, Christopher A [Albuquerque, NM; Rodacy, Phillip J [Albuquerque, NM; Denton, M Bonner [Tucson, AZ; Sperline, Roger [Tucson, AZ

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.

Atmospheric Solid Analysis Probe Coupled to Ion Mobility Spectrometry-Mass Spectrometry, a Fast and Simple Method for Polyalphaolefin Characterization

NASA Astrophysics Data System (ADS)

Mendes Siqueira, Anna Luiza; Beaumesnil, Mathieu; Hubert-Roux, Marie; Loutelier-Bourhis, Corinne; Afonso, Carlos; Bai, Yang; Courtiade, Marion; Racaud, Amandine

2018-05-01

Polyalphaolefins (PAOs) are polymers produced from linear alpha olefins through catalytic oligomerization processes. The PAOs are known as synthetic high-performance base stock fluids used to improve the efficiency of many other synthetic products. In this study, we report the direct characterization of PAOs using atmospheric solid analysis probe (ASAP) coupled with ion mobility spectrometry-mass spectrometry (IMS-MS). We studied different PAOs grades exhibiting low- and high-viscosity index. Specific adjustments of the ASAP source parameters permitted the monitoring of ionization processes as three mechanisms could occur for these compounds: hydride abstraction, nitrogen addition, and/or the formation of [M-2H]+• ions. Several series of fragment ions were obtained, which allowed the identification of the alpha olefin used to synthesize the PAO. The use of the ion mobility separation dimension provides information on isomeric species. In addition, the drift time versus m/z plots permitted rapid comparison between PAO samples and to evidence their complexity. These 2D plots appear as fingerprints of PAO samples. To conclude, the resort to ASAP-IMS-MS provides a rapid characterization of the PAO samples in a direct analysis approach, without any sample preparation.

Mixed-Isotope Labeling with LC-IMS-MS for Characterization of Protein–Protein Interactions by Chemical Cross-Linking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merkley, Eric D.; Baker, Erin S.; Crowell, Kevin L.

2013-02-20

Chemical cross-linking of proteins followed by proteolysis and mass spectrometric analysis of the resulting cross-linked peptides can provide insights into protein structure and protein-protein interactions. However, cross-linked peptides are by necessity of low stoichometry and have different physicochemical properties than linear peptides, routine unambiguous identification of the cross-linked peptides has remained difficult. To address this challenge, we demonstrated the use of liquid chromatography and ion mobility separations coupled with mass spectrometry in combination with a heavy-isotope labeling method. The combination of mixed-isotope cross-linking and ion mobility provided unique and easily interpretable spectral multiplet features for the intermolecular cross-linked peptides. Applicationmore » of the method to two different homodimeric proteins - SrfN, a virulence factor from Salmonella Typhimurium and SO_2176, a protein of unknown function from Shewanella oneidensis- revealed several cross-linked peptides from both proteins that were identified with a low false discovery rate (estimated using a decoy approach). A greater number of cross-linked peptides were identified using ion mobility drift time information in the analysis than when the data were summed across the drift time dimension before analysis. The identified cross-linked peptides migrated more quickly in the ion mobility drift tube than the unmodified peptides.« less

Collision cross section measurements for biomolecules within a high-resolution FT-ICR cell: theory.

PubMed

Guo, Dan; Xin, Yi; Li, Dayu; Xu, Wei

2015-04-14

In this study, an energetic hard-sphere ion-neutral collision model was proposed to bridge-link ion collision cross section (CCS) with the image current collected from a high-resolution Fourier transform ion cyclotron resonance (FT-ICR) cell. By investigating the nonlinear effects induced by high-order electric fields and image charge forces, the energetic hard-sphere collision model was validated through experiments. Suitable application regions for the energetic hard-sphere collision model, as well as for the conventional Langevin and hard-sphere collision models, were also discussed. The energetic hard-sphere collision model was applied in the extraction of ion CCSs from high-resolution FT-ICR mass spectra. Discussions in the present study also apply to FT-Orbitraps and FT-quadrupole ion traps.

Carrier mobility degradation due to high dose implantation in ultrathin unstrained and strained silicon-on-insulator films

NASA Astrophysics Data System (ADS)

Dupré, C.; Ernst, T.; Hartmann, J.-M.; Andrieu, F.; Barnes, J.-P.; Rivallin, P.; Faynot, O.; Deleonibus, S.; Fazzini, P. F.; Claverie, A.; Cristoloveanu, S.; Ghibaudo, G.; Cristiano, F.

2007-11-01

Based on electrical measurements and transmission electron microscopy (TEM) imaging, we propose an explanation for the electron and hole mobility degradation with gate length reduction in metal-oxide-semiconductor field effect transistors (MOSFETs). We demonstrate that ion implantation, normally used for source/drain doping, is responsible for transport degradation for short-channel devices. Implantation impact on electrons and holes mobility was investigated both on silicon-on-insulator (SOI) and tensile strained silicon-on-insulator (sSOI) substrates. Wafers with ultrathin Si films (from 8 to 35 nm) were Ge implanted at 3 keV and various concentrations (from 5×1014 to 2×1015 atoms cm-2), then annealed at 600 °C for 1 h. Secondary ion mass spectrometry enabled us to quantify the Ge-implanted atoms concentrations. The end-of-range defects impact on mobility was investigated with the pseudo-MOSFET technique. Measurements showed a mobility decrease as the implantation dose increased. We demonstrated that sSOI mobility is more sensitive to implantation than SOI mobility, without any implantation-induced strain relaxation in sSOI (checked using the ultraviolet Raman technique). A 36% (25%) holes (electrons) mobility degradation was measured for sSOI, while SOI presented a 21% mobility degradation for holes and 5% for electrons. Finally, the electrical results were compared with morphological studies. Plan-view TEM showed the presence of interstitial defects formed during ion implantation and annealing. The defect density was estimated to be two times higher in sSOI than in SOI, which is in full agreement with electrical results mentioned before. The results are relevant for the optimization of the source and drain regions of advanced nanoscale SOI and sSOI transistors.

The influence of addition of ion-pairing acid and organic modifier of the mobile phase on retention and migration of peptides in pressurized planar electrochromatography system with octadecyl silica-based adsorbent.

PubMed

Gwarda, Radosław Ł; Dzido, Tadeusz H

2018-07-13

In our previous papers we have investigated the influence of the mobile phase composition on mechanism of retention, selectivity and efficiency of peptide separation in various high-performance thin-layer chromatography (HPTLC) systems with commercially available silica-based adsorbents. We have also investigated the influence of pH of the mobile phase buffer on migration and separation of peptides in pressurized planar electrochromatography (PPEC). Here we investigate the influence of concentration of ion-pairing additive, and concentration and type of organic modifier of the mobile phase on migration of peptides in PPEC system with octadecyl silica-based adsorbent, and with the same set of the solutes as before. We compare our current results with the results obtained before for similar HPTLC and PPEC systems, and discuss the influence of particular variables on retention, electrophoretic mobility of solutes and electroosmotic flow of the mobile phase. We show, that the final selectivity of peptide separation results from co-influence of all the three factors mentioned. Concentration of organic modifier of the mobile phase, as well as concentration of ion-pairing additive, affect the retention, the electrophoretic mobility, and the electroosmotic flow simultaneously. This makes independent optimization of these factors rather difficult. Anyway PPEC offers much faster separation of peptides with quite different selectivity, in comparison to HPTLC, with similar adsorbents and similar mobile phase composition. However, we also present and discuss the issue of extensive tailing of peptide zones in the PPEC in comparison to similar HPTLC systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

PubMed

Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

2015-03-04

In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration.

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.

Publications - GMC 414 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 414 Publication Details Title: Sensitive High Resolution Ion Micro Probe (SHRIMP) data of Gottlieb, E., 2012, Sensitive High Resolution Ion Micro Probe (SHRIMP) data of outcrop samples from the

Physicochemical characteristics of LR3-IGF1 protein inclusion bodies: electrophoretic mobility studies.

PubMed

Wangsa-Wirawan, N D; O'Neill, B K; Middelberg, A P

2001-01-01

A knowledge of the physicochemical properties of inclusion bodies is important for the rational design of potential recovery processes such as flotation and precipitation. In this study, measurement of the size and electrophoretic mobility of protein inclusion bodies and cell debris was undertaken. SDS-PAGE analysis of protein inclusion bodies subjected to different cleaning regimes suggested that electrophoretic mobility provides a qualitative measure of protein inclusion body purity. Electrophoretic mobility as a function of electrolyte type and ionic strength was investigated. The presence of divalent ions produced a stronger effect on electrophoretic mobility compared with monovalent ions. The isoelectric point of cell debris was significantly lower than that for the inclusion bodies. Hence, the contaminating cell debris may be separated from inclusion bodies using flotation by exploiting this difference in isoelectric points. Separation by this method is simple, convenient, and a possible alternative to the conventional route of centrifugation.

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

PubMed

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

2016-06-09

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

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

PubMed Central

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

2010-01-01

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

Interface and process for enhanced transmission of non-circular ion beams between stages at unequal pressure

DOEpatents

Tang, Keqi [Richland, WA; Shvartsburg, Alexandre A [Richland, WA; Smith, Richard D [Richland, WA

2008-03-04

The invention discloses a new interface with non-circular conductance limit aperture(s) useful for effective transmission of non-circular ion beams between stages with different gas pressure. In particular, the invention provides an improved coupling of field asymmetric waveform ion mobility spectrometry (FAIMS) analyzers of planar or side-to-side geometry to downstream stages such as mass spectrometry or ion mobility spectrometry. In this case, the non-circular aperture is rectangular; other geometries may be optimum in other applications. In the preferred embodiment, the non-circular aperture interface is followed by an electrodynamic ion funnel that may focus wide ion beams of any shape into tight circular beams with virtually no losses. The jet disrupter element of the funnel may also have a non-circular geometry, matching the shape of arriving ion beam. The improved sensitivity of planar FAIMS/MS has been demonstrated in experiments using a non-contiguous elongated aperture but other embodiments (e.g., with a contiguous slit aperture) may be preferable, especially in conjunction with an ion funnel operated at high pressures.

Hydrogen-deuterium exchange mass spectrometry reveals folding and allostery in protein-protein interactions.

PubMed

Ramirez-Sarmiento, Cesar A; Komives, Elizabeth A

2018-04-06

Hydrogen-deuterium exchange mass spectrometry (HDXMS) has emerged as a powerful approach for revealing folding and allostery in protein-protein interactions. The advent of higher resolution mass spectrometers combined with ion mobility separation and ultra performance liquid chromatographic separations have allowed the complete coverage of large protein sequences and multi-protein complexes. Liquid-handling robots have improved the reproducibility and accurate temperature control of the sample preparation. Many researchers are also appreciating the power of combining biophysical approaches such as stopped-flow fluorescence, single molecule FRET, and molecular dynamics simulations with HDXMS. In this review, we focus on studies that have used a combination of approaches to reveal (re)folding of proteins as well as on long-distance allosteric changes upon interaction. Copyright © 2018 Elsevier Inc. All rights reserved.

Infrared vibrational nanocrystallography and nanoimaging

PubMed Central

Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A.; van Blerkom, Peter; Raschke, Markus B.

2016-01-01

Molecular solids and polymers can form low-symmetry crystal structures that exhibit anisotropic electron and ion mobility in engineered devices or biological systems. The distribution of molecular orientation and disorder then controls the macroscopic material response, yet it is difficult to image with conventional techniques on the nanoscale. We demonstrated a new form of optical nanocrystallography that combines scattering-type scanning near-field optical microscopy with both optical antenna and tip-selective infrared vibrational spectroscopy. From the symmetry-selective probing of molecular bond orientation with nanometer spatial resolution, we determined crystalline phases and orientation in aggregates and films of the organic electronic material perylenetetracarboxylic dianhydride. Mapping disorder within and between individual nanoscale domains, the correlative hybrid imaging of nanoscale heterogeneity provides insight into defect formation and propagation during growth in functional molecular solids. PMID:27730212

Structural Investigation of Fluoridated POSS Cages Using Ion Mobility Mass Spectrometry and Molecular Mechanics (Preprint)

DTIC Science & Technology

2008-01-09

organic polymer. For example, the low surface energy properties of fluorinated POSS compounds have been used to augment both fluorinated and non... fluorinated polymers.10-13 Many POSS monomers have been successfully characterized using MALDI techniques14-16 in conjunction with ion mobility mass...nucleophilic attack, are shown in blue. Negative contours, showing susceptibility to electrophilic attack, are shown in red. The positive contour of

A novel approach to increasing cocaine detection confidence utilizing ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Jadamec, J. Richard; Su, Chih-Wu; Rigdon, Stephen; Norwood, Lavan

1995-01-01

When a positive detection of a narcotic occurs during the search of a vessel, a decision has to be made whether further intensive search is warranted. In terms of unwarranted delays of vessels and possible property damage, the accuracy of the analytical determination is very important. Analytical accuracy becomes critical when the data may be used in court actions as evidence. For this purpose, the U.S. Coast Guard has been investigating several confirmatory ion mobility spectrometry (IMS) field methods for the detection and identification of cocaine. This paper presents the findings of our investigations on the use of catalytic pyrolysis and base hydrolysis as confirmatory methods. The catalytic effects of various metals on the pyrolysis reaction are reported. In addition, the effects of several different ion mobility spectrometer sample transfer mediums and varying laboratory conditions on the base hydrolysis of the cocaine molecule are also be reported.

Portable Solid Phase Micro-Extraction Coupled with Ion Mobility Spectrometry System for On-Site Analysis of Chemical Warfare Agents and Simulants in Water Samples

PubMed Central

Yang, Liu; Han, Qiang; Cao, Shuya; Yang, Jie; Yang, Junchao; Ding, Mingyu

2014-01-01

On-site analysis is an efficient approach to facilitate analysis at the location of the system under investigation as it can result in more accurate, more precise and quickly available analytical data. In our work, a novel self-made thermal desorption based interface was fabricated to couple solid-phase microextraction with ion mobility spectrometry for on-site water analysis. The portable interface can be connected with the front-end of an ion mobility spectrometer directly without other modifications. The analytical performance was evaluated via the extraction of chemical warfare agents and simulants in water samples. Several parameters including ionic strength and extraction time have been investigated in detail. The application of the developed method afforded satisfactory recoveries ranging from 72.9% to 114.4% when applied to the analysis of real water samples. PMID:25384006

An Attention-Information-Based Spatial Adaptation Framework for Browsing Videos via Mobile Devices

NASA Astrophysics Data System (ADS)

Li, Houqiang; Wang, Yi; Chen, Chang Wen

2007-12-01

With the growing popularity of personal digital assistant devices and smart phones, more and more consumers are becoming quite enthusiastic to appreciate videos via mobile devices. However, limited display size of the mobile devices has been imposing significant barriers for users to enjoy browsing high-resolution videos. In this paper, we present an attention-information-based spatial adaptation framework to address this problem. The whole framework includes two major parts: video content generation and video adaptation system. During video compression, the attention information in video sequences will be detected using an attention model and embedded into bitstreams with proposed supplement-enhanced information (SEI) structure. Furthermore, we also develop an innovative scheme to adaptively adjust quantization parameters in order to simultaneously improve the quality of overall encoding and the quality of transcoding the attention areas. When the high-resolution bitstream is transmitted to mobile users, a fast transcoding algorithm we developed earlier will be applied to generate a new bitstream for attention areas in frames. The new low-resolution bitstream containing mostly attention information, instead of the high-resolution one, will be sent to users for display on the mobile devices. Experimental results show that the proposed spatial adaptation scheme is able to improve both subjective and objective video qualities.

The 1.3 A resolution structure of the RNA tridecamer r(GCGUUUGAAACGC): metal ion binding correlates with base unstacking and groove contraction.

PubMed

Timsit, Youri; Bombard, Sophie

2007-12-01

Metal ions play a key role in RNA folding and activity. Elucidating the rules that govern the binding of metal ions is therefore an essential step for better understanding the RNA functions. High-resolution data are a prerequisite for a detailed structural analysis of ion binding on RNA and, in particular, the observation of monovalent cations. Here, the high-resolution crystal structures of the tridecamer duplex r(GCGUUUGAAACGC) crystallized under different conditions provides new structural insights on ion binding on GAAA/UUU sequences that exhibit both unusual structural and functional properties in RNA. The present study extends the repertory of RNA ion binding sites in showing that the two first bases of UUU triplets constitute a specific site for sodium ions. A striking asymmetric pattern of metal ion binding in the two equivalent halves of the palindromic sequence demonstrates that sequence and its environment act together to bind metal ions. A highly ionophilic half that binds six metal ions allows, for the first time, the observation of a disodium cluster in RNA. The comparison of the equivalent halves of the duplex provides experimental evidences that ion binding correlates with structural alterations and groove contraction.

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

PubMed Central

2013-01-01

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

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

PubMed

Benjamin, Ashlee M; Thompson, J Will; Soderblom, Erik J; Geromanos, Scott J; Henao, Ricardo; Kraus, Virginia B; Moseley, M Arthur; Lucas, Joseph E

2013-12-16

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

Selective detection of underivatized 2,4-dichlorophenoxyacetic acid in soil by supercritical fluid chromatography with ion mobility detection.

PubMed

Morrissey, M A; Hill, H H

1989-09-01

A simplified procedure was developed for the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in soils. Soil samples were separated by supercritical fluid chromatography after extraction without derivatization and without the use of column chromatography for cleanup. Interferences in the chromatographic separation were eliminated by using a tunably selective ion mobility detector. An atmospheric pressure ion formed by the free acid was selectively monitored so the detector could monitor 2,4-D in the presence of other electron-capturing compounds. For a randomly chosen soil sample, the level of 2,4-D detected was estimated at 500 ppb.

Breaking the news on mobile TV: user requirements of a popular mobile content

NASA Astrophysics Data System (ADS)

Knoche, Hendrik O.; Sasse, M. Angela

2006-02-01

This paper presents the results from three lab-based studies that investigated different ways of delivering Mobile TV News by measuring user responses to different encoding bitrates, image resolutions and text quality. All studies were carried out with participants watching News content on mobile devices, with a total of 216 participants rating the acceptability of the viewing experience. Study 1 compared the acceptability of a 15-second video clip at different video and audio encoding bit rates on a 3G phone at a resolution of 176x144 and an iPAQ PDA (240x180). Study 2 measured the acceptability of video quality of full feature news clips of 2.5 minutes which were recorded from broadcast TV, encoded at resolutions ranging from 120x90 to 240x180, and combined with different encoding bit rates and audio qualities presented on an iPAQ. Study 3 improved the legibility of the text included in the video simulating a separate text delivery. The acceptability of News' video quality was greatly reduced at a resolution of 120x90. The legibility of text was a decisive factor in the participants' assessment of the video quality. Resolutions of 168x126 and higher were substantially more acceptable when they were accompanied by optimized high quality text compared to proportionally scaled inline text. When accompanied by high quality text TV news clips were acceptable to the vast majority of participants at resolutions as small as 168x126 for video encoding bitrates of 160kbps and higher. Service designers and operators can apply this knowledge to design a cost-effective mobile TV experience.

Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

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

PubMed

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

2016-07-01

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

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.

Isomer Information from Ion Mobility Separation of High-Mannose Glycan Fragments.

PubMed

Harvey, David J; Seabright, Gemma E; Vasiljevic, Snezana; Crispin, Max; Struwe, Weston B

2018-05-01

Extracted arrival time distributions of negative ion CID-derived fragments produced prior to traveling-wave ion mobility separation were evaluated for their ability to provide structural information on N-linked glycans. Fragmentation of high-mannose glycans released from several glycoproteins, including those from viral sources, provided over 50 fragments, many of which gave unique collisional cross-sections and provided additional information used to assign structural isomers. For example, cross-ring fragments arising from cleavage of the reducing terminal GlcNAc residue on Man 8 GlcNAc 2 isomers have unique collision cross-sections enabling isomers to be differentiated in mixtures. Specific fragment collision cross-sections enabled identification of glycans, the antennae of which terminated in the antigenic α-galactose residue, and ions defining the composition of the 6-antenna of several of the glycans were also found to have different cross-sections from isomeric ions produced in the same spectra. Potential mechanisms for the formation of the various ions are discussed and the estimated collisional cross-sections are tabulated. Graphical Abstract ᅟ.

Differential mobility spectroscopy for chemical agent detection

NASA Astrophysics Data System (ADS)

Griffin, M. Todd

2006-05-01

General Dynamics ATP (GDATP) and Sionex Corporation (Sionex) are carrying out a cooperative development for a handheld chemical agent detector, being called JUNO TM, which will have lower false positives, higher sensitivity, and improved interference rejection compared with presently available detectors. This enhanced performance is made possible by the use of a new principle of ion separation called Differential Mobility Spectrometry (DMS). The enhanced selectivity is provided by the field tunable nature of the Sionex differential mobility technology (microDMxTM) which forms the analytical heart of the JUNO system and enables fingerprinting of molecules by characterization of the ionized molecular behavior under multiple electric field conditions. This enhanced selectivity is valuable in addressing not only the traditional list of chemical warfare agents (CWA) but also the substantial list of Toxic Industrial Compounds (TICs) and Toxic Industrial Materials (TIMs) which may be released in warfare or terrorist situations. Experimental results showing the ability of the microDMx to reject interferences, detect and resolve live agents are presented. An additional breakthrough in the technology was realized by operating the device at a reduced pressure of around 0.5 atmospheres. This reduced pressure operation resulted in roughly doubling the spectrometers resolution over what has previously been reported [1]. Advances have also been made in power consumption and packaging leading to a device suitable for portable, handheld, applications. Experimental results illustrating the performance of the microDMx technology employed in JUNO are highlighted.

Protonation of caffeine: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Bahrami, Hamed; Tabrizchi, Mahmoud; Farrokhpour, Hossein

2013-03-01

Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources, corona discharge (CD) and UV photoionization. Three peaks were observed in ion mobility spectrum by simultaneously running the two ionization sources. Experimental and theoretical evidence was collected to link the observed peaks to caffeine related ionic species. One peak was attributed to the M+ ion while the other two were assigned to different protonated isomers of caffeine. In the case of CD ionization source, it was observed that different sites of caffeine compete for protonation and their relative intensities, depends on the sample concentration as well as the nature of the reactant ions. The new concept of "internal proton affinity" (IPA) was defined to express the tendency of holding the added proton for each atom in a molecule.

Dynamic multiplexed analysis method using ion mobility spectrometer

DOEpatents

Belov, Mikhail E [Richland, WA

2010-05-18

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

Imaging of single cells and tissue using MeV ions

NASA Astrophysics Data System (ADS)

Watt, F.; Bettiol, A. A.; van Kan, J. A.; Ynsa, M. D.; Minqin, Ren; Rajendran, R.; Huifang, Cui; Fwu-Shen, Sheu; Jenner, A. M.

2009-06-01

With the attainment of sub-100 nm high energy (MeV) ion beams, comes the opportunity to image cells and tissue at nano-dimensions. The advantage of MeV ion imaging is that the ions will penetrate whole cells, or relatively thick tissue sections, without any significant loss of resolution. In this paper, we demonstrate that whole cells (cultured N2A neuroblastoma cells ATCC) and tissue sections (rabbit pancreas tissue) can be imaged at sub-100 nm resolutions using scanning transmission ion microscopy (STIM), and that sub-cellular structural details can be identified. In addition to STIM imaging we have also demonstrated for the first time, that sub-cellular proton induced fluorescence imaging (on cultured N2A neuroblastoma cells ATCC) can also be carried out at resolutions of 200 nm, compared with 300-400 nm resolutions achieved by conventional optical fluorescence imaging. The combination of both techniques offers a potentially powerful tool in the quest for elucidating cell function, particularly when it should be possible in the near future to image down to sub-50 nm.

Secure steganography designed for mobile platforms

NASA Astrophysics Data System (ADS)

Agaian, Sos S.; Cherukuri, Ravindranath; Sifuentes, Ronnie R.

2006-05-01

Adaptive steganography, an intelligent approach to message hiding, integrated with matrix encoding and pn-sequences serves as a promising resolution to recent security assurance concerns. Incorporating the above data hiding concepts with established cryptographic protocols in wireless communication would greatly increase the security and privacy of transmitting sensitive information. We present an algorithm which will address the following problems: 1) low embedding capacity in mobile devices due to fixed image dimensions and memory constraints, 2) compatibility between mobile and land based desktop computers, and 3) detection of stego images by widely available steganalysis software [1-3]. Consistent with the smaller available memory, processor capabilities, and limited resolution associated with mobile devices, we propose a more magnified approach to steganography by focusing adaptive efforts at the pixel level. This deeper method, in comparison to the block processing techniques commonly found in existing adaptive methods, allows an increase in capacity while still offering a desired level of security. Based on computer simulations using high resolution, natural imagery and mobile device captured images, comparisons show that the proposed method securely allows an increased amount of embedding capacity but still avoids detection by varying steganalysis techniques.

Native mass spectrometry and ion mobility characterization of trastuzumab emtansine, a lysine-linked antibody drug conjugate.

PubMed

Marcoux, Julien; Champion, Thierry; Colas, Olivier; Wagner-Rousset, Elsa; Corvaïa, Nathalie; Van Dorsselaer, Alain; Beck, Alain; Cianférani, Sarah

2015-08-01

Antibody-drug conjugates (ADCs) are biochemotherapeutics consisting of a cytotoxic chemical drug linked covalently to a monoclonal antibody. Two main classes of ADCs, namely cysteine and lysine conjugates, are currently available on the market or involved in clinical trials. The complex structure and heterogeneity of ADCs makes their biophysical characterization challenging. For cysteine conjugates, hydrophobic interaction chromatography is the gold standard technique for studying drug distribution, the naked antibody content, and the average drug to antibody ratio (DAR). For lysine ADC conjugates on the other hand, which are not amenable to hydrophobic interaction chromatography because of their higher heterogeneity, denaturing mass spectrometry (MS) and UV/Vis spectroscopy are the most powerful approaches. We report here the use of native MS and ion mobility (IM-MS) for the characterization of trastuzumab emtansine (T-DM1, Kadcyla(®)). This lysine conjugate is currently being considered for the treatment of human epidermal growth factor receptor 2 (HER2)-positive breast cancer, and combines the anti-HER2 antibody trastuzumab (Herceptin(®)), with the cytotoxic microtubule-inhibiting maytansine derivative, DM1. We show that native MS combined with high-resolution measurements and/or charge reduction is beneficial in terms of the accurate values it provides of the average DAR and the drug load profiles. The use of spectral deconvolution is discussed in detail. We report furthermore the use of native IM-MS to directly determine DAR distribution profiles and average DAR values, as well as a molecular modeling investigation of positional isomers in T-DM1. © 2015 The Protein Society.

E/N effects on K0 values revealed by high precision measurements under low field conditions

NASA Astrophysics Data System (ADS)

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

2016-07-01

Ion mobility spectrometry (IMS) is used to detect chemical warfare agents, explosives, and narcotics. While IMS has a low rate of false positives, their occurrence causes the loss of time and money as the alarm is verified. Because numerous variables affect the reduced mobility (K0) of an ion, wide detection windows are required in order to ensure a low false negative response rate. Wide detection windows, however, reduce response selectivity, and interferents with similar K0 values may be mistaken for targeted compounds and trigger a false positive alarm. Detection windows could be narrowed if reference K0 values were accurately known for specific instrumental conditions. Unfortunately, there is a lack of confidence in the literature values due to discrepancies in the reported K0 values and their lack of reported error. This creates the need for the accurate control and measurement of each variable affecting ion mobility, as well as for a central accurate IMS database for reference and calibration. A new ion mobility spectrometer has been built that reduces the error of measurements affecting K0 by an order of magnitude less than ±0.2%. Precise measurements of ±0.002 cm2 V-1 s-1 or better have been produced and, as a result, an unexpected relationship between K0 and the electric field to number density ratio (E/N) has been discovered in which the K0 values of ions decreased as a function of E/N along a second degree polynomial trend line towards an apparent asymptote at approximately 4 Td.

Negative corona discharge-ion mobility spectrometry as a detection system for low density extraction solvent-based dispersive liquid-liquid microextraction.

PubMed

Ebrahimi, Amir; Jafari, Mohammad T

2015-03-01

This paper deals with a method based on negative corona discharge ionization ion mobility spectrometry (NCD-IMS) for the analysis of ethion (as an organophosphorus pesticide). The negative ions such as O2(-) and NO(x)(-) were eliminated from the background spectrum to increase the instrument sensitivity. The method was used to specify the sample extracted via dispersive liquid-liquid microextraction (DLLME) based on low density extraction solvent. The ion mobility spectrum of ethion in the negative mode and the reduced mobility value for its ion peak are firstly reported and compared with those of the positive mode. In order to combine the low density solvent DLLME directly with NCD-IMS, cyclohexane was selected as the extraction solvent, helping us to have a direct injection up to 20 µL solution, without any signal interference. The method was exhaustively validated in terms of sensitivity, enrichment factor, relative recovery, and repeatability. The linear dynamic range of 0.2-100.0 µg L(-1), detection limit of 0.075 µg L(-1), and the relative standard deviation (RSD) of about 5% were obtained for the analysis of ethion through this method. The average recoveries were calculated about 68% and 92% for the grape juice and underground water, respectively. Finally, some real samples were analyzed and the feasibility of the proposed method was successfully verified by the efficient extraction of the analyte using DLLME before the analysis by NCD-IMS. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct Liquid Sampling for Corona Discharge Ion Mobility Spectrometry.

PubMed

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

2015-07-21

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

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

Ion mobility spectrometer, spectrometer analyte detection and identification verification system, and method

DOEpatents

Atkinson, David A.

2002-01-01

Methods and apparatus for ion mobility spectrometry and analyte detection and identification verification system are disclosed. The apparatus is configured to be used in an ion mobility spectrometer and includes a plurality of reactant reservoirs configured to contain a plurality of reactants which can be reacted with the sample to form adducts having varying ion mobilities. A carrier fluid, such as air or nitrogen, is used to carry the sample into the spectrometer. The plurality of reactants are configured to be selectively added to the carrier stream by use inlet and outlet manifolds in communication with the reagent reservoirs, the reservoirs being selectively isolatable by valves. The invention further includes a spectrometer having the reagent system described. In the method, a first reactant is used with the sample. Following a positive result, a second reactant is used to determine whether a predicted response occurs. The occurrence of the second predicted response tends to verify the existence of a component of interest within the sample. A third reactant can also be used to provide further verification of the existence of a component of interest. A library can be established of known responses of compounds of interest with various reactants and the results of a specific multi-reactant survey of a sample can be compared against the library to determine whether a component detected in the sample is likely to be a specific component of interest.

Multi-capillary column-ion mobility spectrometry: a potential screening system to differentiate virgin olive oils.

PubMed

Garrido-Delgado, Rocío; Arce, Lourdes; Valcárcel, Miguel

2012-01-01

The potential of a headspace device coupled to multi-capillary column-ion mobility spectrometry has been studied as a screening system to differentiate virgin olive oils ("lampante," "virgin," and "extra virgin" olive oil). The last two types are virgin olive oil samples of very similar characteristics, which were very difficult to distinguish with the existing analytical method. The procedure involves the direct introduction of the virgin olive oil sample into a vial, headspace generation, and automatic injection of the volatiles into a gas chromatograph-ion mobility spectrometer. The data obtained after the analysis by duplicate of 98 samples of three different categories of virgin olive oils, were preprocessed and submitted to a detailed chemometric treatment to classify the virgin olive oil samples according to their sensory quality. The same virgin olive oil samples were also analyzed by an expert's panel to establish their category and use these data as reference values to check the potential of this new screening system. This comparison confirms the potential of the results presented here. The model was able to classify 97% of virgin olive oil samples in their corresponding group. Finally, the chemometric method was validated obtaining a percentage of prediction of 87%. These results provide promising perspectives for the use of ion mobility spectrometry to differentiate virgin olive oil samples according to their quality instead of using the classical analytical procedure.

Experimental ion mobility measurements in Xe-C2H6

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.

2017-10-01

In this paper we present the results of the ion mobility measurements made in gaseous mixtures of xenon (Xe) with ethane (C2H6) for pressures ranging from 6 to 10 Torr (8-10.6 mbar) and for low reduced electric fields in the 10 Td to 25 Td range (2.4-6.1 kVṡcm-1ṡ bar-1), at room temperature. The time of arrival spectra revealed two peaks throughout the entire range studied which were attributed to ion species with 3-carbons (C3H5+, C3H6+ C3H8+ and C3H9+) and with 4-carbons (C4H7+, C4H9+ and C4H10+). Besides these, and for Xe concentrations above 70%, a bump starts to appear at the right side of the main peak for reduced electric fields higher than 20 Td, which was attributed to the resonant charge transfer of C2H6+ to C2H6 that affects the mobility of its ion products (C3H8+ and C3H9+). The time of arrival spectra for Xe concentrations of 20%, 50%, 70% and 90% are presented, together with the reduced mobilities as a function of the Xe concentration calculated from the peaks observed for the low reduced electric fields and pressures studied.

Sensitive detection of trimethylamine based on dopant-assisted positive photoionization ion mobility spectrometry.

PubMed

Cheng, Shasha; Li, Haitao; Jiang, Dandan; Chen, Chuang; Zhang, Tan; Li, Yong; Wang, Haitao; Zhou, Qinghua; Li, Haiyang; Tan, Mingqian

2017-01-01

Biogenic amines are degradation products generated through enzymatic and microbial processes during food spoilage, which may pose a health hazard to consumers at elevated levels. Trimethylamine (TMA) is a good target for the detection of biogenic amines due to its volatility and fishy odor. In this study, we developed a stand-alone dopant-assisted positive photoionization ion mobility spectrometry (DAPP-IMS) for rapid and sensitive detection of TMA. Response of TMA was enhanced by the addition of dopants and characteristic product ions with reduced mobility 2.26cm 2 V -1 s -1 were formed. 2-Butaone was chosen as the dopant for better separation between reagent ion peak and TMA product ion peak as well as higher sensitivity and the limit of detections (LODs) for TMA standard sample was 1ppb. The potential application of DAAP-IMS was evaluated by the detection of TMA generated by oyster and shrimp during 4°C storage. Analysis of two kinds of seafood showed the same characteristic peak to TMA standard sample, and the intensity of TMA increased over the storage time. The results of this study testify to the potential of DAPP-IMS for qualitative and quantitative determination of TMA in real food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Transport Properties of Anatase-TiO2 Polycrystalline-Thin-Film Field-Effect Transistors with Electrolyte Gate Layers

NASA Astrophysics Data System (ADS)

Horita, Ryohei; Ohtani, Kyosuke; Kai, Takahiro; Murao, Yusuke; Nishida, Hiroya; Toya, Taku; Seo, Kentaro; Sakai, Mio; Okuda, Tetsuji

2013-11-01

We have fabricated anatase-TiO2 polycrystalline-thin-film field-effect transistors (FETs) with poly(vinyl alcohol) (PVA), ion-liquid (IL), and ion-gel (IG) gate layers, and have tried to improve the response to gate voltage by varying the concentration of mobile ions in these electrolyte gate layers. The increase in the concentration of mobile ions by doping NaOH into the PVA gate layer or reducing the gelator in the IG gate layer markedly increases the drain-source current and reduces the driving gate voltage, which show that the mobile ions in the PVA, IL, and IG gate layers cause the formation of electric double layers (EDLs), which act as nanogap capacitors. In these TiO2-EDL-FETs, the slow formation of EDLs and the oxidation reaction at the interface between the surface of the TiO2 film and the electrolytes cause unideal FET properties. In the optimized IL and IG TiO2-EDL-FETs, the driving gate voltage is less than 1 V and the ON/OFF ratios of the transfer characteristics are about 1×104 at RT, and the nearly metallic state is realized at the interface purely by applying a gate voltage.

Design of a TW-SLIM Module for Dual Polarity Confinement, Transport, and Reactions

NASA Astrophysics Data System (ADS)

Garimella, Sandilya V. B.; Webb, Ian K.; Prabhakaran, Aneesh; Attah, Isaac K.; Ibrahim, Yehia M.; Smith, Richard D.

2017-07-01

Here we describe instrumental approaches for performing dual polarity ion confinement, transport, ion mobility separations, and reactions in structures for lossless ion manipulations (SLIM). Previous means of ion confinement in SLIM, based upon rf-generated pseudopotentials and DC fields for lateral confinement, cannot trap ions of opposite polarity simultaneously. Here we explore alternative approaches to provide simultaneous lateral confinement of both ion polarities. Traveling wave ion mobility (IM) separations experienced in such SLIM cause ions of both polarities to migrate in the same directions and exhibit similar separations. The ion motion (and relative motion of the two polarities) under both surfing and IM separation conditions are discussed. In surfing conditions the two polarities are transported losslessly and non-reactively in their respective potential minima (higher absolute voltage regions confine negative polarities, and lower absolute potential regions are populated by positive polarities). In separation mode, where ions roll over an overtaking traveling wave, the two polarities can interact during the rollovers. Strategies to minimize overlap of the two ion populations to prevent reactive losses during separations are presented. A theoretical treatment of the time scales over which two populations (injected into a DC field-free region of the dual polarity SLIM device) interact is considered, and SLIM designs for allowing ion/ion interactions and other manipulations with dual polarities at 4 Torr are presented.

Mobility and fluorescence of barium ions in xenon gas for the exo experiment

NASA Astrophysics Data System (ADS)

Benitez Medina, Julio Cesar

The Enriched Xenon Observatory (EXO) is an experiment which aims to observe the neutrinoless double beta decay of 136Xe. The measurement of this decay would give information about the absolute neutrino mass and whether or not the neutrino is its own antiparticle. Since this is a very rare decay, the ability to reject background events by detecting the barium ion daughter from the double beta decay would be a major advantage. EXO is currently operating a detector with 200 kg of enriched liquid xenon, and there are plans to build a ton scale xenon detector. Measurements of the purity of liquid xenon in our liquid xenon test cell are reported. These results are relevant to the research on detection of single barium ions by our research group at Colorado State University. Details of the operation of the purity monitor are described. The effects of using a purifier, recirculation and laser ablation on the purity of liquid xenon are discussed. Mobility measurements of barium in xenon gas are reported for the first time. The variation of mobility with xenon gas pressure suggests that a significant fraction of molecular ions are formed when barium ions interact with xenon gas at high pressures. The measured mobility of Ba+ in Xe gas at different pressures is compared with the predicted theoretical value, and deviations are explained by a model that describes the fraction of molecular ions in Xe gas as a function of pressure. The results are useful for the analysis of experiments of fluorescence of Ba+ in xenon gas. It is also important to know the mobility of the ions in order to calculate the time they interact with an excitation laser in fluorescence experiments and in proposed 136 Ba+ daughter detection schemes. This thesis presents results of detection of laser induced fluorescence of Ba+ ions in Xe gas. Measurements of the pressure broadening of the excitation spectra of Ba+ in xenon gas are presented. Nonradiative decays due to gas collisions and optical pumping affect the number of fluorescence counts detected. A model that treats the barium ion as a three level system is used to predict the total number of fluorescence counts and correct for optical pumping. A pressure broadening coefficient for Ba+ in xenon gas is extracted and limits for p-d and d-s nonradiative decay rates are extracted. Although fluorescence is reduced significantly at 5-10 atm xenon pressure, the measurements in this thesis indicate that it is still feasible to detect 136Ba+ ions directly in high pressure xenon gas, e.g. in a double beta decay detector.

Low-temperature field ion microscopy of carbon nanotubes

NASA Astrophysics Data System (ADS)

Ksenofontov, V. A.; Gurin, V. A.; Gurin, I. V.; Kolosenko, V. V.; Mikhailovskij, I. M.; Sadanov, E. V.; Mazilova, T. I.; Velikodnaya, O. A.

2007-10-01

The methods of high-resolution field ion microscopy with sample cooling to liquid helium temperature are used in a study of the products of gas-phase catalytic pyrolysis of hydrocarbons in the form of graphitized fibers containing carbon nanotubes. Full atomic resolution of the end cap of closed carbon nanotubes is achieved for the first time. It is found that the atomic structure of the tops of the caps of subnanometer carbon tubes consists predominantly of hexagonal rings. A possible reason for the improvement of the resolution of field ion images of nanotubes upon deep cooling is discussed.

Extending the frontiers of mass spectrometric instrumentation and methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schieffer, Gregg Martin

2010-01-01

The focus of this dissertation is two-fold: developing novel analysis methods using mass spectrometry and the implementation and characterization of a novel ion mobility mass spectrometry instrumentation. The novel mass spectrometry combines ion trap for ion/ion reactions coupled to an ion mobility cell. The long term goal of this instrumentation is to use ion/ion reactions to probe the structure of gas phase biomolecule ions. The three ion source - ion trap - ion mobility - qTOF mass spectrometer (IT - IM - TOF MS) instrument is described. The analysis of the degradation products in coal (Chapter 2) and the imagingmore » plant metabolites (Appendix III) fall under the methods development category. These projects use existing commercial instrumentation (JEOL AccuTOF MS and Thermo Finnigan LCQ IT, respectively) for the mass analysis of the degraded coal products and the plant metabolites, respectively. The coal degradation paper discusses the use of the DART ion source for fast and easy sample analysis. The sample preparation consisted of a simple 50 fold dilution of the soluble coal products in water and placing the liquid in front of the heated gas stream. This is the first time the DART ion source has been used for analysis of coal. Steven Raders under the guidance of John Verkade came up with the coal degradation projects. Raders performed the coal degradation reactions, worked up the products, and sent them to me. Gregg Schieffer developed the method and wrote the paper demonstrating the use of the DART ion source for the fast and easy sample analysis. The plant metabolite imaging project extends the use of colloidal graphite as a sample coating for atmospheric pressure LDI. DC Perdian and I closely worked together to make this project work. Perdian focused on building the LDI setup whereas Schieffer focused on the MSn analysis of the metabolites. Both Perdian and I took the data featured in the paper. Perdian was the primary writer of the paper and used it as a chapter in his dissertation. Perdian and Schieffer worked together to address the revisions and publish it in Rapid Communications in Mass Spectrometry Journal.« less

Understanding the conductive channel evolution in Na:WO3-x-based planar devices

NASA Astrophysics Data System (ADS)

Shang, Dashan; Li, Peining; Wang, Tao; Carria, Egidio; Sun, Jirong; Shen, Baogen; Taubner, Thomas; Valov, Ilia; Waser, Rainer; Wuttig, Matthias

2015-03-01

An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices.An ion migration process in a solid electrolyte is important for ion-based functional devices, such as fuel cells, batteries, electrochromics, gas sensors, and resistive switching systems. In this study, a planar sandwich structure is prepared by depositing tungsten oxide (WO3-x) films on a soda-lime glass substrate, from which Na+ diffuses into the WO3-x films during the deposition. The entire process of Na+ migration driven by an alternating electric field is visualized in the Na-doped WO3-x films in the form of conductive channel by in situ optical imaging combined with infrared spectroscopy and near-field imaging techniques. A reversible change of geometry between a parabolic and a bar channel is observed with the resistance change of the devices. The peculiar channel evolution is interpreted by a thermal-stress-induced mechanical deformation of the films and an asymmetric Na+ mobility between the parabolic and the bar channels. These results exemplify a typical ion migration process driven by an alternating electric field in a solid electrolyte with a low ion mobility and are expected to be beneficial to improve the controllability of the ion migration in ion-based functional devices, such as resistive switching devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07545e

Higher sensitivity secondary ion mass spectrometry of biological molecules for high resolution, chemically specific imaging.

PubMed

McDonnell, Liam A; Heeren, Ron M A; de Lange, Robert P J; Fletcher, Ian W

2006-09-01

To expand the role of high spatial resolution secondary ion mass spectrometry (SIMS) in biological studies, numerous developments have been reported in recent years for enhancing the molecular ion yield of high mass molecules. These include both surface modification, including matrix-enhanced SIMS and metal-assisted SIMS, and polyatomic primary ions. Using rat brain tissue sections and a bismuth primary ion gun able to produce atomic and polyatomic primary ions, we report here how the sensitivity enhancements provided by these developments are additive. Combined surface modification and polyatomic primary ions provided approximately 15.8 times more signal than using atomic primary ions on the raw sample, whereas surface modification and polyatomic primary ions yield approximately 3.8 and approximately 8.4 times more signal. This higher sensitivity is used to generate chemically specific images of higher mass biomolecules using a single molecular ion peak.

A simple and rapid method for high-resolution visualization of single-ion tracks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Omichi, Masaaki; Center for Collaborative Research, Anan National College of Technology, Anan, Tokushima 774-0017; Choi, Wookjin

2014-11-15

Prompt determination of spatial points of single-ion tracks plays a key role in high-energy particle induced-cancer therapy and gene/plant mutations. In this study, a simple method for the high-resolution visualization of single-ion tracks without etching was developed through the use of polyacrylic acid (PAA)-N, N’-methylene bisacrylamide (MBAAm) blend films. One of the steps of the proposed method includes exposure of the irradiated films to water vapor for several minutes. Water vapor was found to promote the cross-linking reaction of PAA and MBAAm to form a bulky cross-linked structure; the ion-track scars were detectable at a nanometer scale by atomic forcemore » microscopy. This study demonstrated that each scar is easily distinguishable, and the amount of generated radicals of the ion tracks can be estimated by measuring the height of the scars, even in highly dense ion tracks. This method is suitable for the visualization of the penumbra region in a single-ion track with a high spatial resolution of 50 nm, which is sufficiently small to confirm that a single ion hits a cell nucleus with a size ranging between 5 and 20 μm.« less

Atmospheric ions and germination of uredospores of Puccinia striiformis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharp, E.L.

1967-06-09

Atmospheric ions, identified by mobility characteristics, were associated with germination of lyophilized uredospores of Puccinia striiformis West. at Bozeman, Montana. Ions of intermediate size were highest in concentration, and percentage germination of spores was lowest during periods conducive to air pollution. In duplicate experiments at an isolated site near Barrow, Alaska, essentially all atmospheric ions were small ions and the fungus spores were consistently germinated near maximum.

Influence of nanoparticle-ion and nanoparticle-polymer interactions on ion transport and viscoelastic properties of polymer electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mogurampelly, Santosh; Sethuraman, Vaidyanathan; Pryamitsyn, Victor

We use atomistic simulations to probe the ion conductivities and mechanical properties of polyethylene oxide electrolytes containing Al{sub 2}O{sub 3} nanoparticles. We specifically study the influence of repulsive polymer-nanoparticle and ion-nanoparticle interactions and compare the results with those reported for electrolytes containing the polymorph β-Al{sub 2}O{sub 3} nanoparticles. We observe that incorporating repulsive nanoparticle interactions generally results in increased ionic mobilities and decreased elastic moduli for the electrolyte. Our results indicate that both ion transport and mechanical properties are influenced by the polymer segmental dynamics in the interfacial zones of the nanoparticle in the ion-doped systems. Such effects were seenmore » to be determined by an interplay between the nanoparticle-polymer, nanoparticle-ion, and ion-polymer interactions. In addition, such interactions were also observed to influence the number of dissociated ions and the resulting conductivities. Within the perspective of the influence of nanoparticles on the polymer relaxation times in ion-doped systems, our results in the context of viscoelastic properties were consistent with the ionic mobilities. Overall, our results serve to highlight some issues that confront the efforts to use nanoparticle dispersions to simultaneously enhance the conductivity and the mechanical strength of polymer electrolyte.« less

Orthogonal time-of-flight mass spectrometry of an ion beam with a broad kinetic energy profile.

PubMed

Miller, S W; Prince, B D; Bemish, R J

2017-10-01

A combined experimental and modeling effort is undertaken to assess a detection system composed of an orthogonal extraction time-of-flight (TOF) mass spectrometer coupled to a continuous ion source emitting an ion beam with kinetic energy of several hundred eV. The continuous ion source comprises an electrospray capillary system employing an undiluted ionic liquid emitting directly into vacuum. The resulting ion beam consists of ions with kinetic energy distributions of width greater than a hundred of eV and mass-to-charge (m/q) ratios ranging from 111 to 500 000 amu/q. In particular, the investigation aims to demonstrate the kinetic energy resolution along the ion beam axis (axial) of orthogonally extracted ions in measurements of the axial kinetic energy-specific mass spectrum, mass flow rate, and total ion current. The described instrument is capable of simultaneous measurement of a broad m/q range in a single acquisition cycle with approximately 25 eV/q axial kinetic energy resolution. Mass resolutions of ∼340 (M/ΔM, FWHM) were obtained for ions at m/q = 1974. Comparison of the orthogonally extracted TOF mass spectrum to mass flow and ion current measurements obtained with a quartz-crystal microbalance and Faraday cup, respectively, shows reasonable numeric agreement and qualitative agreement in the trend as a function of energy defect.

Importance of pH-regulated charge density on the electrophoresis of soft particles

NASA Astrophysics Data System (ADS)

Gopmandal, Partha P.; Ohshima, H.

2017-02-01

The present study deals with the electrophoresis of spherical soft particles consisting of an ion and liquid-penetrable but liquid-flow-impenetrable inner core surrounded by an ion and fluid-penetrable polyelectrolyte layer. The inner core is considered to be dielectric and bearing basic functional group coated with polyelectrolyte layer containing acidic functional group. An approximate expression for the electrophoretic mobility of such a particle is obtained under a low potential limit. The electrophoretic behaviour of the undertaken particle is investigated for a wide range of bulk pH values and electrolyte concentrations. Our study also indicates some remarkable features of the electrophoresis e.g., occurrence of zero mobility, mobility reversal etc.

Metal-induced crystallization of amorphous zinc tin oxide semiconductors for high mobility thin-film transistors

NASA Astrophysics Data System (ADS)

Hwang, Ah Young; Kim, Sang Tae; Ji, Hyuk; Shin, Yeonwoo; Jeong, Jae Kyeong

2016-04-01

Transition tantalum induced crystallization of amorphous zinc tin oxide (a-ZTO) was observed at low temperature annealing of 300 °C. Thin-film transistors (TFTs) with an a-ZTO channel layer exhibited a reasonable field-effect mobility of 12.4 cm2/V s, subthreshold swing (SS) of 0.39 V/decade, threshold voltage (VTH) of 1.5 V, and ION/OFF ratio of ˜107. A significant improvement in the field-effect mobility (up to ˜33.5 cm2/V s) was achieved for crystallized ZTO TFTs: this improvement was accomplished without compromising the SS, VTH, or ION/OFF ratio due to the presence of a highly ordered microstructure.

Investigating the role of ion-pair strategy in regulating nicotine release from patch: Mechanistic insights based on intermolecular interaction and mobility of pressure sensitive adhesive.

PubMed

Li, Qiaoyun; Wan, Xiaocao; Liu, Chao; Fang, Liang

2018-07-01

The aim of this study was to prepare a drug-in-adhesive patch of nicotine (NIC) and use ion-pair strategy to regulate drug delivery rate. Moreover, the mechanism of how ion-pair strategy regulated drug release was elucidated at molecular level. Formulation factors including pressure sensitive adhesives (PSAs), drug loading and counter ions (C 4 , C 6 , C 8 , C 10 , and C 12 ) were screened. In vitro release experiment and in vitro transdermal experiment were conducted to determine the rate-limiting step in drug delivery process. FT-IR and molecular modeling were used to characterize the interaction between drug and PSA. Thermal analysis and rheology study were conducted to investigate the mobility variation of PSA. The optimized patch prepared with NIC-C 8 had the transdermal profile fairly close to that of the commercial product (p > 0.05). The release rate constants (k) of NIC, NIC-C 4 and NIC-C 10 were 21.1, 14.4 and 32.4, respectively. Different release rates of NIC ion-pair complexes were attributed to the dual effect of ion-pair strategy on drug release. On one hand, ion-pair strategy enhanced the interaction between drug and PSA, which inhibited drug release. On the other hand, using ion-pair strategy improved the mobility of PSA, which facilitated drug release. Drug release behavior was determined by combined effect of two aspects above. These conclusions provided a new idea for us to regulate drug release behavior from patch. Copyright © 2018 Elsevier B.V. All rights reserved.

Determination of Collision Cross Sections Using a Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Dziekonski, Eric T.; Johnson, Joshua T.; Lee, Kenneth W.; McLuckey, Scott A.

2018-02-01

Collision cross sections (CCSs) were determined from the frequency-domain linewidths in a Fourier transform electrostatic linear ion trap. With use of an ultrahigh-vacuum precision leak valve and nitrogen gas, transients were recorded as the background pressure in the mass analyzer chamber was varied between 4× 10-8 and 7 × 10-7 Torr. The energetic hard-sphere ion-neutral collision model, described by Xu and coworkers, was used to relate the recorded image charge to the CCS of the molecule. In lieu of our monoisotopically isolating the mass of interest, the known relative isotopic abundances were programmed into the Lorentzian fitting algorithm such that the linewidth was extracted from a sum of Lorentzians. Although this works only if the isotopic distribution is known a priori, it prevents ion loss, preserves the high signal-to-noise ratio, and minimizes the experimental error on our homebuilt instrument. Six tetraalkylammonium cations were used to correlate the CCS measured in the electrostatic linear ion trap with that measured by drift-tube ion mobility spectrometry, for which there was an excellent correlation ( R 2 ≈ 0.9999). Although the absolute CCSs derived with our method differ from those reported, the extracted linear correlation can be used to correct the raw CCS. With use of [angiotensin II]2+ and reserpine, the corrected CCSs (334.9 ± 2.1 and 250.1 ± 0.5, respectively) were in good agreement with the reported ion mobility spectrometry CCSs (335 and 254.3, respectively). With sufficient signal-to-noise ratio, the CCSs determined are reproducible to within a fraction of a percent, comparable to the uncertainties reported on dedicated ion mobility instruments.

High sensitivity field asymmetric ion mobility spectrometer

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Ion Conductivity and Sensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bychkov, E.; Tveryanovich, Y.; Vlasov, Y.

2005-03-02

Ionic transport in glasses was discovered in the 19th century following the classical work of Warburg (1884). Since then, considerable progress has been achieved in both theoretical understanding and practical applications of ion-conducting vitreous systems (see Frischat, 1975; Malugani and Robert, 1980; Ribes, Barrau and Souquet, 1980; Kennedy and Yang, 1987; Vlasov and Bychkov, 1987; Hayashi, Tatsumisago and Minami, 1999; Doremus, 1962 and references therein). Nevertheless, this topic and especially the ion-conducting mechanisms in disordered solids need additional study using traditional macroscopic methods (ac and dc electrical conductivity, tracer diffusion, and ion transport number measurements), as well as advanced structuralmore » techniques on third generation synchrotron light sources and spallation neutron sources over a large range of the scattering vector Q. This approach led to the discovery of important features: in particular, different transport regimes at low and high mobile ion content that are closely related to a competition between the stochastic scenario and a non-random distribution of the mobile ions in the glass network. Well-known experimental findings such as compositional dependence of the Haven ratio H{sub R}, interpreted earlier by a number of drastically different ion transport models, can also be explained using a unified approach. Many of the new experimental results were obtained for silver and copper chalcogenide glasses which appear to be useful model materials, in part because of a large accessible composition domain, as well as coverage of five orders of magnitude in the mobile cation content, and corresponding dramatic changes in the ionic transport up to 10 orders of magnitude.« less

A fast integrated mobility spectrometer for rapid measurement of sub-micrometer aerosol size distribution, Part I: Design and model evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jian; Pikridas, Michael; Spielman, Steven R.

This study discusses, a fast integrated mobility spectrometer (FIMS) was previously developed to characterize submicron aerosol size distributions at a frequency of 1 Hz and with high size resolution and counting statistics. However, the dynamic size range of the FIMS was limited to one decade in particle electrical mobility. It was proposed that the FIMS dynamic size range can be greatly increased by using a spatially varying electric field. This electric field creates regions with drastically different field strengths in the separator, such that particles of a wide diameter range can be simultaneously classified and subsequently measured. A FIMS incorporatingmore » this spatially varying electric field is developed. This paper describes the theoretical frame work and numerical simulations of the FIMS with extended dynamic size range, including the spatially varying electric field, particle trajectories, activation of separated particles in the condenser, and the transfer function, transmission efficiency, and mobility resolution. The influences of the particle Brownian motion on FIMS transfer function and mobility resolution are examined. The simulation results indicate that the FIMS incorporating the spatially varying electric field is capable of measuring aerosol size distribution from 8 to 600 nm with high time resolution. As a result, the experimental characterization of the FIMS is presented in an accompanying paper.« less

A fast integrated mobility spectrometer for rapid measurement of sub-micrometer aerosol size distribution, Part I: Design and model evaluation

DOE PAGES

Wang, Jian; Pikridas, Michael; Spielman, Steven R.; ...

2017-06-01

This study discusses, a fast integrated mobility spectrometer (FIMS) was previously developed to characterize submicron aerosol size distributions at a frequency of 1 Hz and with high size resolution and counting statistics. However, the dynamic size range of the FIMS was limited to one decade in particle electrical mobility. It was proposed that the FIMS dynamic size range can be greatly increased by using a spatially varying electric field. This electric field creates regions with drastically different field strengths in the separator, such that particles of a wide diameter range can be simultaneously classified and subsequently measured. A FIMS incorporatingmore » this spatially varying electric field is developed. This paper describes the theoretical frame work and numerical simulations of the FIMS with extended dynamic size range, including the spatially varying electric field, particle trajectories, activation of separated particles in the condenser, and the transfer function, transmission efficiency, and mobility resolution. The influences of the particle Brownian motion on FIMS transfer function and mobility resolution are examined. The simulation results indicate that the FIMS incorporating the spatially varying electric field is capable of measuring aerosol size distribution from 8 to 600 nm with high time resolution. As a result, the experimental characterization of the FIMS is presented in an accompanying paper.« less

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

NASA Astrophysics Data System (ADS)

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

1991-11-01

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

Soft ionization device with characterization systems and methods of manufacture

NASA Technical Reports Server (NTRS)

Hartley, Frank T. (Inventor)

2004-01-01

Various configurations of characterization systems such as ion mobility spectrometers and mass spectrometers are disclosed that are coupled to an ionization device. The ionization device is formed of a membrane that houses electrodes therein that are located closer to one another than the mean free path of the gas being ionized. Small voltages across the electrodes generate large electric fields which act to ionize substantially all molecules passing therethrough without fracture. Methods to manufacture the mass spectrometer and ion mobility spectrometer systems are also described.

Storage Reliability of Missile Materiel Program. Storage Reliability Analysis Summary Report. Volume 1. Electrical and Electronic Devices

DTIC Science & Technology

1976-05-01

since the platinum silicide and titanium metals also offer very low mobility to the alkaline ions, the BLSJ . is inert to sodium . Inversion and...gettering agents for sodium ions, thus making the cont&-nination far less mobile. The stability of the structural and electrical properties of the oxide...to be an effective barrier to sodium migration. In Beam Lead Sealed ,unction (BLSJ) devices, the silicon nitride seals the devices from sodium and

Storage Reliability of Missile Materiel Program. Storage Reliability Analysis Summary Report. Volume 1. Electrical and Electronic Devices

DTIC Science & Technology

1978-01-01

silicon nitride seals the devices from sodium and since the platinum silicide and titanium metals also offer very low mobility to the alkaline ions, the...of bipolar devices. These materials act as gettering agents for sodium ions, thus making the contamination far less mobile. The stability of the...parameter instability. Silicon nitride has been shown to be an effective barrier to sodium migration. In Beam Lead Sealed Junction (BLSJ) devices, the

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

PubMed Central

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

2012-01-01

Differential ion mobility spectrometry (FAIMS) can baseline-resolve multiple variants of post-translationally modified peptides extending to the 3 - 4 kDa range, which differ in the localization of a PTM as small as acetylation. Essentially orthogonal separations for different charge states expand the total peak capacity in proportion to the number of observed states that increases for longer polypeptides. This might enable resolving localization variants for yet larger peptides and even intact proteins. PMID:22559289

Analysis of psilocybin and psilocin in Psilocybe subcubensis Guzmán by ion mobility spectrometry and gas chromatography-mass spectrometry.

PubMed

Keller, T; Schneider, A; Regenscheit, P; Dirnhofer, R; Rücker, T; Jaspers, J; Kisser, W

1999-01-11

A new method has been developed for the rapid analysis of psilocybin and/or psilocin in fungus material using ion mobility spectrometry. Quantitative analysis was performed by gas chromatography-mass spectrometry after a simple one-step extraction involving homogenization of the dried fruit bodies of fungi in chloroform and derivatization with MSTFA. The proposed methods resulted in rapid procedures useful in analyzing psychotropic fungi for psilocybin and psilocin.

Simulation of Ion Motion in FAIMS through Combined Use of SIMION and Modified SDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, Satendra; Tang, Keqi; Manura, David

2009-11-01

Over the years, the use of Field Asymmetric Ion Mobility Spectrometry (FAIMS) has grown with applications spanning from explosives detection to separation of complex biological mixtures. Although, the principles of ion separation in FAIMS is understood and comprehensively characterized, little effort has been made in developing commercially available computational tools that can simulate ion motion in FAIMS. Such a tool could be of great value for refining theory, optimizing the performance of the instrument for specific applications, and in modeling the fringe-fields caused by rf decay at the entrance and exit of FAIMS which can significantly affect ion transmission. Anmore » algorithm using SIMIONTM as its core structure was developed in this study to realistically compute ion trajectory at different ratios of electric field to buffer gas number density (E/N). The E/N can vary from a few Td to ~80 Td in FAIMS as created by an asymmetric square waveform. The Statistical Diffusion Simulation (SDS) model was further incorporated in the algorithm to simulate the ion diffusion in the FAIMS gap. The algorithm was validated using a FAIMS analyzer model similar to the Sionex Corporation model SVAC in terms of its dimensions and geometry. Hydroxyproline and Leucine ions with similar reduced mobility Ko (2.17 and 2.18 cm2.V-1.s-1, respectively) were used as model ions to test the new algorithm and demonstrate the effects of gas flow and waveform (voltage pulse amplitude and frequency) on peak shape and ion current transmission. Simulation results from three ion types: O2-(H2O)3, (A type), (C3H6O)2H+ (B type), and (C12H24O)2H+ (C type) were then compared with the experimental data (available in the literature). The SIMION-SDS-Field Dependent Mobility Calculation (FDMC) algorithm provided good agreement with experimental measurements of the ion peak position in FAIMS compensation voltage (CV) spectrum, peak width, and the ion transmission over a broad range of E/N.« less

Surface analysis by means of high resolution energy loss spectroscopy of 180° elastic scattered protons in the 100 keV regime

NASA Astrophysics Data System (ADS)

Jun-ichi, Kanasaki; Noriaki, Matsunami; Noriaki, Itoh; Tomoki, Oku; Kensin, Kitoh; Masahiko, Aoki; Koji, Matsuda

1988-06-01

The design and computer simulation of the performance of a new ion-beam surface analyzer has been presented. The analyzer has the capability of analyzing the energy of ions incident at 100 keV and scattered by 180° at surfaces with a resolution of 5 eV. The analyzer consists of an ion source, an accelerating-decelerating tube and a multichannel analyzer. Computer simulation of the energy spectra of ions scattered from GaAs is reported.

Contribution of capillary electrophoresis to an integrated vision of humic substances size and charge characterizations

DOE Office of Scientific and Technical Information (OSTI.GOV)

D'Orlye, Fanny; Reiller, Pascal E.

2014-02-15

The physicochemical properties of three different humic substances (HS) are probed using capillary zone electrophoresis in alkaline carbonate buffers, pH 10. Special attention is drawn to the impact of the electrolyte ionic strength and counter-ion nature, chosen within the alkali-metal series, on HS electrophoretic mobility. Taylor-Aris dispersion analysis provides insights into the hydrodynamic radius (R-H) distributions of HS. The smallest characterized entities are of nano-metric dimensions, showing neither ionic strength- nor alkali-metal-induced aggregation. These results are compared with the entities evidenced in dynamic light scattering measurements, the size of which is two order of magnitude higher, ca. 100 nm. Themore » extended Onsager model provides a reasonable description of measured electrophoretic mobilities in the ionic strength range 1-50 mM, thus allowing the estimation of limiting mobilities and ionic charge numbers for the different HS samples. An unexpected HS electrophoretic mobility increase (in absolute value) is observed in the order Li{sup +} ≤ Na{sup +} ≤ K{sup +} ≤ Cs{sup +} and discussed either in terms of retarding forces or in terms of ion-ion interactions. (authors)« less

Ion size effects on the electrokinetics of spherical particles in salt-free concentrated suspensions

NASA Astrophysics Data System (ADS)

Roa, Rafael; Carrique, Felix; Ruiz-Reina, Emilio

2012-02-01

In this work we study the influence of the counterion size on the electrophoretic mobility and on the dynamic mobility of a suspended spherical particle in a salt-free concentrated colloidal suspension. Salt-free suspensions contain charged particles and the added counterions that counterbalance their surface charge. A spherical cell model approach is used to take into account particle-particle electro-hydrodynamic interactions in concentrated suspensions. The finite size of the counterions is considered including an entropic contribution, related with the excluded volume of the ions, in the free energy of the suspension, giving rise to a modified counterion concentration profile. We are interested in studying the linear response of the system to an electric field, thus we solve the different electrokinetic equations by using a linear perturbation scheme. We find that the ionic size effect is quite important for moderate to high particles charges at a given particle volume fraction. In addition for such particle surface charges, both the electrophoretic mobility and the dynamic mobility suffer more important changes the larger the particle volume fraction for each ion size. The latter effects are more relevant the larger the ionic size.

Ultrahigh-resolution FT-ICR mass spectrometry characterization of a-pinene ozonolysis SOA

EPA Science Inventory

Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were i...

MASS MEASUREMENTS BY AN ACCURATE AND SENSITIVE SELECTED ION RECORDING TECHNIQUE

EPA Science Inventory

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

Structure of human thymidylate synthase under low-salt conditions.

PubMed

Lovelace, Leslie L; Minor, Wladek; Lebioda, Lukasz

2005-05-01

Human thymidylate synthase, a target in cancer chemotherapy, was crystallized from PEG 3350 with 30 mM ammonium sulfate (AS) in the crystallization medium. The crystals are isomorphous with the high-salt crystals ( approximately 2.0 M AS) and the structure has been solved and refined (R = 22.6%, R(free) = 24.3%) at 1.8 A resolution. The high- and low-AS-concentration structures are quite similar, with loop 181-197 is in the inactive conformation. Also, residues 95-106 and 129-135 (eukaryotic inserts region) show high mobility as assessed by poor electron density and high values of crystallographic temperature factors (residues 1-25 and 108-129 are disordered in both structures). The high mobility of this region may reflect the situation at physiological ionic strength. Of the four sulfate ions observed bound at 2.0 M AS, only two are present at 30 mM AS. The inactive conformation appears to be stabilized by the side chain of Val3 or a leucine residue from the disordered regions. The low-salt conditions of these crystals should be much more suitable for the study of thymidylate synthase inhibitors, especially those that utilize sulfate-binding sites to stabilize the inactive conformation of loop 181-197.

High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

PubMed

Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

2012-11-01

A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

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

NASA Technical Reports Server (NTRS)

Kanik, I.; Johnson, P. V.; Beegle, L. W.; Cooks, R. G.; Laughlin, B. C.; Hill, H. H.

2003-01-01

The potential of an Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer (ESI/IMS/CIT-MS) as an analytical instrument for analyzing material extracted from rock and soil samples as part of a suite of instruments on the proposed 2009 Mars Science Lander (MSL) will be demonstrated. This instrument will be able to identify volatile compounds as well as resident organic molecules on the parts-per-billion (ppb) level. Also, it will be able to obtain an inventory of chemical species on the surface of Mars which will result in a better understanding of ongoing surface chemistry. Finally, questions relevant to biological processes will be answered with the complete inventory of surface and near surface organic molecules that the ESI/IMS/CIT is capable of performing.

Analysis techniques for diagnosing runaway ion distributions in the reversed field pinch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, J., E-mail: jkim536@wisc.edu; Anderson, J. K.; Capecchi, W.

2016-11-15

An advanced neutral particle analyzer (ANPA) on the Madison Symmetric Torus measures deuterium ions of energy ranges 8-45 keV with an energy resolution of 2-4 keV and time resolution of 10 μs. Three different experimental configurations measure distinct portions of the naturally occurring fast ion distributions: fast ions moving parallel, anti-parallel, or perpendicular to the plasma current. On a radial-facing port, fast ions moving perpendicular to the current have the necessary pitch to be measured by the ANPA. With the diagnostic positioned on a tangent line through the plasma core, a chord integration over fast ion density, background neutral density,more » and local appropriate pitch defines the measured sample. The plasma current can be reversed to measure anti-parallel fast ions in the same configuration. Comparisons of energy distributions for the three configurations show an anisotropic fast ion distribution favoring high pitch ions.« less

Cross Sections and Transport Properties of BR- Ions in AR

NASA Astrophysics Data System (ADS)

Jovanovic, Jasmina; Stojanovic, Vladimir; Raspopovic, Zoran; Petrovic, Zoran

2014-10-01

We have used a combination of a simple semi-analytic theory - Momentum Transfer Theory (MTT) and exact Monte Carlo (MC) simulations to develop Br- in Ar momentum transfer cross section based on the available data for reduced mobility at the temperature T = 300 K over the range 10 Td <= E / N <= 300 Td. At very low energies, we have extrapolated obtained cross sections towards Langevin's cross section. Also, we have extrapolated data to somewhat higher energies based on behavior of similar ions in similar gases and by the addition of the total detachment cross section that was used from the threshold around 7.7 eV. Relatively complete set was derived which can be used in modeling of plasmas by both hybrid, particle in cell (PIC) and fluid codes. A good agreement between calculated and measured ion mobilities and longitudinal diffusion coefficients is an independent proof of the validity of the cross sections that were derived for the negative ion mobility data. In addition to transport coefficients we have also calculated the net rate coefficients of elastic scattering and detachment. Author acknowledge Ministry of Education, Science and Technology, Proj. Nos. 171037 and 410011.

Selection and preliminary evaluation of three structures as potential solid conductors of alkali ions: Two hollandites, a titanate, and a tungstate

NASA Technical Reports Server (NTRS)

Singer, J.; Kautz, H. E.; Fielder, W. L.; Fordyce, J. S.

1973-01-01

Utilization of crystal-chemical criteria has suggested three structure types in which alkali ions may be mobile: (1)hollandites K(x)Mg(x/2)Ti(8-x/2)O16 and K(x)Al(x)Ti(8-x)O16 for 1.6 less than or equal to x less than or equal to 2.0 tungstate K2W4013; and (3) sodium hexatitante Na2Ti6O13. Each is a tunnel structure. An electrical screening procedure, previously tested on beta-alumina, has indicated high K(+) ion mobility in the hollandites and in the tungstate, but not in the hexatitanate. Specimens were polycrystalline disks near 90 percent of theoretical density. The ac conductivity calculated from dielectric and capacitance measurements has been attributed to ion mobility. This ac conductivity was up to 0.01/ohm-cm for hollandites and about 0.0001/ohm-cm for the tungstate, with approximate activation energies of 21 to 25 and 16 kJ/mole (5 to 6 and 4 kcal/mole), respectively. Electronic conduction and chemical reactivity have eliminated the tungstate from further consideration. The hollandites have been considered worthy of further development and evaluation.

Toward artifact-free data in Hadamard transform-based double multiplexing of ion mobility-Orbitrap mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tummalacherla, Meghasyam; Garimella, Sandilya V. B.; Prost, Spencer A.

The integration of ion mobility spectrometry (IMS) with trap-based mass spectrometer (MS) such as Orbitrap using the dual gate approach suffers from low duty cycle. Efforts to improve the duty cycle involve the utilization of Hadamard transform based double multiplexing which significantly improve the signal to noise ratio and duty cycle of the ion mobility – Orbitrap mass spectrometry (IM – Orbitrap MS) platform. However, significant fluctuations in ion intensity and the temporal shifts in the encoded data give rise to artifacts and noise in the demultiplexed data which significantly reduce the data quality and negate the benefits of multiplexing.more » We propose a new approach that identifies the true IM peaks and helps in eliminating the artifacts in the demultiplexed data leading to a decrease in false positives in subsequent data processing. The algorithm takes an analytical approach to first identify the position of the IM peak in the temporal domain, and then demultiplex and identify the true data making it easier for subsequent data processing. After the application of the algorithm, the quality of the IM-Orbitrap MS measurements was greatly improved because of the reduction in artifacts.« less

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.

Application of design of experiments for formulation development and mechanistic evaluation of iontophoretic tacrine hydrochloride delivery.

PubMed

Patel, Niketkumar; Jain, Shashank; Madan, Parshotam; Lin, Senshang

2016-11-01

The objective of this investigation is to develop mathematical equation to understand the impact of variables and establish statistical control over transdermal iontophoretic delivery of tacrine hydrochloride. In addition, possibility of using conductivity measurements as a tool of predicting ionic mobility of the participating ions for the application of iontophoretic delivery was explored. Central composite design was applied to study effect of independent variables like current strength, buffer molarity, and drug concentration on iontophoretic tacrine permeation flux. Molar conductivity was determined to evaluate electro-migration of tacrine ions with application of Kohlrausch's law. The developed mathematic equation not only reveals drug concentration as the most significant variable regulating tacrine permeation, followed by current strength and buffer molarity, but also is capable to optimize tacrine permeation with respective combination of independent variables to achieve desired therapeutic plasma concentration of tacrine in treatment of Alzheimer's disease. Moreover, relative higher mobility of sodium and chloride ions was observed as compared to estimated tacrine ion mobility. This investigation utilizes the design of experiment approach and extends the primary understanding of imapct of electronic and formulation variables on the tacrine permeation for the formulation development of iontophoretic tacrine delivery.

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

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

Low-cost mobile phone microscopy with a reversed mobile phone camera lens.

PubMed

Switz, Neil A; D'Ambrosio, Michael V; Fletcher, Daniel A

2014-01-01

The increasing capabilities and ubiquity of mobile phones and their associated digital cameras offer the possibility of extending low-cost, portable diagnostic microscopy to underserved and low-resource areas. However, mobile phone microscopes created by adding magnifying optics to the phone's camera module have been unable to make use of the full image sensor due to the specialized design of the embedded camera lens, exacerbating the tradeoff between resolution and field of view inherent to optical systems. This tradeoff is acutely felt for diagnostic applications, where the speed and cost of image-based diagnosis is related to the area of the sample that can be viewed at sufficient resolution. Here we present a simple and low-cost approach to mobile phone microscopy that uses a reversed mobile phone camera lens added to an intact mobile phone to enable high quality imaging over a significantly larger field of view than standard microscopy. We demonstrate use of the reversed lens mobile phone microscope to identify red and white blood cells in blood smears and soil-transmitted helminth eggs in stool samples.

Low-Cost Mobile Phone Microscopy with a Reversed Mobile Phone Camera Lens

PubMed Central

Fletcher, Daniel A.

2014-01-01

The increasing capabilities and ubiquity of mobile phones and their associated digital cameras offer the possibility of extending low-cost, portable diagnostic microscopy to underserved and low-resource areas. However, mobile phone microscopes created by adding magnifying optics to the phone's camera module have been unable to make use of the full image sensor due to the specialized design of the embedded camera lens, exacerbating the tradeoff between resolution and field of view inherent to optical systems. This tradeoff is acutely felt for diagnostic applications, where the speed and cost of image-based diagnosis is related to the area of the sample that can be viewed at sufficient resolution. Here we present a simple and low-cost approach to mobile phone microscopy that uses a reversed mobile phone camera lens added to an intact mobile phone to enable high quality imaging over a significantly larger field of view than standard microscopy. We demonstrate use of the reversed lens mobile phone microscope to identify red and white blood cells in blood smears and soil-transmitted helminth eggs in stool samples. PMID:24854188

Characterizing and Optimizing the TITAN facility from Energy Spread Determinations with a Retarding Energy Field Analyzer

NASA Astrophysics Data System (ADS)

Champagne, Christian

The TITAN (TRIUMF's Ion Trap for Atomic and Nuclear science) experiment uses a Measurement Penning Trap (MPET) to perform high precision mass measurements (deltam/m ≈ 10--8) on short-lived (t1/2 ≈ 10 ms) isotopes. The ISAC (Isotope Separation and ACceleration) facility provides a 60 keV rare isotope beam to the experiments. A Radio-Frequency Quadrupole (RFQ) ion trap cools and bunches the incoming radioactive beam. An Electron Beam Ion Trap (EBIT) charge breeds the ions to a high charged state q. Since the MPET mass resolution is proportional to the charge state q, an improvement up to two orders of magnitude can be achieved. Further enhancements are obtained by the reduction of the uncertainty on the MPET measurements, such as from the ion bunch longitudinal kinetic energy spread. A Retarding Field energy Analyzer (RFA) was designed and constructed to measure this uncertainty. An energy resolution DeltaE/E ≈ 10--3 was expected from to simulated RFQ ion extraction longitudinal energy spread measurements. An experimental energy resolution DeltaE/E = 2.4x10--3 was obtained. Suggestions to improve the energy resolution are provided. Two testing sessions were undertaken using the RFQ and TITAN ion source to provide a singly charged pulsed ion beam. The first session used a 6Li+ beam with a 1--4 keV energy range. The RFA collimating slits were removed to insure the beam entered the RFA, increasing the energy resolution to DeltaE/E = 5 x 10 --3. An energy resolution DeltaE/E = (1.4 +/- 0.5) x 10--2 was obtained from the longitudinal energy spread measurements as a function of the beam energy. No correlation between the RFQ buffer gas pressure and the longitudinal energy spread was observed. The second session used 6,7Li, 23Na, 39,41K beams with a 1--5 keV energy range and the slits were reincorporated. A linear correlation with the RFQ extraction potentials magnitude is visible with both 2.5 keV 7Li+ and 23Na+ beams. No correlations between the RFQ buffer gas pressure, the space charge, beamgate size and beam composition with respect to the longitudinal energy spread were otherwise found. Further reduction of the RFA energy resolution is necessary to resolve longitudinal energy spread variations under different RFQ parameter settings.

Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li 3PS 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C.

The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice,more » maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, for β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less

Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li 3PS 4

DOE PAGES

Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C.; ...

2016-12-09

The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice,more » maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, for β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less

Gaseous phase ion detection method based on laser-induced fluorescence for ion mobility spectrometer

NASA Astrophysics Data System (ADS)

Guo, Kaitai; Ni, Kai; Ou, Guangli; Zhang, Xiaoguo; Yu, Quan; Qian, Xiang; Wang, Xiaohao

2015-08-01

Ion mobility spectrometry (IMS) is widely used in the field of chemical composition analysis. Faraday cup is the most classical method to detect ions for IMS in the atmospheric pressure. However, the performance of Faraday plate was limited by many kinds of factors, including interfering electromagnetic waves, thermal(Johnson) noise, induced current , gain bandwidth product, etc. There is a theoretical limit in detection of ions at ambient condition which is approximately 106 ions per second. In this paper, we introduced a novel way using laser-induced fluorescence (LIF) to bypass the limitation of Faraday plate. Fluorescent ions which were selected by IMS get excited when they fly through the laser excitation area. The fluorescence emitted by the excited ions was captured exponentially and amplified through proper optoelectronic system. Rhodamine 6G (R6G) was selected as the fluorochrome for the reason that excitation wavelength, emission wavelength, and fluorescence quantum yield were more appropriate than others. An orthometric light path is designed to eliminate the adverse impact which was caused by induced laser. The experiment result shows that a fluorescence signal from the sample ions of the IMS could be observed. Compared with Faraday plate, the LIF-IMS may find a potential application in more system at the atmosphere condition.

Atmospheric ions, boreal forests and impacts on climate

NASA Astrophysics Data System (ADS)

Manninen, H. E.; Nieminen, T.; Franchin, A.; Järvinen, E.; Kontkanen, J.; Hirsikko, A.; Hõrrak, U.; Mirme, A.; Tammet, H.; Kerminen, V.-M.; Petäjä, T.; Kulmala, M.

2012-04-01

Aerosol particles play an important role in the Earth's atmosphere and in the climate system: They scatter and absorb solar radiation, facilitate chemical processes, and serve as seeds for cloud formation. The aerosol particles have direct cooling and warming effects on climate (IPCC, 2007). Secondary new particle formation (NPF) is a globally important source of aerosol particles (Kulmala and Kerminen, 2008). Currently, the mechanisms of particle formation and the vapors participating in this process are, however, not truly understood. Several formation and growth mechanisms have been proposed for the very first steps of the process: homogeneous, heterogeneous, ion-induced and kinetic nucleation and activation type cluster growth. Small ions are part of the atmospheric aerosol spectrum, and in atmospheric sciences study of ion-aerosol interactions is essential. Small ions are small molecular clusters carrying a net electric charge. They are produced by ionisation of molecules in the air. Typically the small ion concentrations vary in the range of 100-2000 cm-3 in both polarities (Hirsikko et al., 2011). Ion-induced NPF is limited by the ion production rate, which typically is around 10 ion pairs cm-3s-1 in the boundary layer over the ground. The ion production rate has strong spatial and temporal dependence. The ionisation mechanisms change with altitude: radon and gamma radiation from the ground and galactic cosmic rays dominate close to the Earth's surface, while higher in the free troposphere cosmic rays become the main driving factor. In order to fully explain atmospheric NPF and subsequent growth, we need to measure directly the very initial steps of the formation processes. Air ion spectrometers measure the mobility distributions of charged aerosol particles in the mobility diameter range of 0.8-42 nm (Mirme et al., 2007; Tammet et al., 2011). Neutral cluster and air ion spectrometers measure additionally the mobility distribution of neutral particles larger than 2 nm in diameter by charging the aerosol sample with unipolar corona chargers (Manninen et al., 2009). According to earlier studies, the atmospheric nucleation and cluster activation take place at the mobility diameter range of 1.5-2 nm. Therefore, the ion spectrometers allow direct measurements at exactly the size where atmospheric nucleation takes place. The results indicate that the ion-induced nucleation contributes ~1-30% to the NPF events in most atmospheric conditions (Manninen et al., 2010). In other words, neutral particle formation seems to dominate over ion-mediated mechanisms, at least in the boreal forest conditions. Acknowledgements. This research was supported by the Academy of Finland Center of Excellence program (project number 1118615). Hirsikko, A. et al.: Atmospheric ions and nucleation: a review of observations, Atmos. Chem. Phys., 11, 767-798, 2011. IPCC, Climate Change 2007: The Physical Science Basis, Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, UK and New York, NY, USA, 996 pp, 2007. Kulmala, M., and Kerminen, V.-M.: On the growth of atmospheric nanoparticles, Atmos. Res., 90, 132-150, 2008. Manninen, H.E. et al.: Long-term field measurements of charged and neutral clusters using Neutral cluster and Air Ion Spectrometer (NAIS). Boreal Env. Res. 14, 591-605, 2009. Manninen, H.E. et al., EUCAARI ion spectrometer measurements at 12 European sites - analysis of new particle formation events, Atmos. Chem. Phys., 10, 7907-7927, 2010. Mirme, A. et al.: A Wide-range multi-channel Air Ion Spectrometer, Boreal Environ. Res., 12, 247-264, 2007. Tammet, H.: Symmetric inclined grid mobility analyzer for the measurement of charged clusters and fine nanoparticles in atmospheric air. Aerosol Science and Technology, 45, 468 - 479, 2011.

Intrinsic H+ ion mobility in the rabbit ventricular myocyte

PubMed Central

Vaughan-Jones, R D; Peercy, B E; Keener, J P; Spitzer, K W

2002-01-01

The intrinsic mobility of intracellular H+ ions was investigated by confocally imaging the longitudinal movement of acid inside rabbit ventricular myocytes loaded with the acetoxymethyl ester (AM) form of carboxy-seminaphthorhodafluor-1 (carboxy-SNARF-1). Acid was diffused into one end of the cell through a patch pipette filled with an isotonic KCl solution of pH 3.0. Intracellular H+ mobility was low, acid taking 20-30 s to move 40 μm down the cell. Inhibiting sarcolemmal Na+-H+ exchange with 1 mm amiloride had no effect on this time delay. Net Hi+ movement was associated with a longitudinal intracellular pH (pHi) gradient of up to 0.4 pH units. Hi+ movement could be modelled using the equations for diffusion, assuming an apparent diffusion coefficient for H+ ions (DappH) of 3.78 × 10−7 cm2 s−1, a value more than 300-fold lower than the H+ diffusion coefficient in a dilute, unbuffered solution. Measurement of the intracellular concentration of SNARF (≈400 μM) and its intracellular diffusion coefficient (0.9 × 10−7 cm2 s−1) indicated that the fluorophore itself exerted an insignificant effect (between 0.6 and 3.3 %) on the longitudinal movement of H+ equivalents inside the cell. The longitudinal movement of intracellular H+ is discussed in terms of a diffusive shuttling of H+ equivalents on high capacity mobile buffers which comprise about half (≈11 mm) of the total intrinsic buffering capacity within the myocyte (the other half being fixed buffer sites on low mobility, intracellular proteins). Intrinsic Hi+ mobility is consistent with an average diffusion coefficient for the intracellular mobile buffers (Dmob) of ≈9 × 10−7 cm2 s−1. PMID:12015426

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toczydlowska, Diana; Kedra-Krolik, Karolina; Nejbert, Krzysztof

The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) duemore » to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Xueyun; Wojcik, Roza; Zhang, Xing

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

IMS applications analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

RODACY,PHILIP J.; REBER,STEPHEN D.; SIMONSON,ROBERT J.

This report examines the market potential of a miniature, hand-held Ion Mobility Spectrometer. Military and civilian markets are discussed, as well as applications in a variety of diverse fields. The strengths and weaknesses of competing technologies are discussed. An extensive Ion Mobility Spectrometry (IMS) bibliography is included. The conclusions drawn from this study are: (1) There are a number of competing technologies that are capable of detecting explosives, drugs, biological, or chemical agents. The IMS system currently represents the best available compromise regarding sensitivity, specificity, and portability. (2) The military market is not as large as the commercial market, butmore » the military services are more likely to invest R and D funds in the system. (3) Military applications should be addressed before commercial applications are addressed. (4) There is potentially a large commercial market for rugged, hand-held Ion Mobility Spectrometer systems. Commercial users typically do not invest R and D funds in this type of equipment rather, they wait for off-the-shelf availability.« less

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

PubMed Central

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

2016-01-01

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