Identification of the chemical constituents of Chinese medicine Yi-Xin-Shu capsule by molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation.

PubMed

Wang, Hong-ping; Chen, Chang; Liu, Yan; Yang, Hong-Jun; Wu, Hong-Wei; Xiao, Hong-Bin

2015-11-01

The incomplete identification of the chemical components of traditional Chinese medicinal formula has been one of the bottlenecks in the modernization of traditional Chinese medicine. Tandem mass spectrometry has been widely used for the identification of chemical substances. Current automatic tandem mass spectrometry acquisition, where precursor ions were selected according to their signal intensity, encounters a drawback in chemical substances identification when samples contain many overlapping signals. Compounds in minor or trace amounts could not be identified because most tandem mass spectrometry information was lost. Herein, a molecular feature orientated precursor ion selection and tandem mass spectrometry structure elucidation method for complex Chinese medicine chemical constituent analysis was developed. The precursor ions were selected according to their two-dimensional characteristics of retention times and mass-to-charge ratio ranges from herbal compounds, so that all precursor ions from herbal compounds were included and more minor chemical constituents in Chinese medicine were identified. Compared to the conventional automatic tandem mass spectrometry setups, the approach is novel and can overcome the drawback for chemical substances identification. As an example, 276 compounds from the Chinese Medicine of Yi-Xin-Shu capsule were identified. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion and aerosol precursor densities in Titan's ionosphere: A multi-instrument case study

NASA Astrophysics Data System (ADS)

Shebanits, O.; Wahlund, J.-E.; Edberg, N. J. T.; Crary, F. J.; Wellbrock, A.; Andrews, D. J.; Vigren, E.; Desai, R. T.; Coates, A. J.; Mandt, K. E.; Waite, J. H.

2016-10-01

The importance of the heavy ions and dust grains for the chemistry and aerosol formation in Titan's ionosphere has been well established in the recent years of the Cassini mission. In this study we combine independent in situ plasma (Radio Plasma and Wave Science Langmuir Probe (RPWS/LP)) and particle (Cassini Plasma Science Electron Spectrometer, Cassini Plasma Science Ion Beam Spectrometer, and Ion and Neutral Mass Spectrometer) measurements of Titan's ionosphere for selected flybys (T16, T29, T40, and T56) to produce altitude profiles of mean ion masses including heavy ions and develop a Titan-specific method for detailed analysis of the RPWS/LP measurements (applicable to all flybys) to further constrain ion charge densities and produce the first empirical estimate of the average charge of negative ions and/or dust grains. Our results reveal the presence of an ion-ion (dusty) plasma below 1100 km altitude, with charge densities exceeding the primary ionization peak densities by a factor ≥2 in the terminator and nightside ionosphere (ne/ni ≤ 0.1). We suggest that ion-ion (dusty) plasma may also be present in the dayside ionosphere below 900 km (ne/ni < 0.5 at 1000 km altitude). The average charge of the dust grains (≥1000 amu) is estimated to be between -2.5 and -1.5 elementary charges, increasing toward lower altitudes.

Electron ionization of SiCl4

NASA Astrophysics Data System (ADS)

King, Simon J.; Price, Stephen D.

2011-02-01

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl4, in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl4. For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl4. Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl2+ fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl42+. The lowest energy dicationic precursor state, leading to SiCl3+ + Cl+ formation, lies 27.4 ± 0.3 eV above the ground state of SiCl4 and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Electron ionization of SiCl4.

PubMed

King, Simon J; Price, Stephen D

2011-02-21

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).

Wakes and precursor soliton excitations by a moving charged object in a plasma

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

Kumar Tiwari, Sanat, E-mail: sanat-tiwari@uiowa.edu; Department of Physics and Astronomy, University of Iowa, Iowa City, Iowa 52242; Sen, Abhijit, E-mail: senabhijit@gmail.com

2016-02-15

We study the evolution of nonlinear ion acoustic wave excitations due to a moving charged source in a plasma. Our numerical investigations of the full set of cold fluid equations go beyond the usual weak nonlinearity approximation and show the existence of a rich variety of solutions including wakes, precursor solitons, and “pinned” solitons that travel with the source velocity. These solutions represent a large amplitude generalization of solutions obtained in the past for the forced Korteweg deVries equation and can find useful applications in a variety of situations in the laboratory and in space, wherever there is a largemore » relative velocity between the plasma and a charged object.« less

Charge Retention by Organometallic Dications on Self-Assembled Monolayer Surfaces

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

Laskin, Julia; Wang, Peng

2014-05-15

Charge retention by mass-selected ruthenium trisbipyridine dications, or Ru(bpy)32+, soft-landed onto self-assembled monolayer (SAM) surfaces of 1H, 1H, 2H, 2H-perfluorodecane-1-thiol (FSAM), 11-mercaptoundecanoic acid (COOH-SAM), and 11-amino-1-undecanethiol (HSAM) on gold was examined using in situ time-resolved secondary ion mass spectrometry in a Fourier transform ion cyclotron resonance apparatus (FT-ICR SIMS). FT-ICR SIMS analysis was performed during ion soft-landing and for 8–15 hours after the ion beam was switched off. Our results demonstrate efficient retention of the doubly charged precursor ion on the FSAM and COOH-SAM surfaces manifested by the abundant Ru(bpy)32+ ions in the SIMS spectra. In contrast, only the singlymore » charged Ru(bpy)3+ and Ru(bpy)2+ ions were observed on HSAM, indicating rapid loss of at least one charge by the deposited dications. The signal of Ru(bpy)32+ on COOH-SAM remained almost constant for more than 8 hours after the end of ion soft-landing, while a relatively fast decay followed by a plateau region was observed on the FSAM surface. However, we found that SIMS analysis of Ru(bpy)32+ ions soft-landed onto FSAM is complicated by facile ion-molecule reactivity occurring either on the surface or in the SIMS plume, making it difficult to accurately measure the charge reduction kinetics. Efficient retention of the doubly charged Ru(bpy)32+ ions on COOH-SAM is remarkably different from facile neutralization of protonated peptides deposited onto this surface reported in previous studies. Our results indicate different mechanisms of charge reduction of protonated molecules and permanent ions, such as Ru(bpy)32+, on SAM surfaces. Thus, we propose that proton loss is the major charge reduction channel for the protonated species, while electron transfer through the insulating SAM is responsible for the charge loss by permanent ions. Fundamental understanding of charge reduction phenomena is essential for controlled preparation of catalytically active substrates using ion soft-landing.« less

Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides

PubMed Central

Liu, Jian; McLuckey, Scott A.

2012-01-01

The effect of cation charge state on product partitioning in the gas-phase ion/ion electron transfer reactions of multiply protonated tryptic peptides, model peptides, and relatively large peptides with singly charged radical anions has been examined. In particular, partitioning into various competing channels, such as proton transfer (PT) versus electron transfer (ET), electron transfer with subsequent dissociation (ETD) versus electron transfer with no dissociation (ET,noD), and fragmentation of backbone bonds versus fragmentation of side chains, was measured quantitatively as a function of peptide charge state to allow insights to be drawn about the fundamental aspects of ion/ion reactions that lead to ETD. The ET channel increases relative to the PT channel, ETD increases relative to ET,noD, and fragmentation at backbone bonds increases relative to side-chain cleavages as cation charge state increases. The increase in ET versus PT with charge state is consistent with a Landau-Zener based curve-crossing model. An optimum charge state for ET is predicted by the model for the ground state-to-ground state reaction. However, when the population of excited product ion states is considered, it is possible that a decrease in ET efficiency as charge state increases will not be observed due to the possibility of the population of excited electronic states of the products. Several factors can contribute to the increase in ETD versus ET,noD and backbone cleavage versus side-chain losses. These factors include an increase in reaction exothermicity and charge state dependent differences in precursor and product ion structures, stabilities, and sites of protonation. PMID:23264749

Effects of Charge State on Fragmentation Pathways, Dynamics, and Activation Energies of Ubiquitin Ions Measured by Blackbody Infrared Radiative Dissociation

PubMed Central

Jockusch, Rebecca A.; Schnier, Paul D.; Price, William D.; Strittmatter, Eric. F.; Demirev, Plamen A.; Williams*, Evan R.

2005-01-01

Blackbody infrared radiative dissociation spectra of the (M + 5H)5+ through (M + 11H)11+ ions of the protein ubiquitin (8.6 kDa) formed by electrospray ionization were measured in a Fourier-transform mass spectrometer. The 5+ ion dissociates exclusively by loss of water and/or ammonia, whereas the 11+ charge state dissociates only by formation of complementary y and b ions. These two processes are competitive for intermediate charge state ions, with the formation of y and b ions increasingly favored for the higher charge states. The y and b ions are formed by cleavage of the backbone amide bond on the C-terminal side of acidic residues exclusively, with cleavage adjacent to aspartic acid favored. Thermal unimolecular dissociation rate constants for the dissociation of each of these charge states were measured. From the temperature dependence of these rates, Arrhenius activation parameters in the rapid energy exchange limit are obtained. The activation energies (Ea) and preexponential factors (A) for the 5+, 8+, and 9+ ions are 1.2 eV and 1012 s−1, respectively. These values for the 6+ and 7+ ions are 0.9–1.0 eV and 109 s−1, and those for the 10+ and 11+ ions are 1.6 eV and 1016–1017 s−1. Thus, with the exception of the 5+ ion, the higher charge states of ubiquitin have larger dissociation activation energies than the lower charge states. The different A factors observed for production of y and b ions from different precursor charge states indicate that they are formed by different mechanisms, ranging from relatively complex rearrangements to direct bond cleavages. These results clearly demonstrate that the relative dissociation rates of large biomolecule ions by themselves are not necessarily a reliable indicator of their relative dissociation energies, even when similar fragment ions are formed. PMID:9075403

Effects of charge state on fragmentation pathways, dynamics, and activation energies of ubiquitin ions measured by blackbody infrared radiative dissociation.

PubMed

Jockusch, R A; Schnier, P D; Price, W D; Strittmatter, E F; Demirev, P A; Williams, E R

1997-03-15

Blackbody infrared radiative dissociation spectra of the (M + 5H)5+ through (M + 11H)11+ ions of the protein ubiquitin (8.6 kDa) formed by electrospray ionization were measured in a Fourier-transform mass spectrometer. The 5+ ion dissociates exclusively by loss of water and/or ammonia, whereas the 11+ charge state dissociates only by formation of complementary y and b ions. These two processes are competitive for intermediate charge state ions, with the formation of y and b ions increasingly favored for the higher charge states. The y and b ions are formed by cleavage of the backbone amide bond on the C-terminal side of acidic residues exclusively, with cleavage adjacent to aspartic acid favored. Thermal unimolecular dissociation rate constants for the dissociation of each of these charge states were measured. From the temperature dependence of these rates, Arrhenius activation parameters in the rapid energy exchange limit are obtained. The activation energies (Ea) and preexponential factors (A) for the 5+, 8+, and 9+ ions are 1.2 eV and 10(12) s-1, respectively. These values for the 6+ and 7+ ions are 0.9-1.0 eV and 10(9) s-1, and those for the 10+ and 11+ ions are 1.6 eV and 10(16)-10(17) s-1. Thus, with the exception of the 5+ ion, the higher charge states of ubiquitin have larger dissociation activation energies than the lower charge states. The different A factors observed for production of y and b ions from different precursor charge states indicate that they are formed by different mechanisms, ranging from relatively complex rearrangements to direct bond cleavages. These results clearly demonstrate that the relative dissociation rates of large biomolecule ions by themselves are not necessarily a reliable indicator of their relative dissociation energies, even when similar fragment ions are formed.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes

NASA Astrophysics Data System (ADS)

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-01

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Innovation Meets Performance Demands of Advanced Lithium-ion Batteries

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

Advancements in high capacity and low density battery technologies have led to a growing need for battery materials with greater charge capacity and therefore stability. NREL's developments in ALD and molecular layer MLD allow for thin film coatings to battery composite electrodes, which can improve battery lifespan, high charge capacity, and stability. Silicon, one of the best high-energy anode materials for Li-ion batteries, can experience capacity fade from volumetric expansion. Using MLD to examine how surface modification could stabilize silicon anode material in Li-ion batteries, researchers discovered a new reaction precursor that leads to a flexible surface coating that accommodatesmore » volumetric expansion of silicon electrodes.« less

Clustering and Filtering Tandem Mass Spectra Acquired in Data-Independent Mode

NASA Astrophysics Data System (ADS)

Pak, Huisong; Nikitin, Frederic; Gluck, Florent; Lisacek, Frederique; Scherl, Alexander; Muller, Markus

2013-12-01

Data-independent mass spectrometry activates all ion species isolated within a given mass-to-charge window ( m/z) regardless of their abundance. This acquisition strategy overcomes the traditional data-dependent ion selection boosting data reproducibility and sensitivity. However, several tandem mass (MS/MS) spectra of the same precursor ion are acquired during chromatographic elution resulting in large data redundancy. Also, the significant number of chimeric spectra and the absence of accurate precursor ion masses hamper peptide identification. Here, we describe an algorithm to preprocess data-independent MS/MS spectra by filtering out noise peaks and clustering the spectra according to both the chromatographic elution profiles and the spectral similarity. In addition, we developed an approach to estimate the m/z value of precursor ions from clustered MS/MS spectra in order to improve database search performance. Data acquired using a small 3 m/z units precursor mass window and multiple injections to cover a m/z range of 400-1400 was processed with our algorithm. It showed an improvement in the number of both peptide and protein identifications by 8 % while reducing the number of submitted spectra by 18 % and the number of peaks by 55 %. We conclude that our clustering method is a valid approach for data analysis of these data-independent fragmentation spectra. The software including the source code is available for the scientific community.

High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

NASA Astrophysics Data System (ADS)

Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

2014-02-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4-10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Effects of Residual Lithium in the precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance

NASA Astrophysics Data System (ADS)

Jo, Minsang; Ku, Heesuk; Park, Sanghyuk; Song, Junho; Kwon, Kyungjung

2018-07-01

Li[Ni1/3Co1/3Mn1/3]O2 cathode active materials are synthesized from co-precipitated hydroxide precursors Lix[Ni1/3Co1/3Mn1/3]1-x(OH)2, and the effect of residual Li in the precursors on the lithium-ion battery (LIB) performance of their corresponding cathode active materials is investigated. Three kinds of precursors that contain different amounts of Li are selected depending on different conditions of the solution composition for the co-precipitation and washing process. It is confirmed that the introduction of Li to the precursors reduces the degree of structural perfection by X-ray diffraction analysis. Undesirable cation mixing occurs with the increasing Li content of the precursors, which is inferred from a decline in lattice parameters and the calculated intensity ratio of (003) and (104) peaks. In the voltage range of 3.0-4.3 V, the initial charge/discharge capacities and the rate capability of the cathode active materials are aggravated when Li exists in the precursors. Therefore, it could be concluded that the strict control of Li in a solution for co-precipitation of precursors is necessary in the resynthesis of cathode active materials from spent LIBs.

Determination of the location of positive charges in gas-phase polypeptide polycations by tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Kjeldsen, Frank; Savitski, Mikhail M.; Adams, Christopher M.; Zubarev, Roman A.

2006-06-01

Location of protonated sites in electrospray-ionized gas-phase peptides and proteins was performed with tandem mass spectrometry using ion activation by both electron capture dissociation (ECD) and collisional activation dissociation (CAD). Charge-carrying sites were assigned based on the increment in the charge state of fragment ions compared to that of the previous fragment in the same series. The property of ECD to neutralize preferentially the least basic site was confirmed by the analysis of three thousand ECD mass spectra of doubly charged tryptic peptides. Multiply charged cations of bradykinin, neurotensin and melittin were studied in detail. For n+ precursors, ECD revealed the positions of (n - 1) most basic sites, while CAD could in principle locate alln charges. However, ECD introduced minimal proton mobilization and produced more conclusive data than CAD, for which N- and C-terminal data often disagreed. Consistent with the dominance of one charge conformer and its preservation in ECD, the average charge states of complementary fragments of n+ ions almost always added up to (n - 1)+, while the similar figure in CAD often deviated from n+, indicating extensive charge isomerization under collisional excitation. For bradykinin and neurotensin, the charge assignments were largely in agreement with the intrinsic gas-phase basicity of the respective amino acid residues. For melittin ions in higher charge states, ECD revealed the charging at both intrinsically basic as well as at less basic residues, which was attributed to charge sharing with other groups due to the presence of secondary and higher order structures in this larger polypeptide.

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

NASA Astrophysics Data System (ADS)

Moss, Christopher L.; Chung, Thomas W.; Wyer, Jean A.; Nielsen, Steen Brøndsted; Hvelplund, Preben; Tureček, František

2011-04-01

Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of low-energy electrons by doubly charged ions in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H2PO4 radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations and H- atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations.

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

Position-dependent effects of polylysine on Sec protein transport.

PubMed

Liang, Fu-Cheng; Bageshwar, Umesh K; Musser, Siegfried M

2012-04-13

The bacterial Sec protein translocation system catalyzes the transport of unfolded precursor proteins across the cytoplasmic membrane. Using a recently developed real time fluorescence-based transport assay, the effects of the number and distribution of positive charges on the transport time and transport efficiency of proOmpA were examined. As expected, an increase in the number of lysine residues generally increased transport time and decreased transport efficiency. However, the observed effects were highly dependent on the polylysine position in the mature domain. In addition, a string of consecutive positive charges generally had a more significant effect on transport time and efficiency than separating the charges into two or more charged segments. Thirty positive charges distributed throughout the mature domain resulted in effects similar to 10 consecutive charges near the N terminus of the mature domain. These data support a model in which the local effects of positive charge on the translocation kinetics dominate over total thermodynamic constraints. The rapid translocation kinetics of some highly charged proOmpA mutants suggest that the charge is partially shielded from the electric field gradient during transport, possibly by the co-migration of counter ions. The transport times of precursors with multiple positively charged sequences, or "pause sites," were fairly well predicted by a local effect model. However, the kinetic profile predicted by this local effect model was not observed. Instead, the transport kinetics observed for precursors with multiple polylysine segments support a model in which translocation through the SecYEG pore is not the rate-limiting step of transport.

Position-dependent Effects of Polylysine on Sec Protein Transport*

PubMed Central

Liang, Fu-Cheng; Bageshwar, Umesh K.; Musser, Siegfried M.

2012-01-01

The bacterial Sec protein translocation system catalyzes the transport of unfolded precursor proteins across the cytoplasmic membrane. Using a recently developed real time fluorescence-based transport assay, the effects of the number and distribution of positive charges on the transport time and transport efficiency of proOmpA were examined. As expected, an increase in the number of lysine residues generally increased transport time and decreased transport efficiency. However, the observed effects were highly dependent on the polylysine position in the mature domain. In addition, a string of consecutive positive charges generally had a more significant effect on transport time and efficiency than separating the charges into two or more charged segments. Thirty positive charges distributed throughout the mature domain resulted in effects similar to 10 consecutive charges near the N terminus of the mature domain. These data support a model in which the local effects of positive charge on the translocation kinetics dominate over total thermodynamic constraints. The rapid translocation kinetics of some highly charged proOmpA mutants suggest that the charge is partially shielded from the electric field gradient during transport, possibly by the co-migration of counter ions. The transport times of precursors with multiple positively charged sequences, or “pause sites,” were fairly well predicted by a local effect model. However, the kinetic profile predicted by this local effect model was not observed. Instead, the transport kinetics observed for precursors with multiple polylysine segments support a model in which translocation through the SecYEG pore is not the rate-limiting step of transport. PMID:22367204

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

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Novel fragmentation pathways of anionic adducts of steroids formed by electrospray anion attachment involving regioselective attachment, regiospecific decompositions, charge-induced pathways, and ion-dipole complex intermediates.

PubMed

Rannulu, Nalaka S; Cole, Richard B

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion](-) adducts of these steroids revealed that fluoride adduct [M + F](-) precursors first lose HF to produce [M - H](-) and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d(4)-pregnenolone, are also discussed.

Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

NASA Astrophysics Data System (ADS)

Rannulu, Nalaka S.; Cole, Richard B.

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

A Distonic Radical-Ion for Detection of Traces of Adventitious Molecular Oxygen (O2) in Collision Gases Used in Tandem Mass Spectrometers

NASA Astrophysics Data System (ADS)

Jariwala, Freneil B.; Hibbs, John A.; Weisbecker, Carl S.; Ressler, John; Khade, Rahul L.; Zhang, Yong; Attygalle, Athula B.

2014-09-01

We describe a diagnostic ion that enables rapid semiquantitative evaluation of the degree of oxygen contamination in the collision gases used in tandem mass spectrometers. Upon collision-induced dissociation (CID), the m/z 359 positive ion generated from the analgesic etoricoxib undergoes a facile loss of a methyl sulfone radical [•SO2(CH3); 79-Da] to produce a distonic radical cation of m/z 280. The product-ion spectrum of this m/z 280 ion, recorded under low-energy activation on tandem-in-space QqQ or QqTof mass spectrometers using nitrogen from a generator as the collision gas, or tandem-in-time ion-trap (LCQ, LTQ) mass spectrometers using purified helium as the buffer gas, showed two unexpected peaks at m/z 312 and 295. This enigmatic m/z 312 ion, which bears a mass-to-charge ratio higher than that of the precursor ion, represented an addition of molecular oxygen (O2) to the precursor ion. The exceptional affinity of the m/z 280 radical cation towards oxygen was deployed to develop a method to determine the oxygen content in collision gases.

Infrared Multiphoton Dissociation for Quantitative Shotgun Proteomics

PubMed Central

Ledvina, Aaron R.; Lee, M. Violet; McAlister, Graeme C.; Westphall, Michael S.; Coon, Joshua J.

2012-01-01

We modified a dual-cell linear ion trap mass spectrometer to perform infrared multiphoton dissociation (IRMPD) in the low pressure trap of a dual-cell quadrupole linear ion trap (dual cell QLT) and perform large-scale IRMPD analyses of complex peptide mixtures. Upon optimization of activation parameters (precursor q-value, irradiation time, and photon flux), IRMPD subtly, but significantly outperforms resonant excitation CAD for peptides identified at a 1% false-discovery rate (FDR) from a yeast tryptic digest (95% confidence, p = 0.019). We further demonstrate that IRMPD is compatible with the analysis of isobaric-tagged peptides. Using fixed QLT RF amplitude allows for the consistent retention of reporter ions, but necessitates the use of variable IRMPD irradiation times, dependent upon precursor mass-to-charge (m/z). We show that IRMPD activation parameters can be tuned to allow for effective peptide identification and quantitation simultaneously. We thus conclude that IRMPD performed in a dual-cell ion trap is an effective option for the large-scale analysis of both unmodified and isobaric-tagged peptides. PMID:22480380

Metal-organic frameworks for lithium ion batteries and supercapacitors

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

Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

2015-03-15

Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefitmore » from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.« less

Sequencing Larger Intact Proteins (30-70 kDa) with Activated Ion Electron Transfer Dissociation

NASA Astrophysics Data System (ADS)

Riley, Nicholas M.; Westphall, Michael S.; Coon, Joshua J.

2018-01-01

The analysis of intact proteins via mass spectrometry can offer several benefits to proteome characterization, although the majority of top-down experiments focus on proteoforms in a relatively low mass range (<30 kDa). Recent studies have focused on improving the analysis of larger intact proteins (up to 75 kDa), but they have also highlighted several challenges to be addressed. One major hurdle is the efficient dissociation of larger protein ions, which often to do not yield extensive fragmentation via conventional tandem MS methods. Here we describe the first application of activated ion electron transfer dissociation (AI-ETD) to proteins in the 30-70 kDa range. AI-ETD leverages infrared photo-activation concurrent to ETD reactions to improve sequence-informative product ion generation. This method generates more product ions and greater sequence coverage than conventional ETD, higher-energy collisional dissociation (HCD), and ETD combined with supplemental HCD activation (EThcD). Importantly, AI-ETD provides the most thorough protein characterization for every precursor ion charge state investigated in this study, making it suitable as a universal fragmentation method in top-down experiments. Additionally, we highlight several acquisition strategies that can benefit characterization of larger proteins with AI-ETD, including combination of spectra from multiple ETD reaction times for a given precursor ion, multiple spectral acquisitions of the same precursor ion, and combination of spectra from two different dissociation methods (e.g., AI-ETD and HCD). In all, AI-ETD shows great promise as a method for dissociating larger intact protein ions as top-down proteomics continues to advance into larger mass ranges. [Figure not available: see fulltext.

Investigation of energy deposited by femtosecond electron transfer in collisions using hydrated ion nanocalorimetry.

PubMed

Holm, Anne I S; Donald, William A; Hvelplund, Preben; Larsen, Mikkel K; Nielsen, Steen Brøndsted; Williams, Evan R

2008-10-30

Ion nanocalorimetry is used to investigate the internal energy deposited into M (2+)(H 2O) n , M = Mg ( n = 3-11) and Ca ( n = 3-33), upon 100 keV collisions with a Cs or Ne atom target gas. Dissociation occurs by loss of water molecules from the precursor (charge retention) or by capture of an electron to form a reduced precursor (charge reduction) that can dissociate either by loss of a H atom accompanied by water molecule loss or by exclusively loss of water molecules. Formation of bare CaOH (+) and Ca (+) by these two respective dissociation pathways occurs for clusters with n up to 33 and 17, respectively. From the threshold dissociation energies for the loss of water molecules from the reduced clusters, obtained from binding energies calculated using a discrete implementation of the Thomson liquid drop model and from quantum chemistry, estimates of the internal energy deposition can be obtained. These values can be used to establish a lower limit to the maximum and average energy deposition. Not taking into account effects of a kinetic shift, over 16 eV can be deposited into Ca (2+)(H 2O) 33, the minimum energy necessary to form bare CaOH (+) from the reduced precursor. The electron capture efficiency is at least a factor of 40 greater for collisions of Ca (2+)(H 2O) 9 with Cs than with Ne, reflecting the lower ionization energy of Cs (3.9 eV) compared to Ne (21.6 eV). The branching ratio of the two electron capture dissociation pathways differs significantly for these two target gases, but the distributions of water molecules lost from the reduced precursors are similar. These results suggest that the ionization energy of the target gas has a large effect on the electron capture efficiency, but relatively little effect on the internal energy deposited into the ion. However, the different branching ratios suggest that different electronic excited states may be accessed in the reduced precursor upon collisions with these two different target gases.

Characteristics and properties of nano-LiCoO2 synthesized by pre-organized single source precursors: Li-ion diffusivity, electrochemistry and biological assessment.

PubMed

Brog, Jean-Pierre; Crochet, Aurélien; Seydoux, Joël; Clift, Martin J D; Baichette, Benoît; Maharajan, Sivarajakumar; Barosova, Hana; Brodard, Pierre; Spodaryk, Mariana; Züttel, Andreas; Rothen-Rutishauser, Barbara; Kwon, Nam Hee; Fromm, Katharina M

2017-08-22

LiCoO 2 is one of the most used cathode materials in Li-ion batteries. Its conventional synthesis requires high temperature (>800 °C) and long heating time (>24 h) to obtain the micronscale rhombohedral layered high-temperature phase of LiCoO 2 (HT-LCO). Nanoscale HT-LCO is of interest to improve the battery performance as the lithium (Li + ) ion pathway is expected to be shorter in nanoparticles as compared to micron sized ones. Since batteries typically get recycled, the exposure to nanoparticles during this process needs to be evaluated. Several new single source precursors containing lithium (Li + ) and cobalt (Co 2+ ) ions, based on alkoxides and aryloxides have been structurally characterized and were thermally transformed into nanoscale HT-LCO at 450 °C within few hours. The size of the nanoparticles depends on the precursor, determining the electrochemical performance. The Li-ion diffusion coefficients of our LiCoO 2 nanoparticles improved at least by a factor of 10 compared to commercial one, while showing good reversibility upon charging and discharging. The hazard of occupational exposure to nanoparticles during battery recycling was investigated with an in vitro multicellular lung model. Our heterobimetallic single source precursors allow to dramatically reduce the production temperature and time for HT-LCO. The obtained nanoparticles of LiCoO 2 have faster kinetics for Li + insertion/extraction compared to microparticles. Overall, nano-sized LiCoO 2 particles indicate a lower cytotoxic and (pro-)inflammogenic potential in vitro compared to their micron-sized counterparts. However, nanoparticles aggregate in air and behave partially like microparticles.

Direct Identification of Tyrosine Sulfation by using Ultraviolet Photodissociation Mass Spectrometry

NASA Astrophysics Data System (ADS)

Robinson, Michelle R.; Moore, Kevin L.; Brodbelt, Jennifer S.

2014-08-01

Sulfation is a common post-translational modification of tyrosine residues in eukaryotes; however, detection using traditional liquid chromatography-mass spectrometry (LC-MS) methods is challenging based on poor ionization efficiency in the positive ion mode and facile neutral loss upon collisional activation. In the present study, 193 nm ultraviolet photodissociation (UVPD) is applied to sulfopeptide anions to generate diagnostic sequence ions, which do not undergo appreciable neutral loss of sulfate even using higher energy photoirradiation parameters. At the same time, neutral loss of SO3 is observed from the precursor and charge-reduced precursor ions, a spectral feature that is useful for differentiating tyrosine sulfation from the nominally isobaric tyrosine phosphorylation. LC-MS detection limits for UVPD analysis in the negative mode were determined to be around 100 fmol for three sulfated peptides, caerulein, cionin, and leu-enkephalin. The LC-UVPD-MS method was applied for analysis of bovine fibrinogen, and its key sulfated peptide was confidently identified.

Direct Identification of Tyrosine Sulfation by using Ultraviolet Photodissociation Mass Spectrometry

PubMed Central

Robinson, Michelle R.; Moore, Kevin L.; Brodbelt, Brodbelt

2014-01-01

Sulfation is a common post-translational modification of tyrosine residues in eukaryotes; however, detection using traditional liquid chromatography-mass spectrometry (LC-MS) methods is challenging based on poor ionization efficiency in the positive ion mode and facile neutral loss upon collisional activation. In the present study, 193 nm ultraviolet photodissociation (UVPD) is applied to sulfopeptide anions to generate diagnostic sequence ions which do not undergo appreciable neutral loss of sulfate even using higher energy photoirradiation parameters. At the same time, neutral loss of sulfate is observed from the precursor and charge reduced precursor ions, a spectral feature that is useful for differentiating tyrosine sulfation from the nominally isobaric tyrosine phosphorylation. LC-MS detection limits for UVPD analysis in the negative mode were determined to be around 100 fmol for three sulfated peptides, caerulein, cionin, and leu-enkephalin. The LC-UVPD-MS method was applied for analysis of bovine fibrinogen, and its key sulfated peptide was confidently identified. PMID:24845354

A table of polyatomic interferences in ICP-MS

USGS Publications Warehouse

May, Thomas W.; Wiedmeyer, Ray H.

1998-01-01

Spectroscopic interferences are probably the largest class of interferences in ICP-MS and are caused by atomic or molecular ions that have the same mass-to-charge as analytes of interest. Current ICP-MS instrumental software corrects for all known atomic “isobaric” interferences, or those caused by overlapping isotopes of different elements, but does not correct for most polyatomic interferences. Such interferences are caused by polyatomic ions that are formed from precursors having numerous sources, such as the sample matrix, reagents used for preparation, plasma gases, and entrained atmospheric gases.

Generation and collision-induced dissociation of ammonium tetrafluoroborate cluster ions.

PubMed

Dain, Ryan P; Van Stipdonk, Michael J

2008-07-01

Singly and doubly charged cluster ions of ammonium tetrafluoroborate (NH4BF4) with general formula [(NH4BF4)nNH4]+ and [(NH4BF4)m(NH4)2]2+, respectively, were generated by electrospray ionization (ESI) and their fragmentation examined using collision-induced dissociation (CID) and ion-trap tandem mass spectrometry. CID of [(NH4BF4)nNH4]+ caused the loss of one or more neutral NH4BF4 units. The n = 2 cluster, [(NH4BF4)2NH4]+, was unique in that it also exhibited a dissociation pathway in which HBF4 was eliminated to create [(NH4BF4)(NH3)NH4]+. Dissociation of [(NH4BF4)m(NH4)2]2+ occurred through two general pathways: (a) 'fission' to produce singly charged cluster ions and (b) elimination of one or more neutral NH4BF4 units to leave doubly charged product ions. CID profiles, and measurements of changing precursor and product ion signal intensity as a function of applied collision voltage, were collected for [(NH4BF4)nNH4]+ and compared with those for analogous [(NaBF4)nNa]+ and [(KBF4)nK]+ ions to determine the influence of the cation on the relative stability of cluster ions. In general, the [(NH4BF4)nNH4]+ clusters were found to be easier to dissociate than both the sodium and potassium clusters of comparable size, with [(KBF4)nK]+ ions the most difficult to dissociate.

Origin of poor doping efficiency in solution processed organic semiconductors.

PubMed

Jha, Ajay; Duan, Hong-Guang; Tiwari, Vandana; Thorwart, Michael; Miller, R J Dwayne

2018-05-21

Doping is an extremely important process where intentional insertion of impurities in semiconductors controls their electronic properties. In organic semiconductors, one of the convenient, but inefficient, ways of doping is the spin casting of a precursor mixture of components in solution, followed by solvent evaporation. Active control over this process holds the key to significant improvements over current poor doping efficiencies. Yet, an optimized control can only come from a detailed understanding of electronic interactions responsible for the low doping efficiencies. Here, we use two-dimensional nonlinear optical spectroscopy to examine these interactions in the course of the doping process by probing the solution mixture of doped organic semiconductors. A dopant accepts an electron from the semiconductor and the two ions form a duplex of interacting charges known as ion-pair complexes. Well-resolved off-diagonal peaks in the two-dimensional spectra clearly demonstrate the electronic connectivity among the ions in solution. This electronic interaction represents a well resolved electrostatically bound state, as opposed to a random distribution of ions. We developed a theoretical model to recover the experimental data, which reveals an unexpectedly strong electronic coupling of ∼250 cm -1 with an intermolecular distance of ∼4.5 Å between ions in solution, which is approximately the expected distance in processed films. The fact that this relationship persists from solution to the processed film gives direct evidence that Coulomb interactions are retained from the precursor solution to the processed films. This memory effect renders the charge carriers equally bound also in the film and, hence, results in poor doping efficiencies. This new insight will help pave the way towards rational tailoring of the electronic interactions to improve doping efficiencies in processed organic semiconductor thin films.

Electron capture dissociation in a branched radio-frequency ion trap.

PubMed

Baba, Takashi; Campbell, J Larry; Le Blanc, J C Yves; Hager, James W; Thomson, Bruce A

2015-01-06

We have developed a high-throughput electron capture dissociation (ECD) device coupled to a quadrupole time-of-flight mass spectrometer using novel branched radio frequency ion trap architecture. With this device, a low-energy electron beam can be injected orthogonally into the analytical ion beam with independent control of both the ion and electron beams. While ions and electrons can interact in a "flow-through" mode, we observed a large enhancement in ECD efficiency by introducing a short ion trapping period at the region of ion and electron beam intersection. This simultaneous trapping mode still provides up to five ECD spectra per second while operating in an information-dependent acquisition workflow. Coupled to liquid chromatography (LC), this LC-ECD workflow provides good sequence coverage for both trypsin and Lys C digests of bovine serum albumin, providing ECD spectra for doubly charged precursor ions with very good efficiency.

Solid-Solution Sulfides Derived from Tunable Layered Double Hydroxide Precursors/Graphene Aerogel for Pseudocapacitors and Sodium-Ion Batteries.

PubMed

Song, Yajie; Li, Hui; Yang, Lan; Bai, Daxun; Zhang, Fazhi; Xu, Sailong

2017-12-13

Transition-metal sulfides (TMSs) are suggested as promising electrode materials for electrochemical pseudocapacitors and lithium- and sodium-ion batteries; however, they typically involve mixed composites or conventionally stoichiometric TMSs (such as NiCo 2 S 4 and Ni 2 CoS 4 ). Herein we demonstrate a preparation of solid-solution sulfide (Ni 0.7 Co 0.3 )S 2 supported on three-dimensional graphene aerogel (3DGA) via a sulfuration of NiCo-layered double hydroxide (NiCo-LDH) precursor/3DGA. The electrochemical tests show that the (Ni 0.7 Co 0.3 )S 2 /3DGA electrode exhibits a capacitance of 2165 F g -1 at 1 A g -1 , 2055 F g -1 at 2 A g -1 , and 1478 F g -1 at 10 A g -1 ; preserves 78.5% capacitance retention upon 1000 cycles for pseudocapacitors; and in particular, possesses a relatively high charge capacity of 388.7 mA h g -1 after 50 cycles at 100 mA g -1 as anode nanomaterials for sodium-ion batteries. Furthermore, the electrochemical performances are readily tuned by varying the cationic type of the tunable LDH precursors to prepare different solid-solution sulfides, such as (Ni 0.7 Fe 0.3 )S 2 /3DGA and (Co 0.7 Fe 0.3 )S 2 /3DGA. Our results show that engineering LDH precursors can offer an alternative for preparing diverse transition-metal sulfides for energy storage.

Simultaneous and Sequential MS/MS Scan Combinations and Permutations in a Linear Quadrupole Ion Trap.

PubMed

Snyder, Dalton T; Szalwinski, Lucas J; Cooks, R Graham

2017-10-17

Methods of performing precursor ion scans as well as neutral loss scans in a single linear quadrupole ion trap have recently been described. In this paper we report methodology for performing permutations of MS/MS scan modes, that is, ordered combinations of precursor, product, and neutral loss scans following a single ion injection event. Only particular permutations are allowed; the sequences demonstrated here are (1) multiple precursor ion scans, (2) precursor ion scans followed by a single neutral loss scan, (3) precursor ion scans followed by product ion scans, and (4) segmented neutral loss scans. (5) The common product ion scan can be performed earlier in these sequences, under certain conditions. Simultaneous scans can also be performed. These include multiple precursor ion scans, precursor ion scans with an accompanying neutral loss scan, and multiple neutral loss scans. We argue that the new capability to perform complex simultaneous and sequential MS n operations on single ion populations represents a significant step in increasing the selectivity of mass spectrometry.

Urea-based hydrothermal synthesis of LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery

NASA Astrophysics Data System (ADS)

Shi, Yang; Zhang, Minghao; Fang, Chengcheng; Meng, Ying Shirley

2018-08-01

A urea-based hydrothermal approach has been applied to synthesize LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode materials with focus on investigating the influence of the reaction conditions on their electrochemical performance. The compositions of the carbonate precursor are precisely controlled by tuning urea concentration, hydrothermal reaction temperature, and time. The mole ratio between urea and transition metal ions and reaction temperature influence the composition of the precursor; while the reaction time influences the electrochemical performance of the final product. The optimized materials show better cyclability and rate capability compared with the materials synthesized with other hydrothermal reaction conditions. The enhancement is attributed to the larger Li+ diffusion coefficient and lower charge transfer resistance, which are due to the lower degree of Li/Ni cation mixing and more uniform distribution of transition metal ions. This work is a systematic study on the synthesis of NCM523 cathode material by a urea-based hydrothermal approach.

Sequencing of Oligourea Foldamers by Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Bathany, Katell; Owens, Neil W.; Guichard, Gilles; Schmitter, Jean-Marie

2013-03-01

This study is focused on sequence analysis of peptidomimetic helical oligoureas by means of tandem mass spectrometry, to build a basis for de novo sequencing for future high-throughput combinatorial library screening of oligourea foldamers. After the evaluation of MS/MS spectra obtained for model compounds with either MALDI or ESI sources, we found that the MALDI-TOF-TOF instrument gave more satisfactory results. MS/MS spectra of oligoureas generated by decay of singly charged precursor ions show major ion series corresponding to fragmentation across both CO-NH and N'H-CO urea bonds. Oligourea backbones fragment to produce a pattern of a, x, b, and y type fragment ions. De novo decoding of spectral information is facilitated by the occurrence of low mass reporter ions, representative of constitutive monomers, in an analogous manner to the use of immonium ions for peptide sequencing.

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

PubMed Central

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

2010-01-01

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

Charge Mediated Compaction and Rearrangement of Gas-Phase Proteins: A Case Study Considering Two Proteins at Opposing Ends of the Structure-Disorder Continuum

NASA Astrophysics Data System (ADS)

Jhingree, Jacquelyn R.; Bellina, Bruno; Pacholarz, Kamila J.; Barran, Perdita E.

2017-07-01

Charge reduction in the gas phase provides a direct means of manipulating protein charge state, and when coupled to ion mobility mass spectrometry (IM-MS), it is possible to monitor the effect of charge on protein conformation in the absence of solution. Use of the electron transfer reagent 1,3-dicyanobenzene, coupled with IM-MS, allows us to monitor the effect of charge reduction on the conformation of two proteins deliberately chosen from opposite sides of the order to disorder continuum: bovine pancreatic trypsin inhibitor (BPTI) and beta casein. The ordered BPTI presents compact conformers for each of three charge states accompanied by narrow collision cross-section distributions (TWCCSDN2→He). Upon reduction of BPTI, irrespective of precursor charge state, the TWCCSN2→He decreases to a similar distribution as found for the nESI generated ion of identical charge. The behavior of beta casein upon charge reduction is more complex. It presents over a wide charge state range (9-28), and intermediate charge states (13-18) have broad TWCCSDN2→He with multiple conformations, where both compaction and rearrangement are seen. Further, we see that the TWCCSDN2→He of the latter charge states are even affected by the presence of radical anions. Overall, we conclude that the flexible nature of some proteins result in broad conformational distributions comprised of many families, even for single charge states, and the barrier between different states can be easily overcome by an alteration of the net charge.

Removal of precursors and disinfection by-products (DBPs) by membrane filtration from water; a review.

PubMed

Zazouli, Mohammad Ali; Kalankesh, Laleh R

2017-01-01

Disinfection by-products (DBPs) have heterogeneous structures which are suspected carcinogens as a result of reactions between NOMs (Natural Organic Matter) and oxidants/disinfectants such as chlorine. Because of variability in DBPs characteristics, eliminate completely from drinking water by single technique is impossible. The current article reviews removal of the precursors and DBPs by different membrane filtration methods such as Microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF) and Reverse Osmosis (RO) techniques. Also, we provide an overview of existing and potentially Membrane filtration techniques, highlight their strengths and drawbacks. MF membranes are a suitable alternative to remove suspended solids and colloidal materials. However, NOMs fractions are effectively removed by negatively charged UF membrane. RO can remove both organic and inorganic DBPs and precursors simultaneously. NF can be used to remove compounds from macromolecular size to multivalent ions.

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

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

Choi, Daiwon; Li, Xiaolin; Henderson, Wesley A.

2016-02-01

Highly crystalline LiCoPO4/C cathode has been synthesized without any impurities via single step solid-state reaction using CoHPO4xH2O nanoplates as a precursor obtained by simple precipitation route. The electrochemical test shows specific capacity as high as 125mAh/g at charge/discharge rate of C/10. Synthesis approach for obtaining CoHPO4xH2O nanoplate precursor and final LiCoPO4/C cathode using single step solid-state reaction have been characterized using X-ray diffraction, thermos gravimetric analyses (TGA) – differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The electrochemical test and cycling stability using different electrolytes, additive and separator have been investigated.

Driven waves in a two-fluid plasma

NASA Astrophysics Data System (ADS)

Roberge, W. G.; Ciolek, Glenn E.

2007-12-01

We study the physics of wave propagation in a weakly ionized plasma, as it applies to the formation of multifluid, magnetohydrodynamics (MHD) shock waves. We model the plasma as separate charged and neutral fluids which are coupled by ion-neutral friction. At times much less than the ion-neutral drag time, the fluids are decoupled and so evolve independently. At later times, the evolution is determined by the large inertial mismatch between the charged and neutral particles. The neutral flow continues to evolve independently; the charged flow is driven by and slaved to the neutral flow by friction. We calculate this driven flow analytically by considering the special but realistic case where the charged fluid obeys linearized equations of motion. We carry out an extensive analysis of linear, driven, MHD waves. The physics of driven MHD waves is embodied in certain Green functions which describe wave propagation on short time-scales, ambipolar diffusion on long time-scales and transitional behaviour at intermediate times. By way of illustration, we give an approximate solution for the formation of a multifluid shock during the collision of two identical interstellar clouds. The collision produces forward and reverse J shocks in the neutral fluid and a transient in the charged fluid. The latter rapidly evolves into a pair of magnetic precursors on the J shocks, wherein the ions undergo force-free motion and the magnetic field grows monotonically with time. The flow appears to be self-similar at the time when linear analysis ceases to be valid.

S/N dual-doped carbon nanosheets decorated with Co x O y nanoparticles as high-performance anodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, XiaoFei; Zhu, Yong; Zhu, Sheng; Fan, JinChen; Xu, QunJie; Min, YuLin

2018-03-01

In this work, we have successfully synthesized the S/N dual-doped carbon nanosheets which are strongly coupled with Co x O y nanoparticles (SNCC) by calcinating cobalt/dithizone complex precursor following KOH activation. The SNCC as anode shows the wonderful charge capacity of 1200 mAh g-1 after 400th cycles at 1000 mA g-1 for Li-ion storage. The superior electrochemical properties illustrate that the SNCC can be a candidate for high-performance anode material of lithium-ion batteries (LIBs) because of the facile preparation method and excellent performance. Significantly, we also discuss the mechanism for the SNCC from the strong synergistic effect perspective.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

PubMed

Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

2018-04-02

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heat-Treatment-Responsive Proteins in Different Developmental Stages of Tomato Pollen Detected by Targeted Mass Accuracy Precursor Alignment (tMAPA).

PubMed

Chaturvedi, Palak; Doerfler, Hannes; Jegadeesan, Sridharan; Ghatak, Arindam; Pressman, Etan; Castillejo, Maria Angeles; Wienkoop, Stefanie; Egelhofer, Volker; Firon, Nurit; Weckwerth, Wolfram

2015-11-06

Recently, we have developed a quantitative shotgun proteomics strategy called mass accuracy precursor alignment (MAPA). The MAPA algorithm uses high mass accuracy to bin mass-to-charge (m/z) ratios of precursor ions from LC-MS analyses, determines their intensities, and extracts a quantitative sample versus m/z ratio data alignment matrix from a multitude of samples. Here, we introduce a novel feature of this algorithm that allows the extraction and alignment of proteotypic peptide precursor ions or any other target peptide from complex shotgun proteomics data for accurate quantification of unique proteins. This strategy circumvents the problem of confusing the quantification of proteins due to indistinguishable protein isoforms by a typical shotgun proteomics approach. We applied this strategy to a comparison of control and heat-treated tomato pollen grains at two developmental stages, post-meiotic and mature. Pollen is a temperature-sensitive tissue involved in the reproductive cycle of plants and plays a major role in fruit setting and yield. By LC-MS-based shotgun proteomics, we identified more than 2000 proteins in total for all different tissues. By applying the targeted MAPA data-processing strategy, 51 unique proteins were identified as heat-treatment-responsive protein candidates. The potential function of the identified candidates in a specific developmental stage is discussed.

Fe{sub 2}O{sub 3} nanowires on HOPG as precursor of new carbon-based anode for high-capacity lithium ion batteries

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

Angelucci, Marco; Frau, Eleonora; Betti, Maria Grazia

Iron Oxides nanostructures are very promising systems for new generation of anode material for Lithium-Ion batteries because of their high capacity associated to their surface area. A core-level photoemission study of Fe{sub 2}O{sub 3} nanowires deposited on highly-oriented pyrolitic graphite (HOPG) under Li exposure is presented. The Fe-2p, Fe-3p, and Li-1s core-level lineshape evolution upon Li exposure in ultra-high-vacuum conditions clearly brings to light the Fe ion reduction from fully trivalent to prevalently divalent at saturation. Furthermore, the graphite substrate allows allocation of a large amount of Li ions surrounding the iron-oxide nanowires, opening a new scenario towards the usemore » of graphene for improving the ionic charge exchange.« less

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.

Gas phase reactions of doubly charged alkaline earth and transition metal(II)-ligand complexes generated by electrospray ionization

NASA Astrophysics Data System (ADS)

Kohler, Martin; Leary, Julie A.

1997-03-01

Doubly charged metal(II)-complexes of [alpha] 1-3, [alpha] 1-6 mannotriose and the conserved trimannosyl core pentasaccharide as well as doubly charged complexes of Co(II), Mn(II), Ca(II) and Sr(II) with acetonitrile generated by electrospray ionization were studied by low energy collision induced dissociation (CID). Two main fragmentation pathways were observed for the metal(II)-oligosaccharide complexes. Regardless of the coordinating metal, loss of a neutral dehydrohexose residue (162 Da) from the doubly charged precursor ion is observed, forming a doubly charged product ion. However, if the oligosaccharide is coordinated to Co(II) or Mn(II), loss of a dehydroxyhexose cation is also observed. Investigation of the low mass region of the mass spectra of the metal coordinated oligosaccharides revealed intense signals corresponding to [metal(II) + (CH3CN)n2+ (where n = 1-6) species which were being formed by the metal(II) ions and the acetonitrile present in the sample. Analysis of these metal(II)-acetonitrile complexes provided further insight into the processes occurring upon low energy CID of doubly charged metal complexes. The metal(II)-acetonitrile system showed neutral loss and ligand cleavage as observed with the oligosaccharide complexes, as well as a series of six different dissociation mechanisms, most notable among them reduction from [metal(II) + (CH3CN)n2+ to the bare [metal(I)]+ species by electron transfer. Depending on the metal and collision gas chosen, one observes electron transfer from the ligand to the metal, electron transfer from the collision gas to the metal, proton transfer between ligands, heterolytic cleavage of the ligands, reactive collisions and loss of neutral ligands.

Screening and identification of glyceollins and their metabolites by electrospray ionization tandem mass spectrometry with precursor ion scanning

USDA-ARS?s Scientific Manuscript database

A method has been developed for screening glyceollins and their metabolites based upon precursor ion scanning. Under higher-energy collision conditions, employing a triple quadrupole mass spectrometer in the negative ion mode, deprotonated glyceollin precursors yield a diagnostic radical product ion...

Methods for producing thin film charge selective transport layers

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

Hammond, Scott Ryan; Olson, Dana C.; van Hest, Marinus Franciscus Antonius Maria

Methods for producing thin film charge selective transport layers are provided. In one embodiment, a method for forming a thin film charge selective transport layer comprises: providing a precursor solution comprising a metal containing reactive precursor material dissolved into a complexing solvent; depositing the precursor solution onto a surface of a substrate to form a film; and forming a charge selective transport layer on the substrate by annealing the film.

On-line LC-MS approach combining collision-induced dissociation (CID), electron-transfer dissociation (ETD), and CID of an isolated charge-reduced species for the trace-level characterization of proteins with post-translational modifications.

PubMed

Wu, Shiaw-Lin; Hühmer, Andreas F R; Hao, Zhiqi; Karger, Barry L

2007-11-01

We have expanded our recent on-line LC-MS platform for large peptide analysis to combine collision-induced dissociation (CID), electron-transfer dissociation (ETD), and CID of an isolated charge-reduced (CRCID) species derived from ETD to determine sites of phosphorylation and glycosylation modifications, as well as the sequence of large peptide fragments (i.e., 2000-10,000 Da) from complex proteins, such as beta-casein, epidermal growth factor receptor (EGFR), and tissue plasminogen activator (t-PA) at the low femtomol level. The incorporation of an additional CID activation step for a charge-reduced species, isolated from ETD fragment ions, improved ETD fragmentation when precursor ions with high m/z (approximately >1000) were automatically selected for fragmentation. Specifically, the identification of the exact phosphorylation sites was strengthened by the extensive coverage of the peptide sequence with a near-continuous product ion series. The identification of N-linked glycosylation sites in EGFR and an O-linked glycosylation site in t-PA were also improved through the enhanced identification of the peptide backbone sequence of the glycosylated precursors. The new strategy is a good starting survey scan to characterize enzymatic peptide mixtures over a broad range of masses using LC-MS with data-dependent acquisition, as the three activation steps can provide complementary information to each other. In general, large peptides can be extensively characterized by the ETD and CRCID steps, including sites of modification from the generated, near-continuous product ion series, supplemented by the CID-MS2 step. At the same time, small peptides (e.g.,

Site-specific N-glycosylation analysis: matrix-assisted laser desorption/ionization quadrupole-quadrupole time-of-flight tandem mass spectral signatures for recognition and identification of glycopeptides.

PubMed

Krokhin, Oleg; Ens, Werner; Standing, Kenneth G; Wilkins, John; Perreault, Hélène

2004-01-01

The identification of glycosylation sites in proteins is often possible through a combination of proteolytic digestion, separation, mass spectrometry (MS) and tandem MS (MS/MS). Liquid chromatography (LC) in combination with MS/MS has been a reliable method for detecting glycopeptides in digestion mixtures, and for assigning glycosylation sites and glycopeptide sequences. Direct interfacing of LC with MS relies on electrospray ionization, which produces ions with two, three or four charges for most proteolytic peptides and glycopeptides. MS/MS spectra of such glycopeptide ions often lead to ambiguous interpretation if deconvolution to the singly charged level is not used. In contrast, the matrix-assisted laser desorption/ionization (MALDI) technique usually produces singly charged peptide and glycopeptide ions. These ions require an extended m/z range, as provided by the quadrupole-quadrupole time-of-flight (QqTOF) instrument used in these experiments, but the main advantages of studying singly charged ions are the simplicity and consistency of the MS/MS spectra. A first aim of the present study is to develop methods to recognize and use glycopeptide [M+H]+ ions as precursors for MS/MS, and thus for glycopeptide/glycoprotein identification as part of wider proteomics studies. Secondly, this article aims at demonstrating the usefulness of MALDI-MS/MS spectra of N-glycopeptides. Mixtures of diverse types of proteins, obtained commercially, were prepared and subjected to reduction, alkylation and tryptic digestion. Micro-column reversed-phase separation allowed deposition of several fractions on MALDI plates, followed by MS and MS/MS analysis of all peptides. Glycopeptide fractions were identified after MS by their specific m/z spacing patterns (162, 203, 291 u) between glycoforms, and then analyzed by MS/MS. In most cases, MS/MS spectra of [M+H]+ ions of glycopeptides featured peaks useful for determining sugar composition, peptide sequence, and thus probable glycosylation site. Peptide-related product ions could be used in database search procedures and allowed the identification of the glycoproteins. Copyright 2004 John Wiley & Sons, Ltd.

MS/MS-Assisted Design of Sequence-Controlled Synthetic Polymers for Improved Reading of Encoded Information

NASA Astrophysics Data System (ADS)

Charles, Laurence; Cavallo, Gianni; Monnier, Valérie; Oswald, Laurence; Szweda, Roza; Lutz, Jean-François

2017-06-01

In order to improve their MS/MS sequencing, structure of sequence-controlled synthetic polymers can be optimized based on considerations regarding their fragmentation behavior in collision-induced dissociation conditions, as demonstrated here for two digitally encoded polymer families. In poly(triazole amide)s, the main dissociation route proceeded via cleavage of the amide bond in each monomer, hence allowing the chains to be safely sequenced. However, a competitive cleavage of an ether bond in a tri(ethylene glycol) spacer placed between each coding moiety complicated MS/MS spectra while not bringing new structural information. Changing the tri(ethylene glycol) spacer to an alkyl group of the same size allowed this unwanted fragmentation pathway to be avoided, hence greatly simplifying the MS/MS reading step for such undecyl-based poly(triazole amide)s. In poly(alkoxyamine phosphodiester)s, a single dissociation pathway was achieved with repeating units containing an alkoxyamine linkage, which, by very low dissociation energy, made any other chemical bonds MS/MS-silent. Structure of these polymers was further tailored to enhance the stability of those precursor ions with a negatively charged phosphate group per monomer in order to improve their MS/MS readability. Increasing the size of both the alkyl coding moiety and the nitroxide spacer allowed sufficient distance between phosphate groups for all of them to be deprotonated simultaneously. Because the charge state of product ions increased with their polymerization degree, MS/MS spectra typically exhibited groups of fragments at one or the other side of the precursor ion depending on the original α or ω end-group they contain, allowing sequence reconstruction in a straightforward manner. [Figure not available: see fulltext.

MS/MS Digital Readout: Analysis of Binary Information Encoded in the Monomer Sequences of Poly(triazole amide)s.

PubMed

Amalian, Jean-Arthur; Trinh, Thanh Tam; Lutz, Jean-François; Charles, Laurence

2016-04-05

Tandem mass spectrometry was evaluated as a reliable sequencing methodology to read codes encrypted in monodisperse sequence-coded oligo(triazole amide)s. The studied oligomers were composed of monomers containing a triazole ring, a short ethylene oxide segment, and an amide group as well as a short alkyl chain (propyl or isobutyl) which defined the 0/1 molecular binary code. Using electrospray ionization, oligo(triazole amide)s were best ionized as protonated molecules and were observed to adopt a single charge state, suggesting that adducted protons were located on every other monomer unit. Upon collisional activation, cleavages of the amide bond and of one ether bond were observed to proceed in each monomer, yielding two sets of complementary product ions. Distribution of protons over the precursor structure was found to remain unchanged upon activation, allowing charge state to be anticipated for product ions in the four series and hence facilitating their assignment for a straightforward characterization of any encoded oligo(triazole amide)s.

Synthesis and electrochemical performance of hole-rich Li4Ti5O12 anode material for lithium-ion secondary batteries

NASA Astrophysics Data System (ADS)

Zhu, Weibo; Zhuang, Zhenyuan; Yang, Yanmin; Zhang, Ruidan; Lin, Zhiya; Lin, Yingbin; Huang, Zhigao

2016-06-01

Hole-rich Li4Ti5O12 composites are synthesized by spray drying using carbon nanotubes as additives in precursor solution, subsequently followed calcinated at high temperature in air. The structure, morphology, and texture of the as-prepared composites are characterized with XRD, Raman, BET and SEM techniques. The electrochemical properties of the as-prepared composites are investigated systematically by charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine Li4Ti5O12, the hole-rich Li4Ti5O12 induced by carbon nanotubes exhibits superior electrochemical performance, especially at high rates. The obtained excellent electrochemical performances of should be attributed to the hole-rich structure of the materials, which offers more connection-area with the electrolyte, shorter diffusion-path length as well faster migration rate for both Li ions and electrons during the charge/discharge process.

Metal-Organic Frameworks Derived Okra-like SnO2 Encapsulated in Nitrogen-Doped Graphene for Lithium Ion Battery.

PubMed

Zhou, Xiangyang; Chen, Sanmei; Yang, Juan; Bai, Tao; Ren, Yongpeng; Tian, Hangyu

2017-04-26

A facile process is developed to prepare SnO 2 -based composites through using metal-organic frameworks (MOFs) as precursors. The nitrogen-doped graphene wrapped okra-like SnO 2 composites (SnO 2 @N-RGO) are successfully synthesized for the first time by using Sn-based metal-organic frameworks (Sn-MOF) as precursors. When utilized as an anode material for lithium-ion batteries, the SnO 2 @N-RGO composites possess a remarkably superior reversible capacity of 1041 mA h g -1 at a constant current of 200 mA g -1 after 180 charge-discharge processes and excellent rate capability. The excellent performance can be primarily ascribed to the unique structure of 1D okra-like SnO 2 in SnO 2 @N-RGO which are actually composed of a great number of SnO 2 primary crystallites and numerous well-defined internal voids, can effectively alleviate the huge volume change of SnO 2 , and facilitate the transport and storage of lithium ions. Besides, the structural stability acquires further improvement when the okra-like SnO 2 are wrapped by N-doped graphene. Similarly, this synthetic strategy can be employed to synthesize other high-capacity metal-oxide-based composites starting from various metal-organic frameworks, exhibiting promising application in novel electrode material field of lithium-ion batteries.

Even-electron [M-H](+) ions generated by loss of AgH from argentinated peptides with N-terminal imine groups.

PubMed

Plaviak, Alexandra; Osburn, Sandra; Patterson, Khiry; van Stipdonk, Michael J

2016-01-15

Experiments were performed to probe the creation of apparent even-electron, [M-H](+) ions by CID of Ag-cationized peptides with N-terminal imine groups (Schiff bases). Imine-modified peptides were prepared using condensation reactions with aldehydes. Ag(+) -cationized precursors were generated by electrospray ionization (ESI). Tandem mass spectrometry (MS(n) ) and collision-induced dissociation (CID) were performed using a linear ion trap mass spectrometer. Loss of AgH from peptide [M + Ag](+) ions, at the MS/MS stage, creates closed-shell [M-H](+) ions from imine-modified peptides. Isotope labeling unambiguously identifies the imine C-H group as the source of H eliminated in AgH. Subsequent CID of the [M-H](+) ions generated sequence ions that are analogous to those produced from [M + H](+) ions of the imine-modified peptides. Experiments show (a) formation of novel even-electron peptide cations by CID and (b) the extent to which sequence ions (conventional b, a and y ions) are generated from peptides with fixed charge site and thus lacking a conventional mobile proton. Copyright © 2015 John Wiley & Sons, Ltd.

The Competitive Influence of Li+, Na+, K+, Ag+, and H+ on the Fragmentation of a PEGylated Polymeric Excipient

NASA Astrophysics Data System (ADS)

Wei, Juan; Bristow, Anthony W. T.; O'Connor, Peter B.

2015-01-01

The collisionally activated dissociation (CAD) and electron capture dissociation (ECD) of doubly charged tocopheryl polyethylene glycol succinate (TPGS) have been examined. Li+, Na+, K+, Ag+, and H+ were selected in the study, and the competitive influence of each ion was investigated by fragmenting TPGS attached with two different cations, [M + X1 + X2]2+ (X1 and X2 refer to Li+, Na+, K+, Ag+, H+). For metallic adducts, CAD results show that the dissociation of ionic adducts from the precursor is most likely depending on the binding strength, where the affinity of each ion to the TPGS is in the order of Ag+ ≈ Li+ ˃ Na+ ˃ K+. Introducing more strongly bound adducts increases fragmentation. During ECD, however, the silver cation is lost most easily compared with the other alkali metal ions, but silver also shows a dominant role in producing fragmentations. Moreover, the charge carriers are lost in an order (Ag+ ˃ Na+ ˃ K+ ≥ Li+ where the loss of Ag is most easily) that appears to correlate with the standard reduction potential of the metallic ions (Ag+ ˃ Na+ ˃ K+ ˃ Li+). The ECD results suggest that the reduction potential of the charge carrier could be an important factor influencing the fragmentation, where the ion with a high reduction potential is more effective in capturing electrons, but may also be lost easily before leading to any fragmentation. Finally, a proton has the weakest binding with the TPGS according to the CAD results, and its dissociation in ECD follows the order of the reduction potential (Ag+ ˃ H+ ˃ Na+ ˃ K+ > Li+).

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Multi-stage tandem mass spectrometric analysis of novel β-cyclodextrin-substituted and novel bis-pyridinium gemini surfactants designed as nanomedical drug delivery agents.

PubMed

Donkuru, McDonald; Chitanda, Jackson M; Verrall, Ronald E; El-Aneed, Anas

2014-04-15

This study aimed at evaluating the collision-induced dissociation tandem mass spectrometric (CID-MS/MS) fragmentation patterns of novel β-cyclodextrin-substituted- and bis-pyridinium gemini surfactants currently being explored as nanomaterial drug delivery agents. In the β-cyclodextrin-substituted gemini surfactants, a β-cyclodextrin ring is grafted onto an N,N-bis(dimethylalkyl)-α,ω-aminoalkane-diammonium moiety using variable succinyl linkers. In contrast, the bis-pyridinium gemini surfactants are based on a 1,1'-(1,1'-(ethane-1,2-diylbis(sulfanediyl))bis(alkane-2,1-diyl))dipyridinium template, defined by two symmetrical N-alkylpyridinium parts connected through a fixed ethane dithiol spacer. Detection of the precursor ion [M](2+) species of the synthesized compounds and the determination of mass accuracies were conducted using a QqTOF-MS instrument. A multi-stage tandem MS analysis of the detected [M](2+) species was conducted using the QqQ-LIT-MS instrument. Both instruments were equipped with an electrospray ionization (ESI) source. Abundant precursor ion [M](2+) species were detected for all compounds at sub-1 ppm mass accuracies. The β-cyclodextrin-substituted compounds, fragmented via two main pathways: Pathway 1: the loss of one head-tail region produces a [M-(N(Me)2-R)](2+) ion, from which sugar moieties (Glc) are sequentially cleaved; Pathway 2: both head-tail regions are lost to give [M-2(N(Me)2-R)](+), followed by consecutive loss of Glc units. Alternatively, the cleavage of the Glc units could also have occurred simultaneously. Nevertheless, the fragmentation evolved around the quaternary ammonium cations, with characteristic cleavage of Glc moieties. For the bis-pyridinium gemini compounds, they either lost neutral pyridine(s) to give doubly charged ions (Pathway A) or formed complementary pyridinium alongside other singly charged ions (Pathway B). Similar to β-cyclodextrin-substituted compounds, the fragmentation was centered on the pyridinium functional groups. The MS(n) analyses of these novel gemini surfactants, reported here for the first time, revealed diagnostic ions for each compound, with a universal fragmentation pattern for each compound series. The diagnostic ions will be employed within liquid chromatography (LC)/MS/MS methods for screening, identification, and quantification of these compounds within biological samples. Copyright © 2014 John Wiley & Sons, Ltd.

End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS).

PubMed

Jackson, Anthony T; Slade, Susan E; Thalassinos, Konstantinos; Scrivens, James H

2008-10-01

The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation-tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis).

The effect of Pb addition on the morphology of CdSe quantum dot

NASA Astrophysics Data System (ADS)

Kim, Young-Kuk; Cho, Young-Sang; Chung, Kookchae; Choi, Chul-Jin

2010-08-01

CdSe quantum dots had been synthesized with a hot injection method. It was shown that the addition of Pb ions in the initial precursor solution changed the morphology of CdSe nanocrystals from slightly prolate ellipsoid to branched rod. Photoluminescence (PL) of the branched nanocrystals showed rapid depression of emission intensity due to the morphological development to the branched nanocrystal induced by Pb addition. Low temperature PL spectrum indicated that the surface recombination of charge carrier resulted in the large depression of emission from the branched nanocrystal.

Extending a Tandem Mass Spectral Library to Include MS2 Spectra of Fragment Ions Produced In-Source and MSn Spectra.

PubMed

Yang, Xiaoyu; Neta, Pedatsur; Stein, Stephen E

2017-11-01

Tandem mass spectral library searching is finding increased use as an effective means of determining chemical identity in mass spectrometry-based omics studies. We previously reported on constructing a tandem mass spectral library that includes spectra for multiple precursor ions for each analyte. Here we report our method for expanding this library to include MS 2 spectra of fragment ions generated during the ionization process (in-source fragment ions) as well as MS 3 and MS 4 spectra. These can assist the chemical identification process. A simple density-based clustering algorithm was used to cluster all significant precursor ions from MS 1 scans for an analyte acquired during an infusion experiment. The MS 2 spectra associated with these precursor ions were grouped into the same precursor clusters. Subsequently, a new top-down hierarchical divisive clustering algorithm was developed for clustering the spectra from fragmentation of ions in each precursor cluster, including the MS 2 spectra of the original precursors and of the in-source fragments as well as the MS n spectra. This algorithm starts with all the spectra of one precursor in one cluster and then separates them into sub-clusters of similar spectra based on the fragment patterns. Herein, we describe the algorithms and spectral evaluation methods for extending the library. The new library features were demonstrated by searching the high resolution spectra of E. coli extracts against the extended library, allowing identification of compounds and their in-source fragment ions in a manner that was not possible before. Graphical Abstract ᅟ.

An EThcD-Based Method for Discrimination of Leucine and Isoleucine Residues in Tryptic Peptides

NASA Astrophysics Data System (ADS)

Zhokhov, Sergey S.; Kovalyov, Sergey V.; Samgina, Tatiana Yu.; Lebedev, Albert T.

2017-08-01

An EThcD-based approach for the reliable discrimination of isomeric leucine and isoleucine residues in peptide de novo sequencing procedure has been proposed. A multistage fragmentation of peptide ions was performed with Orbitrap Elite mass spectrometer in electrospray ionization mode. At the first stage, z-ions were produced by ETD or ETcaD fragmentation of doubly or triply charged peptide precursor ions. These primary ions were further fragmented by HCD with broad-band ion isolation, and the resulting w-ions showed different mass for leucine and isoleucine residues. The procedure did not require manual isolation of specific z-ions prior to HCD stage. Forty-three tryptic peptides (3 to 27 residues) obtained by trypsinolysis of human serum albumin (HSA) and gp188 protein were analyzed. To demonstrate a proper solution for radical site migration problem, three non-tryptic peptides were also analyzed. A total of 93 leucine and isoleucine residues were considered and 83 of them were correctly identified. The developed approach can be a reasonable substitution for additional Edman degradation procedure, which is still used in peptide sequencing for leucine and isoleucine discrimination.

Wavelet-Based Peak Detection and a New Charge Inference Procedure for MS/MS Implemented in ProteoWizard’s msConvert

PubMed Central

2015-01-01

We report the implementation of high-quality signal processing algorithms into ProteoWizard, an efficient, open-source software package designed for analyzing proteomics tandem mass spectrometry data. Specifically, a new wavelet-based peak-picker (CantWaiT) and a precursor charge determination algorithm (Turbocharger) have been implemented. These additions into ProteoWizard provide universal tools that are independent of vendor platform for tandem mass spectrometry analyses and have particular utility for intralaboratory studies requiring the advantages of different platforms convergent on a particular workflow or for interlaboratory investigations spanning multiple platforms. We compared results from these tools to those obtained using vendor and commercial software, finding that in all cases our algorithms resulted in a comparable number of identified peptides for simple and complex samples measured on Waters, Agilent, and AB SCIEX quadrupole time-of-flight and Thermo Q-Exactive mass spectrometers. The mass accuracy of matched precursor ions also compared favorably with vendor and commercial tools. Additionally, typical analysis runtimes (∼1–100 ms per MS/MS spectrum) were short enough to enable the practical use of these high-quality signal processing tools for large clinical and research data sets. PMID:25411686

Constructing effective photocatalytic purification system with P-introduced g-C3N4 for elimination of UO22+

NASA Astrophysics Data System (ADS)

Wu, Xi; Jiang, Shujuan; Song, Shaoqing; Sun, Chuanzhi

2018-02-01

Due to the inherent defects of precursor molecular structure, the limited effect of structure in the formed g-C3N4 will weaken the extension of delocalization of π electrons between the adjacent tri-s-triazine or heptazine units of g-C3N4, which thus leads to poor visible-light absorption, low utilization efficiency of charge carrier. Herein, P-introduced g-C3N4 (PC3N4) photocatalysts were constructed by partially replacing C with tributyl phosphate as precursor, and the as-designed PC3N4 photocatalysts were used to eliminate aqueous uranyl ion by photocatalytic reduction technology under visible-light irradiation. Experimental and DFT revealed that introduction of P into g-C3N4 significantly modified its electronic structure, as reflected by the narrowed band gap, enhanced visible-light absorption as well as improved transfer capability of photogenerated charge. Therefore, photocatalytic activity of PC3N4 was much better than that of pristine g-C3N4 and conventional reducing-type photocatalysts. This study suggests an efficient strategy for construct effective visible-light-responsive photocatalysts for radioactive environmental remediation.

Wavelet-based peak detection and a new charge inference procedure for MS/MS implemented in ProteoWizard's msConvert.

PubMed

French, William R; Zimmerman, Lisa J; Schilling, Birgit; Gibson, Bradford W; Miller, Christine A; Townsend, R Reid; Sherrod, Stacy D; Goodwin, Cody R; McLean, John A; Tabb, David L

2015-02-06

We report the implementation of high-quality signal processing algorithms into ProteoWizard, an efficient, open-source software package designed for analyzing proteomics tandem mass spectrometry data. Specifically, a new wavelet-based peak-picker (CantWaiT) and a precursor charge determination algorithm (Turbocharger) have been implemented. These additions into ProteoWizard provide universal tools that are independent of vendor platform for tandem mass spectrometry analyses and have particular utility for intralaboratory studies requiring the advantages of different platforms convergent on a particular workflow or for interlaboratory investigations spanning multiple platforms. We compared results from these tools to those obtained using vendor and commercial software, finding that in all cases our algorithms resulted in a comparable number of identified peptides for simple and complex samples measured on Waters, Agilent, and AB SCIEX quadrupole time-of-flight and Thermo Q-Exactive mass spectrometers. The mass accuracy of matched precursor ions also compared favorably with vendor and commercial tools. Additionally, typical analysis runtimes (∼1-100 ms per MS/MS spectrum) were short enough to enable the practical use of these high-quality signal processing tools for large clinical and research data sets.

MnO Nanoparticle@Mesoporous Carbon Composites Grown on Conducting Substrates Featuring High-performance Lithium-ion Battery, Supercapacitor and Sensor

PubMed Central

Wang, Tianyu; Peng, Zheng; Wang, Yuhang; Tang, Jing; Zheng, Gengfeng

2013-01-01

We demonstrate a facile, two-step coating/calcination approach to grow a uniform MnO nanoparticle@mesoporous carbon (MnO@C) composite on conducting substrates, by direct coating of the Mn-oleate precursor solution without any conducting/binding reagents, and subsequent thermal calcination. The monodispersed, sub-10 nm MnO nanoparticles offer high theoretical energy storage capacities and catalytic properties, and the mesoporous carbon coating allows for enhanced electrolyte transport and charge transfer towards/from MnO surface. In addition, the direct growth and attachment of the MnO@C nanocomposite in the supporting conductive substrates provide much reduced contact resistances and efficient charge transfer. These excellent features allow the use of MnO@C nanocomposites as lithium-ion battery and supercapacitor electrodes for energy storage, with high reversible capacity at large current densities, as well as excellent cycling and mechanical stabilities. Moreover, this MnO@C nanocomposite has also demonstrated a high sensitivity for H2O2 detection, and also exhibited attractive potential for the tumor cell analysis. PMID:24045767

Microwave synthesis of molybdenum doped LiFePO4/C and its electrochemical studies.

PubMed

Naik, Amol; P, Sajan C

2016-05-10

A Mo-doped LiFePO4 composite was prepared successfully from an iron carbonyl complex by adopting a facile and rapid microwave assisted solid state method. The evolution of gases from the iron precursor produces a highly porous product. The formation and substitution of Mo in LiFePO4 were confirmed by X-ray diffraction; surface analysis was carried out by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical properties of the substituted LiFePO4 were examined by cyclic voltammetry, electrochemical impedance spectroscopy and by recording charge-discharge cycles. It was observed that the as prepared composites consisted of a single phase orthorhombic olivine-type structure, where Mo(6+) was successfully introduced into the M2(Fe) sites. Incorporation of supervalent Mo(6+) introduced Li(+) ion vacancies in LiFePO4. The synthesized material facilitated lithium ion diffusion during charging/discharging due to the charge compensation effect and porosity. The battery performance studies showed that LiMo0.05Fe0.095PO4 exhibited a maximum capacity of 169.7 mA h g(-1) at 0.1 C current density, with admirable stability retention. Even at higher current densities, the retention of the specific capacity was exceptional.

Electronic structure and fragmentation properties of [Fe4S4(SEt)4-x(SSEt)x]2-

NASA Astrophysics Data System (ADS)

Fu, You-Jun; Laskin, Julia; Wang, Lai-Sheng

2007-06-01

A limited exposure of (n-Bu4N)2[Fe4S4(SEt)4] solutions in acetonitrile to air was found to produce a new series of [4Fe-4S] cluster complexes, [Fe4S4(SEt)4-x(SSEt)x]2- (x = 1-4), with the original -SEt ligands substituted by -SSEt di-sulfide ligands, which were formed due to partial decomposition of the [4Fe-4S] core in parent [Fe4S4(SEt)4]2-. The products were first observed in the experiments with an ESI-ion Trap-TOF mass spectrometer and were further identified using high resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Photoelectron spectra of the [Fe4S4(SEt)4-x(SSEt)x]2- dianions revealed that the -SSEt coordination induced little change in the electronic structure of the [4Fe-4S] cluster, but the electron binding energies of [Fe4S4(SEt)4-x(SSEt)x]2- increased from 0.52 to 0.73 eV with increase in x from 0 to 4, suggesting a greater electron withdrawing ability of -SSEt than -SEt. In high resolution MS/MS experiments on [Fe4S4(SEt)3(SSEt)]2-/1-, clusters with both charge states yielded fragment [Fe4S4(SEt)3]-, suggesting that -SSEt could be lost either as a negatively charged ion SSEt- from the doubly charged precursor, or as a radical SSEt from the singly charged species. The biological implication of the interaction between [Fe4S4(SEt)4]2- and O2 is discussed in comparison to the air exposure of [4Fe-4S] proteins to the air.

Top-down MALDI-in-source decay-FTICR mass spectrometry of isotopically resolved proteins.

PubMed

Nicolardi, Simone; Switzar, Linda; Deelder, André M; Palmblad, Magnus; van der Burgt, Yuri E M

2015-03-17

An accurate mass measurement of a known protein provides information on potential amino acid deletions and post-translational modifications. Although this field is dominated by strategies based on electrospray ionization, mass spectrometry (MS) methods using matrix-assisted laser desorption/ionization (MALDI) have the advantage of yielding predominantly singly charged precursor ions, thus avoiding peak overlap from different charge states of multiple species. Such MALDI-MS methods require mass measurement at ultrahigh resolution, which is provided by Fourier transform ion cyclotron resonance (FTICR) mass analyzers. Recently, using a MALDI-FTICR-MS platform equipped with a 15 T magnet, we reported on the mass analysis of intact human serum peptides and small proteins with isotopic resolution up to ∼15 kDa and identified new proteoforms from an accurate measurement of mass distances. In the current study, we have used this FTICR system after an upgrade with a novel dynamically harmonized ICR cell, i.e., ParaCell, for mapping isotopically resolved intact proteins up to about 17 kDa and performed top-down MALDI in-source decay (ISD) analysis. Standard proteins myoglobin (m/z-value 16,950) and ribonuclease B (m/z-value 14,900) were measured with resolving powers of 62,000 and 61,000, respectively. Furthermore, it will be shown that (singly charged) MALDI-ISD fragment ions can be measured at isotopic resolution up to m/z-value 12,000 (e.g., resolving power 39,000 at m/z-value 12,000) providing more reliable identifications. Moreover, examples are presented of pseudo-MS(3) experiments on ISD fragment ions from RNase B by collisional-induced dissociation (CID).

Database searching and accounting of multiplexed precursor and product ion spectra from the data independent analysis of simple and complex peptide mixtures.

PubMed

Li, Guo-Zhong; Vissers, Johannes P C; Silva, Jeffrey C; Golick, Dan; Gorenstein, Marc V; Geromanos, Scott J

2009-03-01

A novel database search algorithm is presented for the qualitative identification of proteins over a wide dynamic range, both in simple and complex biological samples. The algorithm has been designed for the analysis of data originating from data independent acquisitions, whereby multiple precursor ions are fragmented simultaneously. Measurements used by the algorithm include retention time, ion intensities, charge state, and accurate masses on both precursor and product ions from LC-MS data. The search algorithm uses an iterative process whereby each iteration incrementally increases the selectivity, specificity, and sensitivity of the overall strategy. Increased specificity is obtained by utilizing a subset database search approach, whereby for each subsequent stage of the search, only those peptides from securely identified proteins are queried. Tentative peptide and protein identifications are ranked and scored by their relative correlation to a number of models of known and empirically derived physicochemical attributes of proteins and peptides. In addition, the algorithm utilizes decoy database techniques for automatically determining the false positive identification rates. The search algorithm has been tested by comparing the search results from a four-protein mixture, the same four-protein mixture spiked into a complex biological background, and a variety of other "system" type protein digest mixtures. The method was validated independently by data dependent methods, while concurrently relying on replication and selectivity. Comparisons were also performed with other commercially and publicly available peptide fragmentation search algorithms. The presented results demonstrate the ability to correctly identify peptides and proteins from data independent acquisition strategies with high sensitivity and specificity. They also illustrate a more comprehensive analysis of the samples studied; providing approximately 20% more protein identifications, compared to a more conventional data directed approach using the same identification criteria, with a concurrent increase in both sequence coverage and the number of modified peptides.

High-Performance Ga2O3 Anode for Lithium-Ion Batteries.

PubMed

Tang, Xun; Huang, Xin; Huang, Yongmin; Gou, Yong; Pastore, James; Yang, Yao; Xiong, Yin; Qian, Jiangfeng; Brock, Joel D; Lu, Juntao; Xiao, Li; Abruña, Héctor D; Zhuang, Lin

2018-02-14

There is a great deal of interest in developing battery systems that can exhibit self-healing behavior, thus enhancing cyclability and stability. Given that gallium (Ga) is a metal that melts near room temperature, we wanted to test if it could be employed as a self-healing anode material for lithium-ion batteries (LIBs). However, Ga nanoparticles (NPs), when directly applied, tended to aggregate upon charge/discharge cycling. To address this issue, we employed carbon-coated Ga 2 O 3 NPs as an alternative. By controlling the pH of the precursor solution, highly dispersed and ultrafine Ga 2 O 3 NPs, embedded in carbon shells, could be synthesized through a hydrothermal carbonization method. The particle size of the Ga 2 O 3 NPs was 2.6 nm, with an extremely narrow size distribution, as determined by high-resolution transmission electron microscopy and Brunauer-Emmett-Teller measurements. A lithium-ion battery anode based on this material exhibited stable charging and discharging, with a capacity of 721 mAh/g after 200 cycles. The high cyclability is due to not only the protective effects of the carbon shell but also the formation of Ga 0 during the lithiation process, as indicated by operando X-ray absorption near-edge spectroscopy.

Surface Surgery of the Nickel-Rich Cathode Material LiNi0.815Co0.15Al0.035O2: Toward a Complete and Ordered Surface Layered Structure and Better Electrochemical Properties.

PubMed

Tang, Zhongfeng; Bao, Junjie; Du, Qingxia; Shao, Yu; Gao, Minghao; Zou, Bangkun; Chen, Chunhua

2016-12-21

A complete and ordered layered structure on the surface of LiNi 0.815 Co 0.15 Al 0.035 O 2 (NCA) has been achieved via a facile surface-oxidation method with Na 2 S 2 O 8 . The field-emission transmission electron microscopy images clearly show that preoxidation of the hydroxide precursor can eliminate the crystal defects and convert Ni(OH) 2 into layered β-NiOOH, which leads to a highly ordered crystalline NCA, with its (006) planes perpendicular to the surface in the sintering process. X-ray photoelectron spectroscopy and Raman shift results demonstrate that the contents of Ni 2+ and Co 2+ ions are reduced with preoxidization on the surface of the hydroxide precursor. The level of Li + /Ni 2+ disordering in the modified NCA determined by the peak intensity ratio I (003) /I (104) in X-ray diffraction patterns decreases. Thanks to the complete and ordered layered structure on the surface of secondary particles, lithium ions can easily intercalate/extract in the discharging-charging process, leading to greatly improved electrochemical properties.

Facile synthesis of multi-shell structured binary metal oxide powders with a Ni/Co mole ratio of 1:2 for Li-Ion batteries

NASA Astrophysics Data System (ADS)

Choi, Seung Ho; Park, Sun Kyu; Lee, Jung-Kul; Kang, Yun Chan

2015-06-01

Multi-shell structured binary transition metal oxide powders with a Ni/Co mole ratio of 1:2 are prepared by a simple spray drying process. Precursor powder particles prepared by spray drying from a spray solution of citric acid and ethylene glycol have completely spherical shape, fine size, and a narrow size distribution. The precursor powders turn into multi-shell powders after a post heat-treatment at temperatures between 250 and 800 °C. The multi-shell structured powders are formed by repeated combustion and contraction processes. The multi-shell powders have mixed crystal structures of Ni1-xCo2O4-x and NiO phases regardless of the post-treatment temperature. The reversible capacities of the powders post-treated at 250, 400, 600, and 800 °C after 100 cycles are 584, 913, 808, and 481 mA h g-1, respectively. The low charge transfer resistance and high lithium ion diffusion rate of the multi-shell powders post-treated at 400 °C with optimum grain size result in superior electrochemical properties even at high current densities.

Precursor and Neutral Loss Scans in an RF Scanning Linear Quadrupole Ion Trap

NASA Astrophysics Data System (ADS)

Snyder, Dalton T.; Szalwinski, Lucas J.; Schrader, Robert L.; Pirro, Valentina; Hilger, Ryan; Cooks, R. Graham

2018-03-01

Methodology for performing precursor and neutral loss scans in an RF scanning linear quadrupole ion trap is described and compared to the unconventional ac frequency scan technique. In the RF scanning variant, precursor ions are mass selectively excited by a fixed frequency resonance excitation signal at low Mathieu q while the RF amplitude is ramped linearly to pass ions through the point of excitation such that the excited ion's m/z varies linearly with time. Ironically, a nonlinear ac frequency scan is still required for ejection of the product ions since their frequencies vary nonlinearly with the linearly varying RF amplitude. In the case of the precursor scan, the ejection frequency must be scanned so that it is fixed on a product ion m/z throughout the RF scan, whereas in the neutral loss scan, it must be scanned to maintain a constant mass offset from the excited precursor ions. Both simultaneous and sequential permutation scans are possible; only the former are demonstrated here. The scans described are performed on a variety of samples using different ionization sources: protonated amphetamine ions generated by nanoelectrospray ionization (nESI), explosives ionized by low-temperature plasma (LTP), and chemical warfare agent simulants sampled from a surface and analyzed with swab touch spray (TS). We lastly conclude that the ac frequency scan variant of these MS/MS scans is preferred due to electronic simplicity. In an accompanying manuscript, we thus describe the implementation of orthogonal double resonance precursor and neutral loss scans on the Mini 12 using constant RF voltage. [Figure not available: see fulltext.

Detection method for dissociation of multiple-charged ions

DOEpatents

Smith, Richard D.; Udseth, Harold R.; Rockwood, Alan L.

1991-01-01

Dissociations of multiple-charged ions are detected and analyzed by charge-separation tandem mass spectrometry. Analyte molecules are ionized to form multiple-charged parent ions. A particular charge parent ion state is selected in a first-stage mass spectrometer and its mass-to-charge ratio (M/Z) is detected to determine its mass and charge. The selected parent ions are then dissociated, each into a plurality of fragments including a set of daughter ions each having a mass of at least one molecular weight and a charge of at least one. Sets of daughter ions resulting from the dissociation of one parent ion (sibling ions) vary in number but typically include two to four ions, one or more multiply-charged. A second stage mass spectrometer detects mass-to-charge ratio (m/z) of the daughter ions and a temporal or temporo-spatial relationship among them. This relationship is used to correlate the daughter ions to determine which (m/z) ratios belong to a set of sibling ions. Values of mass and charge of each of the sibling ions are determined simultaneously from their respective (m/z) ratios such that the sibling ion charges are integers and sum to the parent ion charge.

Hydroxide precursors to produce nanometric YCrO{sub 3}: Characterization and conductivity analysis

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

Durán, A., E-mail: dural@cnyn.unam.mx; Meza F, C.; Arizaga, Gregorio Guadalupe Carbajal, E-mail: gregoriocarbajal@yahoo.com.mx

2012-06-15

Highlights: ► Y/Cr mixed hydroxide was precipitated with gaseous ammonia. ► The hydroxide treated at 1373 K formed YCrO{sub 3} crystals with 20 nm diameter. ► Electrical properties were different than those found in other methods of synthesis. ► E{sub act} suggests small-polarons as conduction mechanisms. -- Abstract: A precursor to produce perovskite-type YCrO{sub 3} was precipitated by bubbling gaseous ammonia into an yttrium/chromium salts solution. X-ray diffraction showed that the as-prepared powders were amorphous. Thermal treatment between 1273 and 1373 K, leads to formation of polycrystalline YCrO{sub 3} with crystal sizes around 20 nm. High resolution X-ray photoelectron spectramore » showed uniform chemical environment for yttrium and chromium in the amorphous hydroxide and crystalline YCrO{sub 3}. Shifts between Y 3d{sub 5/2} and Cr 2p{sub 3/2} binding energy suggest redistribution or charge transfer between yttrium and chromium ions in the YCrO{sub 3} structure. The electrical properties of YCrO{sub 3}, whose precursors were precipitated with gaseous ammonia are different than those prepared by combustion synthesis. Electrical conductivity presents a sudden increase at ∼473 K, which is associated to the grain size and morphology of the crystallites. The redistribution of charge between Y(III) and Cr(III) is thermally activated by the hopping of small-polarons, which are characterized by the Arrhenius law as the conductive mechanism.« less

Highly sensitive derivatization reagents possessing positively charged structures for the determination of oligosaccharides in glycoproteins by high-performance liquid chromatography electrospray ionization tandem mass spectrometry.

PubMed

Min, Jun Zhe; Nagai, Keisuke; Shi, Qing; Zhou, Wenjun; Todoroki, Kenichiro; Inoue, Koichi; Lee, Yong-Ill; Toyo'oka, Toshimasa

2016-09-23

We have developed three kinds of novel derivatization reagents (4-CEBTPP, 4-CBBTPP, 5-COTPP) with triphenylphosphine (TPP) as a basic structure carrying a permanent positive charge for resolution of the oligosaccharides in glycoprotein using high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The synthesized reagents reacted with the sialylglycosylamine of the sialylglycopeptide after treatment by PNGase F. The final derivatives were analyzed by ESI-MS and sensitively detected in the selected reaction monitoring (SRM) mode. Furthermore, the limits of detection (S/N=3) on the SRM chromatograms were at the fmol level (30fmol). Therefore, we used the limit of detection of the reagent products detected by the SRM and evaluated the utility of each reagent. Among the reagents, the positively charged 4-CEBTPP derivative's peak area was the highest; 4-CEBTPP with a positively charged structure showed about a 20 times greater sensitivity for the glycosylamine of the SGP product compared to the conventional fluorescence reagent, Fmoc-Cl. In addition, various fragment ions based on the carbohydrate units also appeared in the MS/MS spectra. Among the fragment ions, m/z 627.37 (CE=40eV) corresponding to 4-CEBTPP-GlcNAc and m/z 120.09 (CE=100eV) corresponding to 4-CEBTPP are the most important ones for identifying the oligosaccharide. 4-CEBTPP-SGA was easily identified by the selected-ion chromatogram in the product ion scan (m/z 120.09) and in the precursor ion scan (m/z 627.37) by MS/MS detection. The derivatized analytes have a high ionization efficiency and they are detected with a high sensitivity in the electrospray ionization. The novel derivatization reagent with a multi-function provided a higher sensitivity for the oligosaccharide analysis, as well as a better specificity and feasibility. Furthermore, several oligosaccharides in fetuin and ribonuclease B were successfully identified by the proposed procedure. Copyright © 2016 Elsevier B.V. All rights reserved.

Optimization by infusion of multiple reaction monitoring transitions for sensitive quantification of peptides by liquid chromatography/mass spectrometry.

PubMed

Alghanem, Bandar; Nikitin, Frédéric; Stricker, Thomas; Duchoslav, Eva; Luban, Jeremy; Strambio-De-Castillia, Caterina; Muller, Markus; Lisacek, Frédérique; Varesio, Emmanuel; Hopfgartner, Gérard

2017-05-15

In peptide quantification by liquid chromatography/mass spectrometry (LC/MS), the optimization of multiple reaction monitoring (MRM) parameters is essential for sensitive detection. We have compared different approaches to build MRM assays, based either on flow injection analysis (FIA) of isotopically labelled peptides, or on the knowledge and the prediction of the best settings for MRM transitions and collision energies (CE). In this context, we introduce MRMOptimizer, an open-source software tool that processes spectra and assists the user in selecting transitions in the FIA workflow. MS/MS spectral libraries with CE voltages from 10 to 70 V are automatically acquired in FIA mode for isotopically labelled peptides. Then MRMOptimizer determines the optimal MRM settings for each peptide. To assess the quantitative performance of our approach, 155 peptides, representing 84 proteins, were analysed by LC/MRM-MS and the peak areas were compared between: (A) the MRMOptimizer-based workflow, (B1) the SRMAtlas transitions set used 'as-is'; (B2) the same SRMAtlas set with CE parameters optimized by Skyline. 51% of the three most intense transitions per peptide were shown to be common to both A and B1/B2 methods, and displayed similar sensitivity and peak area distributions. The peak areas obtained with MRMOptimizer for transitions sharing either the precursor ion charge state or the fragment ions with the SRMAtlas set at unique transitions were increased 1.8- to 2.3-fold. The gain in sensitivity using MRMOptimizer for transitions with different precursor ion charge state and fragment ions (8% of the total), reaches a ~ 11-fold increase. Isotopically labelled peptides can be used to optimize MRM transitions more efficiently in FIA than by searching databases. The MRMOptimizer software is MS independent and enables the post-acquisition selection of MRM parameters. Coefficients of variation for optimal CE values are lower than those obtained with the SRMAtlas approach (B2) and one additional peptide was detected. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Synthesis of Olive-Like Nitrogen-Doped Carbon with Embedded Ge Nanoparticles for Ultrahigh Stable Lithium Battery Anodes.

PubMed

Ma, Xiaomei; Zhou, Yongning; Chen, Min; Wu, Limin

2017-05-01

The development of environment-friendly and high-performance carbon materials for energy applications has remained a great challenge. Here, a novel and facile method for synthesis of olive-like nitrogen-doped carbon embedded with germanium (Ge) nanoparticles using widespread and nontoxic dopamine as carbon and nitrogen precursors is demonstrated, especially by understanding the tendency of pure GeO 2 nanoparticles forming ellipsoidal aggregation, and the chelating reaction of the catechol structure in dopamine with metal ions. The as-synthesized Ge/N-C composites show an olive-like porous carbon structure with a loading weight of as high as 68.5% Ge nanoparticles. A lithium ion battery using Ge/N-C as the anode shows 1042 mAh g -1 charge capacity after 2000 cycles (125 d) charge/discharge at C/2 (1C = 1600 mA g -1 ) with a capacity maintaining efficiency of 99.6%, significantly exceeding those of the previously reported Ge/C-based anode materials. This prominent cyclic charge/discharge performance of the Ge/N-C anode is attributed to the well-dispersed Ge nanoparticles in graphitic N-doped carbon matrix, which facilitates high rates (0.5-15 C) of charge/discharge and increases the anode structure integrity. The synthesis strategy presented here may be a very promising approach to prepare a series of active nanoparticle-carbon hybrid materials with nitrogen doping for more and important applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Doping of carbon foams for use in energy storage devices

DOEpatents

Mayer, Steven T.; Pekala, Richard W.; Morrison, Robert L.; Kaschmitter, James L.

1994-01-01

A polymeric foam precursor, wetted with phosphoric acid, is pyrolyzed in an inert atmosphere to produce an open-cell doped carbon foam, which is utilized as a lithium intercalation anode in a secondary, organic electrolyte battery. Tests were conducted in a cell containing an organic electrolyte and using lithium metal counter and reference electrodes, with the anode located therebetween. Results after charge and discharge cycling, for a total of 6 cycles, indicated a substantial increase in the energy storage capability of the phosphorus doped carbon foam relative to the undoped carbon foam, when used as a rechargeable lithium ion battery.

Carrier-envelope phase dependence of the directional fragmentation and hydrogen migration in toluene in few-cycle laser fields.

PubMed

Li, Hui; Kling, Nora G; Förg, Benjamin; Stierle, Johannes; Kessel, Alexander; Trushin, Sergei A; Kling, Matthias F; Kaziannis, Spyros

2016-07-01

The dissociative ionization of toluene initiated by a few-cycle laser pulse as a function of the carrier envelope phase (CEP) is investigated using single-shot velocity map imaging. Several ionic fragments, CH3 (+), H2 (+), and H3 (+), originating from multiply charged toluene ions present a CEP-dependent directional emission. The formation of H2 (+) and H3 (+) involves breaking C-H bonds and forming new bonds between the hydrogen atoms within the transient structure of the multiply charged precursor. We observe appreciable intensity-dependent CEP-offsets. The experimental data are interpreted with a mechanism that involves laser-induced coupling of vibrational states, which has been found to play a role in the CEP-control of molecular processes in hydrocarbon molecules, and appears to be of general importance for such complex molecules.

Precursor Ion Scan Mode-Based Strategy for Fast Screening of Polyether Ionophores by Copper-Induced Gas-Phase Radical Fragmentation Reactions.

PubMed

Crevelin, Eduardo J; Possato, Bruna; Lopes, João L C; Lopes, Norberto P; Crotti, Antônio E M

2017-04-04

The potential of copper(II) to induce gas-phase fragmentation reactions in macrotetrolides, a class of polyether ionophores produced by Streptomyces species, was investigated by accurate-mass electrospray tandem mass spectrometry (ESI-MS/MS). Copper(II)/copper(I) transition directly induced production of diagnostic acylium ions with m/z 199, 185, 181, and 167 from α-cleavages of [macrotetrolides + Cu] 2+ . A UPLC-ESI-MS/MS methodology based on the precursor ion scan of these acylium ions was developed and successfully used to identify isodinactin (1), trinactin (2), and tetranactin (3) in a crude extract of Streptomyces sp. AMC 23 in the precursor ion scan mode. In addition, copper(II) was also used to induce radical fragmentation reactions in the carboxylic acid polyether ionophore nigericin. The resulting product ions with m/z 755 and 585 helped to identify nigericin in a crude extract of Streptomyces sp. Eucal-26 by means of precursor ion scan experiments, demonstrating that copper-induced fragmentation reactions can potentially identify different classes of polyether ionophores rapidly and selectively.

Correlation between y-type ions observed in ion trap and triple quadrupole mass spectrometers.

PubMed

Sherwood, Carly A; Eastham, Ashley; Lee, Lik Wee; Risler, Jenni; Vitek, Olga; Martin, Daniel B

2009-09-01

Multiple reaction monitoring mass spectrometry (MRM-MS) is a technique for high-sensitivity targeted analysis. In proteomics, MRM-MS can be used to monitor and quantify a peptide based on the production of expected fragment peaks from the selected peptide precursor ion. The choice of which fragment ions to monitor in order to achieve maximum sensitivity in MRM-MS can potentially be guided by existing MS/MS spectra. However, because the majority of discovery experiments are performed on ion trap platforms, there is concern in the field regarding the generalizability of these spectra to MRM-MS on a triple quadrupole instrument. In light of this concern, many operators perform an optimization step to determine the most intense fragments for a target peptide on a triple quadrupole mass spectrometer. We have addressed this issue by targeting, on a triple quadrupole, the top six y-ion peaks from ion trap-derived consensus library spectra for 258 doubly charged peptides from three different sample sets and quantifying the observed elution curves. This analysis revealed a strong correlation between the y-ion peak rank order and relative intensity across platforms. This suggests that y-type ions obtained from ion trap-based library spectra are well-suited for generating MRM-MS assays for triple quadrupoles and that optimization is not required for each target peptide.

Improving Charging-Breeding Simulations with Space-Charge Effects

NASA Astrophysics Data System (ADS)

Bilek, Ryan; Kwiatkowski, Ania; Steinbrügge, René

2016-09-01

Rare-isotope-beam facilities use Highly Charged Ions (HCI) for accelerators accelerating heavy ions and to improve measurement precision and resolving power of certain experiments. An Electron Beam Ion Trap (EBIT) is able to create HCI through successive electron impact, charge breeding trapped ions into higher charge states. CBSIM was created to calculate successive charge breeding with an EBIT. It was augmented by transferring it into an object-oriented programming language, including additional elements, improving ion-ion collision factors, and exploring the overlap of the electron beam with the ions. The calculation is enhanced with the effects of residual background gas by computing the space charge due to charge breeding. The program assimilates background species, ionizes and charge breeds them alongside the element being studied, and allows them to interact with the desired species through charge exchange, giving fairer overview of realistic charge breeding. Calculations of charge breeding will be shown for realistic experimental conditions. We reexamined the implementation of ionization energies, cross sections, and ion-ion interactions when charge breeding.

Hierarchically ordered mesoporous Co3O4 materials for high performance Li-ion batteries.

PubMed

Sun, Shijiao; Zhao, Xiangyu; Yang, Meng; Wu, Linlin; Wen, Zhaoyin; Shen, Xiaodong

2016-01-19

Highly ordered mesoporous Co3O4 materials have been prepared via a nanocasting route with three-dimensional KIT-6 and two-dimensional SBA-15 ordered mesoporous silicas as templates and Co(NO3)2 · 6H2O as precursor. Through changing the hydrothermal treating temperature of the silica template, ordered mesoporous Co3O4 materials with hierarchical structures have been developed. The larger pores around 10 nm provide an efficient transport for Li ions, while the smaller pores between 3-5 nm offer large electrochemically active areas. Electrochemical impedance analysis proves that the hierarchical structure contributes to a lower charge transfer resistance in the mesoporous Co3O4 electrode than the mono-sized structure. High reversible capacities around 1141 mAh g(-1) of the hierarchically mesoporous Co3O4 materials are obtained, implying their potential applications for high performance Li-ion batteries.

Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries.

PubMed

David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

2016-03-30

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm(-2)) delivers a charge capacity of ∼588 mAh g(-1)electrode (∼393 mAh cm(-3)electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

Porous Fe2O3 Microspheres as Anode for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Noerochim, L.; Indra, M. A. T.; Purwaningsih, H.; Subhan, A.

2018-05-01

In this work, Fe2O3 was successfully synthesized by the hydrothermal process at low temperature. FeCl3.6H2O as precursor and variation of lysine as hydrolyzing agent were used to preparing Fe2O3. SEM images show that the morphology of Fe2O3 is porous microsphere with sizes in the range of (1 to 5) µm in diameter. The as-prepared Fe2O3 with the 2 M of lysine exhibits excellent cycling performance when used as the anode for lithium ion batteries, obtaining reversible discharge capacity of 172.33 mA·h·g‑1 at 0.5 C after 50 cycles. It is attributed to the unique structure of porous microspheres providing a large surface area which maintains good electronic contact between particles during charge-discharge process. This result demonstrates that Fe2O3 porous microsphere has a high potential as anode material for application of lithium-ion battery.

Matrix-assisted laser desorption/ionization coupled with quadrupole/orthogonal acceleration time-of-flight mass spectrometry for protein discovery, identification, and structural analysis.

PubMed

Baldwin, M A; Medzihradszky, K F; Lock, C M; Fisher, B; Settineri, T A; Burlingame, A L

2001-04-15

The design and operation of a novel UV-MALDI ionization source on a commercial QqoaTOF mass spectrometer (Applied Biosystem/MDS Sciex QSTAR Pulsar) is described. Samples are loaded on a 96-well target plate, the movement of which is under software control and can be readily automated. Unlike conventional high-energy MALDI-TOF, the ions are produced with low energies (5-10 eV) in a region of relatively low vacuum (8 mTorr). Thus, they are cooled by extensive low-energy collisions before selection in the quadrupole mass analyzer (Q1), potentially giving a quasi-continuous ion beam ideally suited to the oaTOF used for mass analysis of the fragment ions, although ion yields from individual laser shots may vary widely. Ion dissociation is induced by collisions with argon in an rf-only quadrupole cell, giving typical low-energy CID spectra for protonated peptide ions. Ions separated in the oaTOF are registered by a four-anode detector and time-to-digital converter and accumulated in "bins" that are 625 ps wide. Peak shapes depend upon the number of ion counts in adjacent bins. As expected, the accuracy of mass measurement is shown to be dependent upon the number of ions recorded for a particular peak. With internal calibration, mass accuracy better than 10 ppm is attainable for peaks that contain sufficient ions to give well-defined Gaussian profiles. By virtue of its high resolution, capability for accurate mass measurements, and sensitivity in the low-femotomole range, this instrument is ideally suited to protein identification for proteomic applications by generation of peptide tags, manual sequence interpretation, identification of modifications such as phosphorylation, and protein structural elucidation. Unlike the multiply charged ions typical of electrospray ionization, the singly charged MALDI-generated peptide ions show a linear dependence of optimal collision energy upon molecular mass, which is advantageous for automated operation. It is shown that the novel pulsing technique of this instrument that increases the sensitivity for precursor ions scans is applicable to the identification of peptides labeled with isotope-coded affinity tags.

Gas-phase synthesis of singly and multiply charged polyoxovanadate anions employing electrospray ionization and collision induced dissociation.

PubMed

Al Hasan, Naila M; Johnson, Grant E; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy(n-) and VxOyCl(n-) ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N(+), tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCl(n-) and VxOyCl(L)((n-1)-) clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl((1-2)-) and VxOy ((1-2)-) anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

NASA Astrophysics Data System (ADS)

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-09-01

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy n- and VxOyCln- ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln- and VxOyCl(L)(n-1)- clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1-2)- and VxOy (1-2)- anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.

Adsorption of Bromine on Gold Nanoclusters

NASA Astrophysics Data System (ADS)

Salvo, Christopher; Keagy, Josiah; Yarmoff, Jory

Small metal nanoclusters are extremely effective as catalysts, with rates that rival those of enzymes in biological systems. The first step in a catalytic reaction is the adsorption of a precursor molecule. The neutralization of alkali projectiles during low energy ion scattering (LEIS), which is acutely sensitive to the local electrostatic potential a few Å's above the surface, is used here to probe Au nanoclusters grown on SiO2 as they are reacted with Br2. Previous work had demonstrated very efficient neutralization in scattering from small catalytically active Au clusters, which was interpreted as an indication that the bare clusters are negatively charged. X-ray photoelectron spectroscopy and LEIS show little or no Br signal after exposing SiO2 and Au foil to Br2, suggesting that adsorption does not occur because the Br-Br bond does not break. Dissociative adsorption occurs rapidly, however, when small Au nanoclusters are reacted with Br2. 1.5 keV Na+ ions scattered from the Au clusters show a decrease in the neutralization probability as Br is reacted, indicating that adsorption results in charge being transferred from the cluster to the Br adatom. This material is based upon work supported by the National Science Foundation under CHE - 1611563.

Fine line structures of ceramic films formed by patterning of metalorganic precursors using photolithography and ion beams

NASA Astrophysics Data System (ADS)

Hung, L. S.; Zheng, L. R.

1992-05-01

Fine line structures of ceramic thin films were fabricated by patterning of metalorganic precursors using photolithography and ion beams. A trilevel structure was developed with an outer resist layer to transfer patterns, a silver delineated layer as an implantation mask, and a planar resist layer protecting the precursor film from chemical attacking and sputtering. Ion irradiation through the Ag stencil rendered metal carboxylates insoluble in 2-ethylhexanoic acid, permitting patterning of the precursor film with patterning features on micron scales. The potential of this technique was demonstrated in patterning of Bi2Sr2CaCu2O(8+x) and Pb(Zr(0.53)Ti(0.47) thin films.

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

Zhang, Qibin; Schepmoes, Athena A; Brock, Jonathan W

Non-enzymatic glycation of tissue proteins has important implications in the development of complications of diabetes mellitus. Herein we report improved methods for the enrichment and analysis of glycated peptides using boronate affinity chromatography and electron transfer dissociation mass spectrometry, respectively. The enrichment of glycated peptides was improved by replacing an off-line desalting step with an on-line wash of column-bound glycated peptides using 50 mM ammonium acetate. The analysis of glycated peptides by MS/MS was improved by considering only higher charged (≥3) precursor-ions during data-dependent acquisition, which increased the number of glycated peptide identifications. Similarly, the use of supplemental collisional activationmore » after electron transfer (ETcaD) resulted in more glycated peptide identifications when the MS survey scan was acquired with enhanced resolution. In general, acquiring ETD-MS/MS data at a normal MS survey scan rate, in conjunction with the rejection of both 1+ and 2+ precursor-ions, increased the number of identified glycated peptides relative to ETcaD or the enhanced MS survey scan rate. Finally, an evaluation of trypsin, Arg-C, and Lys-C showed that tryptic digestion of glycated proteins was comparable to digestion with Lys-C and that both were better than Arg-C in terms of the number glycated peptides identified by LC-MS/MS.« less

Isoelectric point and adsorption activity of porous g-C3N4

NASA Astrophysics Data System (ADS)

Zhu, Bicheng; Xia, Pengfei; Ho, Wingkei; Yu, Jiaguo

2015-07-01

The isoelectric point (IEP) is an important physicochemical parameter of many compounds, such as oxides, hydroxides, and nitrides, and can contribute to estimation of the surface charges of compound particles at various pH conditions. In this work, three types of graphitic carbon nitrides (g-C3N4) were synthesized by directly heating melamine, thiourea, and urea. The prepared samples showed different microstructures and IEPs that influenced their adsorption activity. Differences in microstructure resulted from the various precursors used during synthesis. The IEPs of the obtained g-C3N4 were measured to be approximately 4-5, which is due to the equilibrium of chemical reactions between hydrogen ions, hydroxyl ions, and amine groups on the g-C3N4 surface. The IEP of g-C3N4 prepared from thiourea was lower than those of the corresponding samples prepared from melamine and urea. The adsorption activity of methylene blue on g-C3N4 prepared from urea and thiourea was excellent, which indicates that g-C3N4 is a promising adsorbent. This work provides a useful reference for choosing precursors with which to prepare g-C3N4 and combining g-C3N4 with other compounds in solution.

Charge exchange molecular ion source

DOEpatents

Vella, Michael C.

2003-06-03

Ions, particularly molecular ions with multiple dopant nucleons per ion, are produced by charge exchange. An ion source contains a minimum of two regions separated by a physical barrier and utilizes charge exchange to enhance production of a desired ion species. The essential elements are a plasma chamber for production of ions of a first species, a physical separator, and a charge transfer chamber where ions of the first species from the plasma chamber undergo charge exchange or transfer with the reactant atom or molecules to produce ions of a second species. Molecular ions may be produced which are useful for ion implantation.

Carrier-envelope phase dependence of the directional fragmentation and hydrogen migration in toluene in few-cycle laser fields

PubMed Central

Li, Hui; Kling, Nora G.; Förg, Benjamin; Stierle, Johannes; Kessel, Alexander; Trushin, Sergei A.; Kling, Matthias F.; Kaziannis, Spyros

2016-01-01

The dissociative ionization of toluene initiated by a few-cycle laser pulse as a function of the carrier envelope phase (CEP) is investigated using single-shot velocity map imaging. Several ionic fragments, CH3+, H2+, and H3+, originating from multiply charged toluene ions present a CEP-dependent directional emission. The formation of H2+ and H3+ involves breaking C-H bonds and forming new bonds between the hydrogen atoms within the transient structure of the multiply charged precursor. We observe appreciable intensity-dependent CEP-offsets. The experimental data are interpreted with a mechanism that involves laser-induced coupling of vibrational states, which has been found to play a role in the CEP-control of molecular processes in hydrocarbon molecules, and appears to be of general importance for such complex molecules. PMID:26958589

Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistry

NASA Technical Reports Server (NTRS)

Sciamma-O'Brien, Ella Marion; Contreras, Cesar; Ricketts, Claire Louise; Salama, Farid

2011-01-01

A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.

[Separation and identification of 5 glycosidic flavor precursors in tobacco by ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry].

PubMed

Wu, Xinhua; Zhu, Ruizhi; Ren, Zhuoying; Wang, Kai; Mou, Dingrong; Wei, Wanzhi; Miao, Mingming

2009-11-01

A qualitative method for the identification of 5 main glycosidic flavor precursors in tobacco was developed by using ultra performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-ESI MS/MS) and gas chromatography-mass spectrometry (GC-MS). The glycosidic flavor precursors in tobacco were extracted with methanol, cleaned up with an XAD-2 column. The aglycones were later released by enzyme-mediated hydrolysis under the condition of pH 5. The 5 volatile aglycone moieties were identified by GC-MS standard spectra library. The precursor ions of glycosides were determined by using electrospray ionization mass spectrometry in negative ion mode, then the 5 glycosidic flavor precursors were identified by using product ion scan (MS2) finally, using UPLC-ESI MS/MS, separation and identification of 5 glycosidic flavor precursors were accomplished on an RP-C,8 column in the multiple reaction monitoring (MRM) mode by using methanol and acetic acid-ammonium acetate aqueous solution as eluent. This work lays a foundation for the analysis of glycosidic flavor precursors without the standards by using liquid chromatography-mass spectrometry.

Layered electrodes for lithium cells and batteries

DOEpatents

Johnson; Christopher S. , Thackeray; Michael M. , Vaughey; John T. , Kahaian; Arthur J. , Kim; Jeom-Soo

2008-04-15

Lithium metal oxide compounds of nominal formula Li.sub.2MO.sub.2, in which M represents two or more positively charged metal ions, selected predominantly and preferably from the first row of transition metals are disclosed herein. The Li.sub.2MO.sub.2 compounds have a layered-type structure, which can be used as positive electrodes for lithium electrochemical cells, or as a precursor for the in-situ electrochemical fabrication of LiMO.sub.2 electrodes. The Li.sub.2MO.sub.2 compounds of the invention may have additional functions in lithium cells, for example, as end-of-discharge indicators, or as negative electrodes for lithium cells.

Doping of carbon foams for use in energy storage devices

DOEpatents

Mayer, S.T.; Pekala, R.W.; Morrison, R.L.; Kaschmitter, J.L.

1994-10-25

A polymeric foam precursor, wetted with phosphoric acid, is pyrolyzed in an inert atmosphere to produce an open-cell doped carbon foam, which is utilized as a lithium intercalation anode in a secondary, organic electrolyte battery. Tests were conducted in a cell containing an organic electrolyte and using lithium metal counter and reference electrodes, with the anode located there between. Results after charge and discharge cycling, for a total of 6 cycles, indicated a substantial increase in the energy storage capability of the phosphorus doped carbon foam relative to the undoped carbon foam, when used as a rechargeable lithium ion battery. 3 figs.

Fragmentation of organic ions bearing fixed multiple charges observed in MALDI MS.

PubMed

Lou, Xianwen; Li, Bao; de Waal, Bas F M; Schill, Jurgen; Baker, Matthew B; Bovee, Ralf A A; van Dongen, Joost L J; Milroy, Lech-Gustav; Meijer, E W

2018-01-01

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS) was used to analyze a series of synthetic organic ions bearing fixed multiple charges. Despite the multiple intrinsic charges, only singly charged ions were recorded in each case. In addition to the pseudo-molecular ions formed by counterion adduction, deprotonation and electron capture, a number of fragment ions were also observed. Charge splitting by fragmentation was found to be a viable route for charge reduction leading to the formation of the observed singly charged fragment ions. Unlike multivalent metal ions, organic ions can rearrange and/or fragment during charge reduction. This fragmentation process will evidently complicate the interpretation of the MALDI MS spectrum. Because MALDI MS is usually considered as a soft ionization technique, the fragment ion peaks can easily be erroneously interpreted as impurities. Therefore, the awareness and understanding of the underlying MALDI-induced fragmentation pathways is essential for a proper interpretation of the corresponding mass spectra. Due to the fragment ions generated during charge reduction, special care should be taken in the MALDI MS analysis of multiply charged ions. In this work, the possible mechanisms by which the organic ions bearing fixed multiple charges fragment are investigated. With an improved understanding of the fragmentation mechanisms, MALDI TOF MS should still be a useful technique for the characterization of organic ions with fixed multiple charges. Copyright © 2017 John Wiley & Sons, Ltd.

Chemical dealloying synthesis of porous silicon anchored by in situ generated graphene sheets as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Feng, Jinkui; Zhang, Zhen; Ci, Lijie; Zhai, Wei; Ai, Qing; Xiong, Shenglin

2015-08-01

A novel one-pot chemical dealloying method has been developed to prepare nanocomposite of reduced graphene oxide (RGO) and silicon dendrite from cheap commercial Al-Si eutectic precursor. The RGO anchoring could act as both conductive agent and buffer layer for Si volume change in the application of lithium ion batteries (LIBs). The Si/RGO composites show an initial reversible capacity of 2280 mAh g-1, excellent capacity retention of 1942 mAh g-1 even after 100 cycles, and a high capacity of 1521 mAh g-1 even at the rate of 4000 mA g-1. Electrochemical impedance spectroscopy (EIS) measurement proved that Si/RGO composite has the lower charge transfer resistance. This work proposes an economic and facile method to prepare silicon based anode material for next generation LIBs with high energy density.

Ion-ion charge exchange processes. Final technical report, June 1, 1977-May 31, 1978

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

Poe, R.T.; Choi, B.H.

Under the auspices of ERDA, we have undertaken a vigorous study of ion-ion charge exchange process pertinent to the storage-ring configurations in the heavy-ion fusion program. One particular reaction, singly charged helium charge exchange, was investigated in detail. General trend of the singly charged heavy-ion charge exchange reaction can be inferred from the present study. Some of our results were presented at Proceedings of the Heavy-Ion Fusion Workshop, Argonne National Laboratory (September 1978) as a paper entitled Charge Exchange Between Singly Ionized Helium Ions, by B.H. Choi, R.T. Poe and K.T. Tang. Here, we briefly describe our method and reportmore » the results.« less

Transport, charge exchange and loss of energetic heavy ions in the earth's radiation belts - Applicability and limitations of theory

NASA Technical Reports Server (NTRS)

Spjeldvik, W. N.

1981-01-01

Computer simulations of processes which control the relative abundances of ions in the trapping regions of geospace are compared with observations from discriminating ion detectors. Energy losses due to Coulomb collisions between ions and exospheric neutrals are considered, along with charge exchange losses and internal charge exchanges. The time evolution of energetic ion fluxes of equatorially mirroring ions under radial diffusion is modelled to include geomagnetic and geoelectric fluctutations. Limits to the validity of diffusion transport theory are discussed, and the simulation is noted to contain provisions for six ionic charge states and the source effect on the radiation belt oxygen ion distributions. Comparisons are made with ion flux data gathered on Explorer 45 and ISEE-1 spacecraft and results indicate that internal charge exchanges cause the radiation belt ion charge state to be independent of source charge rate characteristics, and relative charge state distribution is independent of the radially diffusive transport rate below the charge state redistribution zone.

Highly charged ion beams and their applications

NASA Astrophysics Data System (ADS)

Marler, Joan

2018-01-01

While much previous work with highly charged ions has been performed with the ions in the plasma state in which they were formed, beams of highly charged ions hold promise for exciting new experiments. Specifically low energy beams with a high degree of charge state purity are a prerequisite for momentum resolved cross section measurements and for efficient loading of highly charged ions into UHV traps for spectroscopy. The Clemson University facility is optimized for the delivery of such beams of highly charged ions with low kinetic energies. Near term experiments include energy resolved charge exchange with neutral targets.

Oxidation of Methionine Residues in Polypeptide Ions via Gas-Phase Ion/Ion Chemistry

PubMed Central

Pilo, Alice L.; McLuckey, Scott A.

2014-01-01

The gas-phase oxidation of methionine residues is demonstrated here using ion/ion reactions with periodate anions. Periodate anions are observed to attach to varying degrees to all polypeptide ions irrespective of amino acid composition. Direct proton transfer yielding a charge reduced peptide ion is also observed. In the case of methionine and, to a much lesser degree, tryptophan containing peptide ions, collisional activation of the complex ion generated by periodate attachment yields an oxidized peptide product (i.e., [M+H+O]+), in addition to periodic acid detachment. Detachment of periodic acid takes place exclusively for peptides that do not contain either a methionine or tryptophan side-chain. In the case of methionine containing peptides, the [M+H+O]+ product is observed at a much greater abundance than the proton transfer product (viz., [M+H]+). Collisional activation of oxidized Met-containing peptides yields a signature loss of 64 Da from the precursor and/or product ions. This unique loss corresponds to the ejection of methanesulfenic acid from the oxidized methionine side chain and is commonly used in solution-phase proteomics studies to determine the presence of oxidized methionine residues. The present work shows that periodate anions can be used to ‘label’ methionine residues in polypeptides in the gas-phase. The selectivity of the periodate anion for the methionine side chain suggests several applications including identification and location of methionine residues in sequencing applications. PMID:24671696

EUV emission spectra in collisions of highly charged tantalum ions with nitrogen and oxygen molecules

NASA Astrophysics Data System (ADS)

Tanuma, Hajime; Numadate, Naoki; Uchikura, Yoshiyuki; Shimada, Kento; Akutsu, Takuto; Long, Elaine; O'Sullivan, Gerry

2017-10-01

We have performed ion beam collision experiments using multiply charged tantalum ions and observed EUV (extreme ultra-violet) emission spectra in collisions of ions with molecular targets, N2 and O2. Broad UTAs (un-resolved transition arrays) from multiply charged Ta ions were observed, and the mean wavelengths of the UTAs shifted and became shorter at higher charge statea of Ta ions. These UTAs may be attributed to the 4f-5d and 4f-5g transitions. Not only the UTA emission from incident ions, but also the sharp emission lines from multiply charged fragment atomic ions were observed. Production of temporary highly charged molecular ions, their kinetic energy and fragmentation processes have been investigated with coincident detection technique. However, the observation of emission from the fragments might be for the first time. The formation mechanisms of the multiply charged fragment atomic ions from target molecules are discussed.

Experimental Evidence for Space-Charge Effects between Ions of the Same Mass-to-Charge in Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry

PubMed Central

Wong, Richard L.; Amster, I. Jonathan

2009-01-01

It is often stated that ions of the same mass-to-charge do not induce space-charge frequency shifts among themselves in an ion cyclotron resonance mass spectrometry measurement. Here, we demonstrate space-charge induced frequency shifts for ions of a single mass-to-charge. The monoisotopic atomic ion, Cs+, was used for this study. The measured frequency is observed to decrease linearly with an increase in the number of ions, as has been reported previously for space-charge effects between ions of different mass-to-charge. The frequency shift between ions of the same m/z value are compared to that induced between ions of different m/z value, and is found to be 7.5 times smaller. Control experiments were performed to ensure that the observed space-charge effects are not artifacts of the measurement or of experimental design. The results can be rationalized by recognizing that the electric forces between ions in a magnetic field conform to the weak form of the Newton's third law, where the action and reaction forces do not cancel exactly. PMID:19562102

Characterization of Long-Chain Fatty Acid as N-(4-Aminomethylphenyl) Pyridinium Derivative by MALDI LIFT-TOF/TOF Mass Spectrometry

NASA Astrophysics Data System (ADS)

Frankfater, Cheryl; Jiang, Xuntian; Hsu, Fong-Fu

2018-05-01

Charge remote fragmentation (CRF) elimination of CnH2n+2 residues along the aliphatic tail of long chain fatty acid is hall mark of keV high-energy CID fragmentation process. It is an important fragmentation pathway leading to structural characterization of biomolecules by CID tandem mass spectrometry. In this report, we describe MALDI LIFT TOF-TOF mass spectrometric approach to study a wide variety of fatty acids (FAs), which were derivatized to N-(4-aminomethylphenyl) pyridinium (AMPP) derivative, and desorbed as M+ ions by laser with or without matrix. The high-energy MALDI LIFT TOF-TOF mass spectra of FA-AMPP contain fragment ions mainly deriving from CRF cleavages of CnH2n+2 residues, as expected. These ions together with ions from specific cleavages of the bond(s) involving the functional group within the molecule provide more complete structural identification than those produced by low-energy CID/HCD using a linear ion-trap instrument. However, this LIFT TOF-TOF mass spectrometric approach inherits low sensitivity, a typical feature of high-energy CID tandem mass spectrometry. Because of the lack of unit mass precursor ion selection with sufficient sensitivity of the current LIFT TOF-TOF technology, product ion spectra from same chain length fatty acids with difference in one or two double bonds in a mixture are not distinguishable.

Charge breeding simulations for radioactive ion beam production

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

Variale, V.; Raino, A. C.; Clauser, T.

2012-02-15

The charge breeding technique is used for radioactive ion beam (RIB) production in order of optimizing the re-acceleration of the radioactive element ions produced by a primary beam in a thick target. Charge breeding is achieved by means of a device capable of increasing the ion charge state from 1+ to a desired value n+. In order to get high intensity RIB, experiments with charge breeding of very high efficiency could be required. To reach this goal, the charge breeding simulation could help to optimize the high charge state production efficiency by finding more proper parameters for the radioactive 1+more » ions. In this paper a device based on an electron beam ion source (EBIS) is considered. In order to study that problem, a code already developed for studying the ion selective containment in an EBIS with RF quadrupoles, BRICTEST, has been modified to simulate the ion charge state breeding rate for different 1+ ion injection conditions. Particularly, the charge breeding simulations for an EBIS with a hollow electron beam have been studied.« less

A singly charged ion source for radioactive {sup 11}C ion acceleration

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

Katagiri, K.; Noda, A.; Nagatsu, K.

2016-02-15

A new singly charged ion source using electron impact ionization has been developed to realize an isotope separation on-line system for simultaneous positron emission tomography imaging and heavy-ion cancer therapy using radioactive {sup 11}C ion beams. Low-energy electron beams are used in the electron impact ion source to produce singly charged ions. Ionization efficiency was calculated in order to decide the geometric parameters of the ion source and to determine the required electron emission current for obtaining high ionization efficiency. Based on these considerations, the singly charged ion source was designed and fabricated. In testing, the fabricated ion source wasmore » found to have favorable performance as a singly charged ion source.« less

Automated tandem mass spectrometry by orthogonal acceleration TOF data acquisition and simultaneous magnet scanning for the characterization of petroleum mixtures.

PubMed

Roussis, S G

2001-08-01

The automated acquisition of the product ion spectra of all precursor ions in a selected mass range by using a magnetic sector/orthogonal acceleration time-of-flight (oa-TOF) tandem mass spectrometer for the characterization of complex petroleum mixtures is reported. Product ion spectra are obtained by rapid oa-TOF data acquisition and simultaneous scanning of the magnet. An analog signal generator is used for the scanning of the magnet. Slow magnet scanning rates permit the accurate profiling of precursor ion peaks and the acquisition of product ion spectra for all isobaric ion species. The ability of the instrument to perform both high- and low-energy collisional activation experiments provides access to a large number of dissociation pathways useful for the characterization of precursor ions. Examples are given that illustrate the capability of the method for the characterization of representative petroleum mixtures. The structural information obtained by the automated MS/MS experiment is used in combination with high-resolution accurate mass measurement results to characterize unknown components in a polar extract of a refinery product. The exhaustive mapping of all precursor ions in representative naphtha and middle-distillate fractions is presented. Sets of isobaric ion species are separated and their structures are identified by interpretation from first principles or by comparison with standard 70-eV EI libraries of spectra. The utility of the method increases with the complexity of the samples.

Analyzing Internal Fragmentation of Electrosprayed Ubiquitin Ions During Beam-Type Collisional Dissociation

NASA Astrophysics Data System (ADS)

Durbin, Kenneth R.; Skinner, Owen S.; Fellers, Ryan T.; Kelleher, Neil L.

2015-05-01

Gaseous fragmentation of intact proteins is multifaceted and can be unpredictable by current theories in the field. Contributing to the complexity is the multitude of precursor ion states and fragmentation channels. Terminal fragment ions can be re-fragmented, yielding product ions containing neither terminus, termed internal fragment ions. In an effort to better understand and capitalize upon this fragmentation process, we collisionally dissociated the high (13+), middle (10+), and low (7+) charge states of electrosprayed ubiquitin ions. Both terminal and internal fragmentation processes were quantified through step-wise increases of voltage potential in the collision cell. An isotope fitting algorithm matched observed product ions to theoretical terminal and internal fragment ions. At optimal energies for internal fragmentation of the 10+, nearly 200 internal fragments were observed; on average each of the 76 residues in ubiquitin was covered by 24.1 internal fragments. A pertinent finding was that formation of internal ions occurs at similar energy thresholds as terminal b- and y-ion types in beam-type activation. This large amount of internal fragmentation is frequently overlooked during top-down mass spectrometry. As such, we present several new approaches to visualize internal fragments through modified graphical fragment maps. With the presented advances of internal fragment ion accounting and visualization, the total percentage of matched fragment ions increased from approximately 40% to over 75% in a typical beam-type MS/MS spectrum. These sequence coverage improvements offer greater characterization potential for whole proteins with no needed experimental changes and could be of large benefit for future high-throughput intact protein analysis.

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

Low charge state heavy ion production with sub-nanosecond laser.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

We have investigated laser ablation plasma of various species using nanosecond and sub-nanosecond lasers for both high and low charge state ion productions. We found that with sub-nanosecond laser, the generated plasma has a long tail which has low charge state ions determined by an electrostatic ion analyzer even under the laser irradiation condition for highly charged ion production. This can be caused by insufficient laser absorption in plasma plume. This property might be suitable for low charge state ion production. We used a nanosecond laser and a sub-nanosecond laser for low charge state ion production to investigate the difference of generated plasma using the Zirconium target.

Low charge state heavy ion production with sub-nanosecond laser

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

Kanesue, T., E-mail: tkanesue@bnl.gov; Okamura, M.; Kumaki, M.

2016-02-15

We have investigated laser ablation plasma of various species using nanosecond and sub-nanosecond lasers for both high and low charge state ion productions. We found that with sub-nanosecond laser, the generated plasma has a long tail which has low charge state ions determined by an electrostatic ion analyzer even under the laser irradiation condition for highly charged ion production. This can be caused by insufficient laser absorption in plasma plume. This property might be suitable for low charge state ion production. We used a nanosecond laser and a sub-nanosecond laser for low charge state ion production to investigate the differencemore » of generated plasma using the Zirconium target.« less

A vacuum spark ion source: High charge state metal ion beams

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

Yushkov, G. Yu., E-mail: gyushkov@mail.ru; Nikolaev, A. G.; Frolova, V. P.

2016-02-15

High ion charge state is often important in ion beam physics, among other reasons for the very practical purpose that it leads to proportionately higher ion beam energy for fixed accelerating voltage. The ion charge state of metal ion beams can be increased by replacing a vacuum arc ion source by a vacuum spark ion source. Since the voltage between anode and cathode remains high in a spark discharge compared to the vacuum arc, higher metal ion charge states are generated which can then be extracted as an ion beam. The use of a spark of pulse duration less thanmore » 10 μs and with current up to 10 kA allows the production of ion beams with current of several amperes at a pulse repetition rate of up to 5 pps. We have demonstrated the formation of high charge state heavy ions (bismuth) of up to 15 + and a mean ion charge state of more than 10 +. The physics and techniques of our vacuum spark ion source are described.« less

Performance and Safety of Lithium Ion Cells

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Smart, M. C.; Whitcanack, L.; Surampudi, S.; Marsh, R.

2001-01-01

This report evaluates the performance and safety of Lithium Ion (Li-Ion) cells when used in batteries. Issues discussed include the cycle life, energy efficiency, tolerance to higher charge voltage, tolerance to extended tapered charge voltage, charge on cycling, specific energy, low temperature discharge, low temperature charge, various charge characteristics, storage characteristics, and more of Li-Ion cells.

Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries

PubMed Central

David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

2016-01-01

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm−2) delivers a charge capacity of ∼588 mAh g−1electrode (∼393 mAh cm−3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries. PMID:27025781

The reactions of a series of terpenoids with H(3) O(+) , NO(+) and O 2+ studied using selected ion flow tube mass spectrometry.

PubMed

Amadei, Gianluca; Ross, Brian M

2011-01-15

The reactions of H(3) O(+) , NO(+) and O 2+ with twelve terpenoids and one terpene, all of which occur naturally in plants and which possess important smell and flavourant properties, were characterized using Selected Ion Flow Tube Mass Spectrometry (SIFT-MS). The H(3) O(+) reactions resulted primarily in the formation of the proton transfer product and occasionally in a water elimination product. The NO(+) reactions instead generated the charge transfer product or NO(+) adducts, and occasionally alkyl fragments, or resulted in hydride abstraction. Reaction with O 2+ caused a higher fragmentation of the terpenoids with the molecular ion being the minor product of most reactions. Identification and quantification of each compound in complex mixtures are probably possible in most cases using the H(3) O(+) and/or NO(+) precursors while O 2+ may be useful for isomer discrimination. Our data suggests that SIFT-MS may be a useful tool for the rapid analysis of these compounds in plants and derived foodstuffs. Copyright © 2010 John Wiley & Sons, Ltd.

Low Temperature Vacuum Synthesis of Triangular CoO Nanocrystal/Graphene Nanosheets Composites with Enhanced Lithium Storage Capacity

PubMed Central

Guan, Qun; Cheng, Jianli; Li, Xiaodong; Wang, Bin; Huang, Ling; Nie, Fude; Ni, Wei

2015-01-01

CoO nanocrystal/graphene nanosheets (GNS) composites, consisting of a triangular CoO nanocrystal of 2~20 nm on the surface of GNS, are synthesized by a mild synthetic method. First, cobalt acetate tetrahydrate is recrystallized in the alcohol solution at a low temperature. Then, graphene oxide mixed with cobalt-precursor followed by high vacuum annealing to form the CoO nanocrystal/GNS composites. The CoO nanocrystal/GNS composites exhibit a high reversible capacity of 1481.9 m Ah g−1 after 30 cycles with a high Coulombic efficiency of over 96% when used as anode materials for lithium ion battery. The excellent electrochemical performances may be attributed to the special structure of the composites. The well-dispersed triangular CoO nanocrystal on the substrate of conductive graphene can not only have a shorter diffusion length for lithium ions, better stress accommodation capability during the charge-discharge processes and more accessible active sites for lithium-ion storage and electrolyte wetting, but also possess a good conductive network, which can significantly improve the whole electrochemical performance. PMID:25961670

Removal of both N-nitrosodimethylamine and trihalomethanes precursors in a single treatment using ion exchange resins.

PubMed

Beita-Sandí, Wilson; Karanfil, Tanju

2017-11-01

Drinking water utilities are relying more than ever on water sources impacted by wastewater effluents. Disinfection/oxidation of these waters during water treatment may lead to the formation of several disinfection by-products, including the probable human carcinogen N-nitrosodimethylamine (NDMA) and the regulated trihalomethanes (THMs). In this study, the potential of ion exchange resins to control both NDMA and THMs precursors in a single treatment is presented. Two ion exchange resins were examined, a cation exchange resin (Plus) to target NDMA precursors and an anion exchange resin (MIEX) for THMs precursors control. We applied the resins, individually and combined, in the treatment of surface and wastewater effluent samples. The treatment with both resins removed simultaneously NDMA (43-85%) and THMs (39-65%) precursors. However, no removal of NDMA precursors was observed in the surface water with low initial NDMA FP (14 ng/L). The removals of NDMA FP and THMs FP with Plus and MIEX resins applied alone were (49-90%) and (41-69%), respectively. These results suggest no interaction between the resins, and thus the feasibility of effectively controlling NDMA and THMs precursors concomitantly. Additionally, the effects of the wastewater impact and the natural attenuation of precursors were studied. The results showed that neither the wastewater content nor the attenuation of the precursor affected the removals of NDMA and THMs precursors. Finally, experiments using a wastewater effluent sample showed that an increase in the calcium concentration resulted in a reduction in the removal of NDMA precursors of about 50%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

2017-02-01

A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

Wall-loss distribution of charge breeding ions in an electron cyclotron resonance ion source

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

Jeong, S. C.; Oyaizu, M.; Imai, N.

2011-03-15

The ion loss distribution in an electron cyclotron resonance ion source (ECRIS) was investigated to understand the element dependence of the charge breeding efficiency in an electron cyclotron resonance (ECR) charge breeder. The radioactive {sup 111}In{sup 1+} and {sup 140}Xe{sup 1+} ions (typical nonvolatile and volatile elements, respectively) were injected into the ECR charge breeder at the Tokai Radioactive Ion Accelerator Complex to breed their charge states. Their respective residual activities on the sidewall of the cylindrical plasma chamber of the source were measured after charge breeding as functions of the azimuthal angle and longitudinal position and two-dimensional distributions ofmore » ions lost during charge breeding in the ECRIS were obtained. These distributions had different azimuthal symmetries. The origins of these different azimuthal symmetries are qualitatively discussed by analyzing the differences and similarities in the observed wall-loss patterns. The implications for improving the charge breeding efficiencies of nonvolatile elements in ECR charge breeders are described. The similarities represent universal ion loss characteristics in an ECR charge breeder, which are different from the loss patterns of electrons on the ECRIS wall.« less

Conducting ion tracks generated by charge-selected swift heavy ions

NASA Astrophysics Data System (ADS)

Gupta, Srashti; Gehrke, H. G.; Krauser, J.; Trautmann, C.; Severin, D.; Bender, M.; Rothard, H.; Hofsäss, H.

2016-08-01

Conducting ion tracks in tetrahedral amorphous carbon (ta-C) thin films were generated by irradiation with swift heavy ions of well-defined charge state. The conductivity of tracks and the surface topography of the films, showing characteristic hillocks at each track position, were investigated using conductive atomic force microscopy measurements. The dependence of track conductivity and hillock size on the charge state of the ions was studied using 4.6 MeV/u Pb ions of charge state 53+, 56+ and 60+ provided by GANIL, as well as 4.8 MeV/u Bi and Au ions of charge state from 50+ to 61+ and 4.2 MeV/u 238U ions in equilibrium charge state provided by UNILAC of GSI. For the charge state selection at GSI, an additional stripper-foil system was installed at the M-branch that now allows routine irradiations with ions of selected charge states. The conductivity of tracks in ta-C increases significantly when the charge state increases from 51+ to 60+. However, the conductivity of individual tracks on the same sample still shows large variations, indicating that tracks formed in ta-C are either inhomogeneous or the conductivity is limited by the interface between ion track and Si substrate.

Coated/Sandwiched rGO/CoSx Composites Derived from Metal-Organic Frameworks/GO as Advanced Anode Materials for Lithium-Ion Batteries.

PubMed

Yin, Dongming; Huang, Gang; Zhang, Feifei; Qin, Yuling; Na, Zhaolin; Wu, Yaoming; Wang, Limin

2016-01-22

Rational composite materials made from transition metal sulfides and reduced graphene oxide (rGO) are highly desirable for designing high-performance lithium-ion batteries (LIBs). Here, rGO-coated or sandwiched CoSx composites are fabricated through facile thermal sulfurization of metal-organic framework/GO precursors. By scrupulously changing the proportion of Co(2+) and organic ligands and the solvent of the reaction system, we can tune the forms of GO as either a coating or a supporting layer. Upon testing as anode materials for LIBs, the as-prepared CoSx -rGO-CoSx and rGO@CoSx composites demonstrate brilliant electrochemical performances such as high initial specific capacities of 1248 and 1320 mA h g(-1) , respectively, at a current density of 100 mA g(-1) , and stable cycling abilities of 670 and 613 mA h g(-1) , respectively, after 100 charge/discharge cycles, as well as superior rate capabilities. The excellent electrical conductivity and porous structure of the CoSx /rGO composites can promote Li(+) transfer and mitigate internal stress during the charge/discharge process, thus significantly improving the electrochemical performance of electrode materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

NASA Astrophysics Data System (ADS)

Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

2017-12-01

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

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).

Direct-write three-dimensional nanofabrication of nanopyramids and nanocones on Si by nanotumefaction using a helium ion microscope

NASA Astrophysics Data System (ADS)

Zhang, L.; Heinig, N. F.; Bazargan, S.; Abd-Ellah, M.; Moghimi, N.; Leung, K. T.

2015-06-01

The recently commercialized helium ion microscope (HIM) has already demonstrated its outstanding imaging capabilities in terms of resolution, surface sensitivity, depth of field and ease of charge compensation. Here, we show its exceptional patterning capabilities by fabricating dense lines and three-dimensional (3D) nanostructures on a Si substrate. Small focusing spot size and confined ion-Si interaction volume of a high-energy helium ion beam account for the high resolution in HIM patterning. We demonstrate that a set of resolvable parallel lines with a half pitch as small as 3.5 nm can be achieved. During helium ion bombardment of the Si surface, implantation outperforms milling due to the small mass of the helium ions, which produces tumefaction instead of depression in the Si surface. The Si surface tumefaction is the result of different kinetic processes including diffusion, coalescence and nanobubble formation of the implanted ions, and is found to be very stable structurally at room temperature. Under appropriate conditions, a linear dependence of the surface swollen height on the ion doses can be observed. This relation has enabled us to fabricate nanopyramids and nanocones, thus demonstrating that HIM patterning provides a new ‘bottom-up’ approach to fabricate 3D nanostructures. This surface tumefaction method is direct, both positioning and height accurate, and free of resist, etch, mode and precursor, and it promises new applications in nanoimprint mold fabrication and photomask clear defect reparation.

Dehydrogenation involved Coulomb explosion of molecular C2H4FBr in an intense laser field

NASA Astrophysics Data System (ADS)

Pei, Minjie; Yang, Yan; Zhang, Jian; Sun, Zhenrong

2018-04-01

The dissociative double ionization (DDI) of molecular 1-fluo-2-bromoethane (FBE) in an intense laser field has been investigated by dc-slice imaging technology. The DDI channels involved with dehydrogenation are revealed and it's believed both the charge distribution and the bound character of real potential energy surfaces of parent ions play important roles in the dissociation process. The relationship between the potential energy surfaces of the precursor species and the photofragment ejection angles are also discussed and analyzed. Furthermore, the competition between the DDI channels has been studied and the Csbnd C bond cleavages dominate the DDI process at relative higher laser intensity.

One-dimensional α-MoO3 nanorods for high energy density pseudocapacitor

NASA Astrophysics Data System (ADS)

Dutta, Shibsankar; Pal, Shreyasi; De, Sukanta

2018-04-01

Ultralong α-MoO3 nanorods having length of 500 nm to 1 µm and uniform width of around ˜50 nm have been synthesized by a simple one step hydrothermal route using a molybdenum organic salt precursor. An evaluation of the electrochemical properties of the nanorods was done by cyclic voltammetry (CV), and galvanometric charging- discharging (GCD) test. Because of the high active sites and rapid ion diffusion and electron transport of the electrodes using as prepared nanorods reveals energy density of 65 Wh/kg at a power density of 940 W/ kg and a maximum specific capacitance of 474 F/g. It also shows excellent cycling stability.

Gas-Phase Synthesis of Singly and Multiply Charged Polyoxovanadate Anions Employing Electrospray Ionization and Collision Induced Dissociation

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

Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia

2013-07-02

Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including V xO y n– and V xO yCl n– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V 14O 36Cl(L) 5 (L = Et 4N +, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged V xO yCl n– and V xOmore » yCl(L) (n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller V xO yCl (1–2)– and V xO y (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged V xO yCl and V xO y species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of V xO yCl and V xO y anions through low-energy CID. Finally and furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.« less

Gated charged-particle trap

DOEpatents

Benner, W.H.

1999-03-09

The design and operation of a new type of charged-particle trap provides simultaneous measurements of mass, charge, and velocity of large electrospray ions. The trap consists of a detector tube mounted between two sets of center-bored trapping plates. Voltages applied to the trapping plates define symmetrically-opposing potential valleys which guide axially-injected ions to cycle back and forth through the charge-detection tube. A low noise charge-sensitive amplifier, connected to the tube, reproduces the image charge of individual ions as they pass through the detector tube. Ion mass is calculated from measurement of ion charge and velocity following each passage through the detector. 5 figs.

[Application of precursor ion scanning method in rapid screening of illegally added phosphodiesterase-5 inhibitors and their unknown derivatives in Chinese traditional patent medicines and health foods].

PubMed

Sun, Jing; Cao, Ling; Feng, Youlong; Tan, Li

2014-11-01

The compounds with similar structure often have similar pharmacological activities. So it is a trend for illegal addition that new derivatives of effective drugs are synthesized to avoid the statutory test. This bring challenges to crack down on illegal addition behavior, however, modified derivatives usually have similar product ions, which allow for precursor ion scanning. In this work, precursor ion scanning mode of a triple quadrupole mass spectrometer was first applied to screen illegally added drugs in complex matrix such as Chinese traditional patent medicines and healthy foods. Phosphodiesterase-5 inhibitors were used as experimental examples. Through the analysis of the structure and mass spectrum characteristics of the compounds, phosphodiesterase-5 inhibitors were classified, and their common product ions were screened by full scan of product ions of typical compounds. Then high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method with precursor ion scanning mode was established based on the optimization of MS parameters. The effect of mass parameters and the choice of fragment ions were also studied. The method was applied to determine actual samples and further refined. The results demonstrated that this method can meet the need of rapid screening of unknown derivatives of phosphodiesterase-5 inhibitors in complex matrix, and prevent unknown derivatives undetected. This method shows advantages in sensitivity, specificity and efficiency, and is worth to be further investigated.

Improved Methods for the Enrichment and Analysis of Glycated Peptides

PubMed Central

Zhang, Qibin; Schepmoes, Athena A.; Brock, Jonathan W. C.; Wu, Si; Moore, Ronald J.; Purvine, Samuel O.; Baynes, John W.; Smith, Richard D.; Metz, Thomas O.

2009-01-01

Nonenzymatic glycation of tissue proteins has important implications in the development of complications of diabetes mellitus. Herein we report improved methods for the enrichment and analysis of glycated peptides using boronate affinity chromatography and electron-transfer dissociation mass spectrometry, respectively. The enrichment of glycated peptides was improved by replacing an off-line desalting step with an online wash of column-bound glycated peptides using 50 mM ammonium acetate, followed by elution with 100 mM acetic acid. The analysis of glycated peptides by MS/MS was improved by considering only higher charged (≥3) precursor ions during data-dependent acquisition, which increased the number of glycated peptide identifications. Similarly, the use of supplemental collisional activation after electron transfer (ETcaD) resulted in more glycated peptide identifications when the MS survey scan was acquired with enhanced resolution. Acquiring ETD-MS/MS data at a normal MS survey scan rate, in conjunction with the rejection of both 1+ and 2+ precursor ions, increased the number of identified glycated peptides relative to ETcaD or the enhanced MS survey scan rate. Finally, an evaluation of trypsin, Arg-C, and Lys-C showed that tryptic digestion of glycated proteins was comparable to digestion with Lys-C and that both were better than Arg-C in terms of the number of glycated peptides and corresponding glycated proteins identified by LC–MS/MS. PMID:18989935

Charged particle measurements on a 30-CM diameter mercury ion engine thrust beam

NASA Technical Reports Server (NTRS)

Sellen, J. M., Jr.; Komatsu, G. K.; Hoffmaster, D. K.; Kemp, R. F.

1974-01-01

Measurements of both thrust ions and charge exchange ions were made in the beam of a 30 centimeter diameter electron bombardment mercury ion thruster. A qualitative model is presented which describes magnitudes of charge exchange ion formation and motions of these ions in the weak electric field structure of the neutralized thrust beam plasma. Areas of agreement and discrepancy between observed and modeled charge exchange properties are discussed.

Lateral charge transport from heavy-ion tracks in integrated circuit chips

NASA Technical Reports Server (NTRS)

Zoutendyk, J. A.; Schwartz, H. R.; Nevill, L. R.

1988-01-01

A 256K DRAM has been used to study the lateral transport of charge (electron-hole pairs) induced by direct ionization from heavy-ion tracks in an IC. The qualitative charge transport has been simulated using a two-dimensional numerical code in cylindrical coordinates. The experimental bit-map data clearly show the manifestation of lateral charge transport in the creation of adjacent multiple-bit errors from a single heavy-ion track. The heavy-ion data further demonstrate the occurrence of multiple-bit errors from single ion tracks with sufficient stopping power. The qualitative numerical simulation results suggest that electric-field-funnel-aided (drift) collection accounts for single error generated by an ion passing through a charge-collecting junction, while multiple errors from a single ion track are due to lateral diffusion of ion-generated charge.

Lithium-Ion Cell Charge-Control Unit Developed

NASA Technical Reports Server (NTRS)

Reid, Concha M.; Manzo, Michelle A.; Buton, Robert M.; Gemeiner, Russel

2005-01-01

A lithium-ion (Li-ion) cell charge-control unit was developed as part of a Li-ion cell verification program. This unit manages the complex charging scheme that is required when Li-ion cells are charged in series. It enables researchers to test cells together as a pack, while allowing each cell to charge individually. This allows the inherent cell-to-cell variations to be addressed on a series string of cells and reduces test costs substantially in comparison to individual cell testing.

Ion-ion Recombination and Chemiion Concentrations In Aircraft Exhaust

NASA Astrophysics Data System (ADS)

Turco, R. P.; Yu, F.

Jet aircraft emit large quantities of ultrafine volatile aerosols, as well as soot parti- cles, into the environment. To determine the long-term effects of these emissions, a better understanding of the mechanisms that control particle formation and evolution is needed, including the number and size dispersion. A recent explanation for aerosol nucleation in a jet wake involves the condensation of sulfuric acid vapor, and cer- tain organic compounds, onto charged molecular clusters (chemiions) generated in the engine combustors (Yu and Turco, 1997). Massive charged aggregates, along with sulfuric acid and organic precursor vapors, have been detected in jet plumes under cruise conditions. In developing the chemiion nucleation theory, Yu and Turco noted that ion-ion recombination in the engine train and jet core should limit the chemiion emission index to 1017/kg-fuel. This value is consistent with ion-ion recombination coefficients of 1×10-7 cm3/s over time scales of 10-2 s. However, the evolution of the ions through the engine has not been adequately studied. The conditions at the combustor exit are extreme-temperatures approach 1500 K, and pressures can reach 30 atmospheres. In this presentation, we show that as the combustion gases expand and cool, two- and three-body ion-ion recombination processes control the chemiion concentration. The concepts of mutual neutralization and Thomson recombination are first summarized, and appropriate temperature and pressure dependent recombination rate coefficients are derived for the aircraft problem. A model for ion losses in jet exhaust is then formulated using an "invariance" principle discussed by Turco and Yu (1997) in the context of a coagulating aerosol in an expanding plume. This recombina- tion model is applied to estimate chemiion emission indices for a range of operational engine conditions. The predicted ion emission rates are found to be consistent with observations. We discuss the sources of variance in chemiion exhaust concentrations based on the physical processes occurring in the exhaust stream. References: Turco, R. P., and F. Yu, Aerosol invariance in expanding, coagulating plumes, Geo- phys. Res. Lett., 24, 1223-1226, 1997. Yu, F., and R. P. Turco, The role of ions in the formation and evolution of particles in aircraft plumes, Geophys. Res. Lett., 24, 1927-1930, 1997.

Simulation of charge breeding of rubidium using Monte Carlo charge breeding code and generalized ECRIS model

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

Zhao, L.; Cluggish, B.; Kim, J. S.

2010-02-15

A Monte Carlo charge breeding code (MCBC) is being developed by FAR-TECH, Inc. to model the capture and charge breeding of 1+ ion beam in an electron cyclotron resonance ion source (ECRIS) device. The ECRIS plasma is simulated using the generalized ECRIS model which has two choices of boundary settings, free boundary condition and Bohm condition. The charge state distribution of the extracted beam ions is calculated by solving the steady state ion continuity equations where the profiles of the captured ions are used as source terms. MCBC simulations of the charge breeding of Rb+ showed good agreement with recentmore » charge breeding experiments at Argonne National Laboratory (ANL). MCBC correctly predicted the peak of highly charged ion state outputs under free boundary condition and similar charge state distribution width but a lower peak charge state under the Bohm condition. The comparisons between the simulation results and ANL experimental measurements are presented and discussed.« less

Interaction of highly charged ions with carbon nano membranes

NASA Astrophysics Data System (ADS)

Gruber, Elisabeth; Wilhelm, Richard A.; Smejkal, Valerie; Heller, René; Facsko, Stefan; Aumayr, Friedrich

2015-09-01

Charge state and energy loss measurements of slow highly charged ions (HCIs) after transmission through nanometer and sub-nanometer thin membranes are presented. Direct transmission measurements through carbon nano membranes (CNMs) show an unexpected bimodal exit charge state distribution, accompanied by charge exchange dependent energy loss. The energy loss of ions in CNMs with large charge loss shows a quadratic dependency on the incident charge state, indicating charge state dependent stopping force values. Another access to the exit charge state distribution is given by irradiating stacks of CNMs and investigating each layer of the stack with high resolution imaging techniques like transmission electron microscopy (TEM) and helium ion microscopy (HIM) independently. The observation of pores created in all of the layers confirms the assumption derived from the transmission measurements that the two separated charge state distributions reflect two different impact parameter regimes, i.e. close collision with large charge exchange and distant collisions with weak ion-target interaction.

Battery Power Management in Heavy-duty HEVs based on the Estimated Critical Surface Charge

DTIC Science & Technology

2011-03-01

health prospects without any penalty on fuel efficiency. Keywords: Lithium - ion battery ; power management; critical surface charge; Lithium-ion...fuel efficiency. 15. SUBJECT TERMS Lithium - ion battery ; power management; critical surface charge; Lithium-ion concentration; estimation; extended...Di Domenico, D., Fiengo, G., and Stefanopoulou, A. (2008) ’ Lithium - ion battery state of charge estimation with a kalman filter based on a

Highly charged ion secondary ion mass spectroscopy

DOEpatents

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

2001-01-01

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

Structural characterization of layered Na0.5Co0.5Mn0.5O2 material as a promising cathode for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Manikandan, Palanisamy; Heo, Seongwoo; Kim, Hyun Woo; Jeong, Hu Young; Lee, Eungje; Kim, Youngsik

2017-09-01

Layered Na0.5Co0.5Mn0.5O2 material is synthesized through a facile mixed hydroxy-carbonate route using (Co0.5Mn0.5)2(OH)2CO3 precursor and well characterized as a hexagonal layered structure under P63/mmc space group. The lattice parameters and unit cell volume (a = 2.8363 Å, c = 11.3152 Å and V = 78.83 Å3) are calculated by Rietveld refinement analysis. A flaky-bundle morphology is obtained to the layered Na0.5Co0.5Mn0.5O2 material with the hexagonal flake size ∼30 nm. Advanced transmission electron microscopic images are revealed the local structure of the layered Na0.5Co0.5Mn0.5O2 material with contrasting bright dots and faint dark dots corresponding to the Co/Mn and Na atoms. Two oxidation and reduction peaks are occurred in a cyclic voltammetric analysis corresponding to Co3+/Co4+ and Mn3+/Mn4+ redox processes. These reversible processes are attributed to the intercalation/de-intercalation of Na+ ions into the host structure of layered Na0.5Co0.5Mn0.5O2 material. Accordingly, the sodium cell is delivered the initial charge-discharge capacity 53/144 mAh g-1 at 0.5 C, which cycling studies are extended to rate capability test at 1 C, 3 C and 5C. Eventually, the Na-ion full-cell is yielded cathode charge-discharge capacity 55/52 mAh g-1 at 0.212 mA and exhibited as a high voltage cathode for Na-ion batteries.

Charging of Proteins in Native Mass Spectrometry

DOE PAGES

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.; ...

2016-10-12

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo protonmore » transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.« less

Charging of Proteins in Native Mass Spectrometry

NASA Astrophysics Data System (ADS)

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.; Tainer, John A.; Williams, Evan R.

2017-02-01

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo proton transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging.

PubMed

He, Yadong; Qiao, Rui; Vatamanu, Jenel; Borodin, Oleg; Bedrov, Dmitry; Huang, Jingsong; Sumpter, Bobby G

2016-01-07

Molecular simulations of the diffusion of EMIM(+) and TFSI(-) ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching ∼5 × 10(-9) m(2)/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

DOE PAGES

He, Yadong; Qiao, Rui; Vatamanu, Jenel; ...

2015-12-07

In molecular simulations of the diffusion of EMIM+ and TESI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching similar to 5 x 10 -9 m 2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Moreover, analysis of these results revealed that the fast (ormore » slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. Finally, the molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.« less

Application of stored waveform ion modulation 2D-FTICR MS/MS to the analysis of complex mixtures.

PubMed

Ross, Charles W; Simonsick, William J; Aaserud, David J

2002-09-15

Component identification of complex mixtures, whether they are from polymeric formulations or combinatorial synthesis, by conventional MS/MS techniques generally requires component separation by chromatography or mass spectrometry. An automated means of acquiring simultaneous MS/MS data from a complex mixture without prior separation is obtained from stored waveform ion modulation (SWIM) two-dimensional FTICR MS/MS. The technique applies a series of SWIFT excitation waveforms whose frequency domain magnitude spectrum is a sinusoid increasing in frequency from one waveform to the next. The controlled dissociation of the precursor ions produces an associated modulation of the product ion abundances. Fourier transformation of these abundances reveals the encoded modulation frequency from which connectivities of precursor and product ions are observed. The final result is total assignment of product ions for each precursor ion in a mixture from one automated experiment. We demonstrated the applicability of SWIM 2D-FTICR MS/MS to two diverse samples of industrial importance. We characterized structured polyester oligomers and products derived from combinatorial synthesis. Fragmentation pathways identified in standard serial ion isolation MS/MS experiments were observed for trimethylolpropane/methyl hexahydrophthalic anhydride. A 20-component sample derived from combinatorial synthesis was fragmented, and the template ion along with another key fragment ion was identified for each of the 20 components.

Ellipticity-dependent of multiple ionisation methyl iodide cluster using 532 nm nanosecond laser

NASA Astrophysics Data System (ADS)

Tang, Bin; Zhao, Wuduo; Wang, Weiguo; Hua, Lei; Chen, Ping; Hou, Keyong; Huang, Yunguang; Li, Haiyang

2016-03-01

The dependence of multiply charged ions on laser ellipticity in methyl iodide clusters with 532 nm nanosecond laser was measured using a time-of-flight mass spectrometer. The intensities of multiply charged ions Iq+(q = 2-4) with circularly polarised laser pulse were clearly higher than those with linearly polarised laser pulse but the intensity of single charged ions I+ was inverse. And the dependences of ions on the optical polarisation state were investigated and a flower petal and square distribution for single charged ions (I+, C+) and multiply charged ions (I2+, I3+, I4+, C2+) were observed, respectively. A theoretical calculation was also proposed to simulate the distributions of ions and theoretical results fitted well with the experimental ones. It indicated that the high multiphoton ionisation probability in the initial stage would result in the disintegration of big clusters into small ones and suppress the production of multiply charged ions.

Salt Bridge Rearrangement (SaBRe) Explains the Dissociation Behavior of Noncovalent Complexes

NASA Astrophysics Data System (ADS)

Loo, Rachel R. Ogorzalek; Loo, Joseph A.

2016-06-01

Native electrospray ionization-mass spectrometry, with gas-phase activation and solution compositions that partially release subcomplexes, can elucidate topologies of macromolecular assemblies. That so much complexity can be preserved in gas-phase assemblies is remarkable, although a long-standing conundrum has been the differences between their gas- and solution-phase decompositions. Collision-induced dissociation of multimeric noncovalent complexes typically distributes products asymmetrically (i.e., by ejecting a single subunit bearing a large percentage of the excess charge). That unexpected behavior has been rationalized as one subunit "unfolding" to depart with more charge. We present an alternative explanation based on heterolytic ion-pair scission and rearrangement, a mechanism that inherently partitions charge asymmetrically. Excessive barriers to dissociation are circumvented in this manner, when local charge rearrangements access a lower-barrier surface. An implication of this ion pair consideration is that stability differences between high- and low-charge state ions usually attributed to Coulomb repulsion may, alternatively, be conveyed by attractive forces from ion pairs (salt bridges) stabilizing low-charge state ions. Should the number of ion pairs be roughly inversely related to charge, symmetric dissociations would be favored from highly charged complexes, as observed. Correlations between a gas-phase protein's size and charge reflect the quantity of restraining ion pairs. Collisionally-facilitated salt bridge rearrangement (SaBRe) may explain unusual size "contractions" seen for some activated, low charge state complexes. That some low-charged multimers preferentially cleave covalent bonds or shed small ions to disrupting noncovalent associations is also explained by greater ion pairing in low charge state complexes.

Salt Bridge Rearrangement (SaBRe) Explains the Dissociation Behavior of Noncovalent Complexes.

PubMed

Loo, Rachel R Ogorzalek; Loo, Joseph A

2016-06-01

Native electrospray ionization-mass spectrometry, with gas-phase activation and solution compositions that partially release subcomplexes, can elucidate topologies of macromolecular assemblies. That so much complexity can be preserved in gas-phase assemblies is remarkable, although a long-standing conundrum has been the differences between their gas- and solution-phase decompositions. Collision-induced dissociation of multimeric noncovalent complexes typically distributes products asymmetrically (i.e., by ejecting a single subunit bearing a large percentage of the excess charge). That unexpected behavior has been rationalized as one subunit "unfolding" to depart with more charge. We present an alternative explanation based on heterolytic ion-pair scission and rearrangement, a mechanism that inherently partitions charge asymmetrically. Excessive barriers to dissociation are circumvented in this manner, when local charge rearrangements access a lower-barrier surface. An implication of this ion pair consideration is that stability differences between high- and low-charge state ions usually attributed to Coulomb repulsion may, alternatively, be conveyed by attractive forces from ion pairs (salt bridges) stabilizing low-charge state ions. Should the number of ion pairs be roughly inversely related to charge, symmetric dissociations would be favored from highly charged complexes, as observed. Correlations between a gas-phase protein's size and charge reflect the quantity of restraining ion pairs. Collisionally-facilitated salt bridge rearrangement (SaBRe) may explain unusual size "contractions" seen for some activated, low charge state complexes. That some low-charged multimers preferentially cleave covalent bonds or shed small ions to disrupting noncovalent associations is also explained by greater ion pairing in low charge state complexes. Graphical Abstract ᅟ.

Formation and fragmentation of quadruply charged molecular ions by intense femtosecond laser pulses.

PubMed

Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

2010-07-22

We investigated the formation and fragmentation of multiply charged molecular ions of several aromatic molecules by intense nonresonant femtosecond laser pulses of 1.4 mum with a 130 fs pulse duration (up to 2 x 10(14) W cm(-2)). Quadruply charged states were produced for 2,3-benzofluorene and triphenylene molecular ion in large abundance, whereas naphthalene and 1,1'-binaphthyl resulted only in up to triply charged molecular ions. The laser wavelength was nonresonant with regard to the electronic transitions of the neutral molecules, and the degree of fragmentation was strongly correlated with the absorption of the singly charged cation radical. Little fragmentation was observed for naphthalene (off-resonant with cation), whereas heavy fragmentation was observed in the case of 1,1'-binaphthyl (resonant with cation). The degree of H(2) (2H) and 2H(2) (4H) elimination from molecular ions increased as the charge states increased in all the molecules examined. A striking difference was found between triply and quadruply charged 2,3-benzofluorene: significant suppression of molecular ions with loss of odd number of hydrogen was observed in the quadruply charged ions. The Coulomb explosion of protons in the quadruply charged state and succeeding fragmentation resulted in the formation of triply charged molecular ions with an odd number of hydrogens. The hydrogen elimination mechanism in the highly charged state is discussed.

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.

Effect of magnetic field configuration on the multiply charged ion and plume characteristics in Hall thruster plasmas

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

Kim, Holak; Lim, Youbong; Choe, Wonho, E-mail: wchoe@kaist.ac.kr

2015-04-13

Multiply charged ions and plume characteristics in Hall thruster plasmas are investigated with regard to magnetic field configuration. Differences in the plume shape and the fraction of ions with different charge states are demonstrated by the counter-current and co-current magnetic field configurations, respectively. The significantly larger number of multiply charged and higher charge state ions including Xe{sup 4+} are observed in the co-current configuration than in the counter-current configuration. The large fraction of multiply charged ions and high ion currents in this experiment may be related to the strong electron confinement, which is due to the strong magnetic mirror effectmore » in the co-current magnetic field configuration.« less

Solution combustion synthesis of the nanocrystalline NCM oxide for lithium-ion battery uses

NASA Astrophysics Data System (ADS)

Habibi, Amirhosein; Jalaly, Maisam; Rahmanifard, Roohollah; Ghorbanzadeh, Milad

2018-02-01

In this study, the NCM cathode with a chemical composition of {{{LiNi}}}1/3}{{{Co}}}1/3}{{{Mn}}}1/3}{{{O}}}2 were synthesized through a solution combustion method. In this method, metal nitrates and urea were used as precursors and fuel, respectively. The powder obtained from combustion were transferred into a alumina crucible and insert to the muffle furnace and calcined at 750 °C for 15 h. The crystallite size of the sample was calculated with sherer equation to be about 41 nm. The prepared cathode were characterized using x-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC) and battery charge-discharge test. The initial charge and discharge capacities of {{{LiNi}}}1/3}{{{Co}}}1/3}{{{Mn}}}1/3}{{{O}}}2 electrode containing 94% active material at a rate of 0.05 C in voltage window of 2.5-4.3 V at room temperature was obtained 168.03 and 150.01 mAh g-1, respectively.

Efficient photodegradation of organic dye using anatase TiO2 plants as catalyst

NASA Astrophysics Data System (ADS)

Bahadur, Jitendra; Pal, Kaushik

2017-11-01

Anatase TiO2 hierarchical nanostructures with higher photocatalytic activity are of special importance in various applications. We have reported the synthesis of TiO2 as water chestnut plants like morphology via facile hydrothermal method, by using Titanium (IV) butoxide (TBOT) as a precursor solution. It is found that TiO2 nanoparticles work as seed and completely convert into water chestnut plants like structure or morphology, which are composed of crystallized anatase nanocrystals. X-ray diffraction spectra confirmed the presence of anatase phase of crystallized TiO2 plants (TPs). The average life time delay for generated charge carriers in TPs was calculated to be around 2.45 ns, which reflects slow recombination of charge carriers. The prepared TPs show excellent photocatalytic performance when applied in photo degradation of Rhodamine B organic dye. The unique features exhibited by TPs make them a promising candidate for vast potential applications in field such as solar cells, photocatalysis, supercapacitor, lithium ion batteries and some related fields.[Figure not available: see fulltext.

Observation of endoplasmic reticulum tubules via TOF-SIMS tandem mass spectrometry imaging of transfected cells.

PubMed

Chini, Corryn E; Fisher, Gregory L; Johnson, Ben; Tamkun, Michael M; Kraft, Mary L

2018-02-26

Advances in three-dimensional secondary ion mass spectrometry (SIMS) imaging have enabled visualizing the subcellular distributions of various lipid species within individual cells. However, the difficulty of locating organelles using SIMS limits efforts to study their lipid compositions. Here, the authors have assessed whether endoplasmic reticulum (ER)-Tracker Blue White DPX ® , which is a commercially available stain for visualizing the endoplasmic reticulum using fluorescence microscopy, produces distinctive ions that can be used to locate the endoplasmic reticulum using SIMS. Time-of-flight-SIMS tandem mass spectrometry (MS 2 ) imaging was used to identify positively and negatively charged ions produced by the ER-Tracker stain. Then, these ions were used to localize the stain and thus the endoplasmic reticulum, within individual human embryonic kidney cells that contained higher numbers of endoplasmic reticulum-plasma membrane junctions on their surfaces. By performing MS 2 imaging of selected ions in parallel with the precursor ion (MS 1 ) imaging, the authors detected a chemical interference native to the cell at the same nominal mass as the pentafluorophenyl fragment from the ER-Tracker stain. Nonetheless, the fluorine secondary ions produced by the ER-Tracker stain provided a distinctive signal that enabled locating the endoplasmic reticulum using SIMS. This simple strategy for visualizing the endoplasmic reticulum in individual cells using SIMS could be combined with existing SIMS methodologies for imaging intracellular lipid distribution and to study the lipid composition within the endoplasmic reticulum.

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.

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.

Effect of multiply charged ions on the performance and beam characteristics in annular and cylindrical type Hall thruster plasmas

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

Kim, Holak; Lim, Youbong; Choe, Wonho, E-mail: wchoe@kaist.ac.kr

2014-10-06

Plasma plume and thruster performance characteristics associated with multiply charged ions in a cylindrical type Hall thruster (CHT) and an annular type Hall thruster are compared under identical conditions such as channel diameter, channel depth, propellant mass flow rate. A high propellant utilization in a CHT is caused by a high ionization rate, which brings about large multiply charged ions. Ion currents and utilizations are much different due to the presence of multiply charged ions. A high multiply charged ion fraction and a high ionization rate in the CHT result in a higher specific impulse, thrust, and discharge current.

Implementation of Precursor and Neutral Loss Scans on a Miniature Ion Trap Mass Spectrometer and Performance Comparison to a Benchtop Linear Ion Trap

NASA Astrophysics Data System (ADS)

Snyder, Dalton T.; Szalwinski, Lucas J.; Hilger, Ryan; Cooks, R. Graham

2018-03-01

Implementation of orthogonal double resonance precursor and neutral loss scans on the Mini 12 miniature rectilinear ion trap mass spectrometer is described, and performance is compared to that of a commercial Thermo linear trap quadropole (LTQ) linear ion trap. The ac frequency scan version of the technique at constant rf voltage is used here because it is operationally much simpler to implement. Remarkably, the Mini 12 shows up to two orders of magnitude higher sensitivity compared to that of the LTQ. Resolution on the LTQ is better than unit at scan speeds of 400 Th/s, whereas peak widths on the Mini 12, on average, range from 0.5 to 2.0 Th full width at half maximum and depend heavily on the precursor ion Mathieu q parameter as well as the pump down time that precedes the mass scan. Both sensitivity and resolution are maximized under higher pressure conditions (short pump down time) on the Mini 12. The effective mass range of the product ion ejection waveform was found to be 5.8 Th on the Mini 12 in the precursor ion scan mode vs. that of 3.9 Th on the LTQ. In the neutral loss scan mode, the product ion selectivity was between 8 and 11 Th on the Mini 12 and between 7 and 8 Th on the LTQ. The effects of nonlinear resonance lines on the Mini 12 were also explored. [Figure not available: see fulltext.

Customized Consensus Spectral Library Building for Untargeted Quantitative Metabolomics Analysis with Data Independent Acquisition Mass Spectrometry and MetaboDIA Workflow.

PubMed

Chen, Gengbo; Walmsley, Scott; Cheung, Gemmy C M; Chen, Liyan; Cheng, Ching-Yu; Beuerman, Roger W; Wong, Tien Yin; Zhou, Lei; Choi, Hyungwon

2017-05-02

Data independent acquisition-mass spectrometry (DIA-MS) coupled with liquid chromatography is a promising approach for rapid, automatic sampling of MS/MS data in untargeted metabolomics. However, wide isolation windows in DIA-MS generate MS/MS spectra containing a mixed population of fragment ions together with their precursor ions. This precursor-fragment ion map in a comprehensive MS/MS spectral library is crucial for relative quantification of fragment ions uniquely representative of each precursor ion. However, existing reference libraries are not sufficient for this purpose since the fragmentation patterns of small molecules can vary in different instrument setups. Here we developed a bioinformatics workflow called MetaboDIA to build customized MS/MS spectral libraries using a user's own data dependent acquisition (DDA) data and to perform MS/MS-based quantification with DIA data, thus complementing conventional MS1-based quantification. MetaboDIA also allows users to build a spectral library directly from DIA data in studies of a large sample size. Using a marine algae data set, we show that quantification of fragment ions extracted with a customized MS/MS library can provide as reliable quantitative data as the direct quantification of precursor ions based on MS1 data. To test its applicability in complex samples, we applied MetaboDIA to a clinical serum metabolomics data set, where we built a DDA-based spectral library containing consensus spectra for 1829 compounds. We performed fragment ion quantification using DIA data using this library, yielding sensitive differential expression analysis.

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.

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

Susa, Anna C.; Xia, Zijie; Tang, Henry Y. H.

Factors that influence the charging of protein ions formed by electrospray ionization from aqueous solutions in which proteins have native structures and function were investigated. Protein ions ranging in molecular weight from 12.3 to 79.7 kDa and pI values from 5.4 to 9.6 were formed from different solutions and reacted with volatile bases of gas-phase basicities higher than that of ammonia in the cell of a Fourier-transform ion cyclotron resonance mass spectrometer. The charge-state distribution of cytochrome c ions formed from aqueous ammonium or potassium acetate is the same. Moreover, ions formed from these two solutions do not undergo protonmore » transfer to 2-fluoropyridine, which is 8 kcal/mol more basic than ammonia. These results provide compelling evidence that proton transfer between ammonia and protein ions does not limit protein ion charge in native electrospray ionization. Both circular dichroism and ion mobility measurements indicate that there are differences in conformations of proteins in pure water and aqueous ammonium acetate, and these differences can account for the difference in the extent of charging and proton-transfer reactivities of protein ions formed from these solutions. The extent of proton transfer of the protein ions with higher gas-phase basicity bases trends with how closely the protein ions are charged to the value predicted by the Rayleigh limit for spherical water droplets approximately the same size as the proteins. These results indicate that droplet charge limits protein ion charge in native mass spectrometry and are consistent with these ions being formed by the charged residue mechanism.« less

Ion funnel ion trap and process

DOEpatents

Belov, Mikhail E [Richland, WA; Ibrahim, Yehia M [Richland, WA; Clowers, Biran H [West Richland, WA; Prior, David C [Hermiston, OR; Smith, Richard D [Richland, WA

2011-02-15

An ion funnel trap is described that includes a inlet portion, a trapping portion, and a outlet portion that couples, in normal operation, with an ion funnel. The ion trap operates efficiently at a pressure of .about.1 Torr and provides for: 1) removal of low mass-to-charge (m/z) ion species, 2) ion accumulation efficiency of up to 80%, 3) charge capacity of .about.10,000,000 elementary charges, 4) ion ejection time of 40 to 200 .mu.s, and 5) optimized variable ion accumulation times. Ion accumulation with low concentration peptide mixtures has shown an increase in analyte signal-to-noise ratios (SNR) of a factor of 30, and a greater than 10-fold improvement in SNR for multiply charged analytes.

Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

1996-01-01

Charge transfer at electron-volt energies between multiply charged atomic ions and neutral atoms and molecules is of considerable importance in astrophysics, plasma physics, and in particular, fusion plasmas. In the year covered by this report, several major tasks were completed. These include: (1) the re-calibration of the ion gauge to measure the absolute particle densities of H2, He, N2, and CO for our current measurements; (2) the analysis of data for charge transfer reactions of N(exp 2 plus) ion and He, H2, N2, and CO; (3) measurement and data analysis of the charge transfer reaction of (Fe(exp 2 plus) ion and H2; (4) charge transfer measurement of Fe(exp 2 plus) ion and H2; and (5) redesign and modification of the ion detection and data acquisition system for the low energy beam facility (reflection time of flight mass spectrometer) dedicated to the study of state select charge transfer.

Magnetic field effect in fluorescence of excited fluorophore equilibrated with exciplex that reversibly dissociates into radical-ion pair undergoing the spin conversion.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2012-07-14

The fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is known to be very sensitive to a magnetic field, assisting the spin conversion in the resulting geminate radical ion pair (RIP), (1, 3)[D(+)...A(-)]. The relative increase of the fluorescence in the highest magnetic field compared to the lowest one, known as the magnetic field effect, crucially depends on the dielectric constant of the solvent, ɛ. This phenomenon first studied experimentally is at first reproduced here theoretically by means of the so called integral encounter theory. It was shown to be very sensitive to the position of the exciplex energy level relative to the levels of exciplex precursors and the charged products of its dissociation. The results obtained strongly depend on the dielectric properties of the solvents as well as on the exciplex and RIP formation rates.

Silicon Oxycarbide/Carbon Nanohybrids with Tiny Silicon Oxycarbide Particles Embedded in Free Carbon Matrix Based on Photoactive Dental Methacrylates.

PubMed

Wang, Meimei; Xia, Yonggao; Wang, Xiaoyan; Xiao, Ying; Liu, Rui; Wu, Qiang; Qiu, Bao; Metwalli, Ezzeldin; Xia, Senlin; Yao, Yuan; Chen, Guoxin; Liu, Yan; Liu, Zhaoping; Meng, Jian-Qiang; Yang, Zhaohui; Sun, Ling-Dong; Yan, Chun-Hua; Müller-Buschbaum, Peter; Pan, Jing; Cheng, Ya-Jun

2016-06-08

A new facile scalable method has been developed to synthesize silicon oxycarbide (SiOC)/carbon nanohybrids using difunctional dental methacrylate monomers as solvent and carbon source and the silane coupling agent as the precursor for SiOC. The content (from 100% to 40% by mass) and structure (ratio of disordered carbon over ordered carbon) of the free carbon matrix have been systematically tuned by varying the mass ratio of methacryloxypropyltrimethoxysilane (MPTMS) over the total mass of the resin monomers from 0.0 to 6.0. Compared to the bare carbon anode, the introduction of MPTMS significantly improves the electrochemical performance as a lithium-ion battery anode. The initial and cycled discharge/charge capacities of the SiOC/C nanohybrid anodes reach maximum with the MPTMS ratio of 0.50, which displays very good rate performance as well. Detailed structures and electrochemical performance as lithium-ion battery anodes have been systematically investigated. The structure-property correlation and corresponding mechanism have been discussed.

H2 Production Under Visible Light Irradiation from Aqueous Methanol Solution on CaTiO3:Cu Prepared by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Lim, Sung Nam; Song, Shin Ae; Jeong, Yong-Cheol; Kang, Hyun Woo; Park, Seung Bin; Kim, Ki Young

2017-10-01

Perovskite-type photocatalysts of CaCu x Ti1- x O3 (0 ≤ x ≤ 0.02) powder were prepared by spray pyrolysis of aqueous solution or aqueous solution with polymeric additive. The effects of the amount of copper ions doped in the photocatalyst and the precursor type on the photocatalytic activity under visible-light irradiation were investigated. The crystal structure, oxidation state, and light adsorption properties of the prepared photocatalysts were analyzed using x-ray diffraction, x-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy, respectively. The doping of copper ions in CaTiO3 allowed visible-light absorption owing to a narrowing of the band gap energy of the host material through the formation of a new donor level for copper ions. Among the doped samples prepared from the aqueous precursor, CaTiO3 doped with 1 mol.% copper ions had the highest hydrogen evolution rate (140.7 μmol g-1 h-1). Notably, the hydrogen evolution rate of the photocatalyst doped with 1 mol.% copper ions prepared from the aqueous precursor with polymeric additive (295.0 μmol g-1 h-1) was two times greater than that prepared from the aqueous precursor, due to the morphology effect.

Preparation and Characterization of Nano Gold Supported over Montmorillonite Clays

NASA Astrophysics Data System (ADS)

Suraja, P. V.; Binitha, N. N.; Yaakob, Z.; Silija, P. P.

2011-02-01

The use of montmorillonite clays as a matrix, or as a host, for obtaining intercalated/supported metal particles has potential applications in catalysis and other areas. The gold nanoparticles were obtained from the most common anionic gold precursor HAuCl4·3H2O by deposition-precipitation (DP) methods. However, it is difficult to prepare nanoscale gold catalysts supported on silica surfaces with lower isoelectric point (IEP). Homogeneous precipitation method using urea also fails on silica surfaces. Reasons for the inefficiency of these methods are the negative charge of the metal precursor as well as the support surface and the high pH required for depositing gold nanoparticles. In the present work, we use glucose as the reductant in the presence of stabilizer for preparation of nano gold supported on montmorillonite clay. There is no need of increasing the pH of the solution to reduce the Au3+ ions. The prepared systems are characterized using various techniques such as using X-ray fluorescence (XRF), UV-VIS Diffuse reflectance spectra (DRS) and Fourier Transform infra red spectra (FTIR) to prove the efficiency of the present method.

A review of studies on ion thruster beam and charge-exchange plasmas

NASA Technical Reports Server (NTRS)

Carruth, M. R., Jr.

1982-01-01

Various experimental and analytical studies of the primary beam and charge-exchange plasmas of ion thrusters are reviewed. The history of plasma beam research is recounted, emphasizing experiments on beam neutralization, expansion of the beam, and determination of beam parameters such as electron temperature, plasma density, and plasma potential. The development of modern electron bombardment ion thrusters is treated, detailing experimental results. Studies on charge-exchange plasma are discussed, showing results such as the relationship between neutralizer emission current and plasma beam potential, ion energies as a function of neutralizer bias, charge-exchange ion current collected by an axially moving Faraday cup-RPA for 8-cm and 30-cm ion thrusters, beam density and potential data from a 15-cm ion thruster, and charge-exchange ion flow around a 30-cm thruster. A 20-cm thruster electrical configuration is depicted and facility effects are discussed. Finally, plasma modeling is covered in detail for plasma beam and charge-exchange plasma.

Spatial atomic layer deposition for coating flexible porous Li-ion battery electrodes

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

Yersak, Alexander S.; Sharma, Kashish; Wallas, Jasmine M.

Ultrathin atomic layer deposition (ALD) coatings on the electrodes of Li-ion batteries can enhance the capacity stability of the Li-ion batteries. To commercialize ALD for Li-ion battery production, spatial ALD is needed to decrease coating times and provide a coating process compatible with continuous roll-to-roll (R2R) processing. The porous electrodes of Li-ion batteries provide a special challenge because higher reactant exposures are needed for spatial ALD in porous substrates. This work utilized a modular rotating cylinder spatial ALD reactor operating at rotation speeds up to 200 revolutions/min (RPM) and substrate speeds up to 200 m/min. The conditions for spatial ALDmore » were adjusted to coat flexible porous substrates. The reactor was initially used to characterize spatial Al2O3 and ZnO ALD on flat, flexible metalized polyethylene terephthalate foils. These studies showed that slower rotation speeds and spacers between the precursor module and the two adjacent pumping modules could significantly increase the reactant exposure. The modular rotating cylinder reactor was then used to coat flexible, model porous anodic aluminum oxide (AAO) membranes. The uniformity of the ZnO ALD coatings on the porous AAO membranes was dependent on the aspect ratio of the pores and the reactant exposures. Larger reactant exposures led to better uniformity in the pores with higher aspect ratios. The reactant exposures were increased by adding spacers between the precursor module and the two adjacent pumping modules. The modular rotating cylinder reactor was also employed for Al2O3 ALD on porous LiCoO2 (LCO) battery electrodes. Uniform Al coverages were obtained using spacers between the precursor module and the two adjacent pumping modules at rotation speeds of 25 and 50 RPM. The LCO electrodes had a thickness of ~49 um and pores with aspect ratios of ~12-25. Coin cells were then constructed using the ALD-coated LCO electrodes and were tested to determine their battery performance. The capacity of the Al2O3 ALD-coated LCO battery electrodes was measured versus the number of charge-discharge cycles. Both temporal and spatial ALD processing methods led to higher capacity stability compared with uncoated LCO battery electrodes. The results for improved battery performance were comparable for temporal and spatial ALD-coated electrodes. The next steps are also presented for scale-up to R2R spatial ALD using the modular rotating cylinder reactor.« less

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen; Prisko, Aniko

1999-01-01

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Method for reduction of selected ion intensities in confined ion beams

DOEpatents

Eiden, Gregory C.; Barinaga, Charles J.; Koppenaal, David W.

1998-01-01

A method for producing an ion beam having an increased proportion of analyte ions compared to carrier gas ions is disclosed. Specifically, the method has the step of addition of a charge transfer gas to the carrier analyte combination that accepts charge from the carrier gas ions yet minimally accepts charge from the analyte ions thereby selectively neutralizing the carrier gas ions. Also disclosed is the method as employed in various analytical instruments including an inductively coupled plasma mass spectrometer.

Method for reduction of selected ion intensities in confined ion beams

DOEpatents

Eiden, G.C.; Barinaga, C.J.; Koppenaal, D.W.

1998-06-16

A method for producing an ion beam having an increased proportion of analyte ions compared to carrier gas ions is disclosed. Specifically, the method has the step of addition of a charge transfer gas to the carrier analyte combination that accepts charge from the carrier gas ions yet minimally accepts charge from the analyte ions thereby selectively neutralizing the carrier gas ions. Also disclosed is the method as employed in various analytical instruments including an inductively coupled plasma mass spectrometer. 7 figs.

Analysis of Intrinsic Peptide Detectability via Integrated Label-Free and SRM-Based Absolute Quantitative Proteomics.

PubMed

Jarnuczak, Andrew F; Lee, Dave C H; Lawless, Craig; Holman, Stephen W; Eyers, Claire E; Hubbard, Simon J

2016-09-02

Quantitative mass spectrometry-based proteomics of complex biological samples remains challenging in part due to the variability and charge competition arising during electrospray ionization (ESI) of peptides and the subsequent transfer and detection of ions. These issues preclude direct quantification from signal intensity alone in the absence of a standard. A deeper understanding of the governing principles of peptide ionization and exploitation of the inherent ionization and detection parameters of individual peptides is thus of great value. Here, using the yeast proteome as a model system, we establish the concept of peptide F-factor as a measure of detectability, closely related to ionization efficiency. F-factor is calculated by normalizing peptide precursor ion intensity by absolute abundance of the parent protein. We investigated F-factor characteristics in different shotgun proteomics experiments, including across multiple ESI-based LC-MS platforms. We show that F-factors mirror previously observed physicochemical predictors as peptide detectability but demonstrate a nonlinear relationship between hydrophobicity and peptide detectability. Similarly, we use F-factors to show how peptide ion coelution adversely affects detectability and ionization. We suggest that F-factors have great utility for understanding peptide detectability and gas-phase ion chemistry in complex peptide mixtures, selection of surrogate peptides in targeted MS studies, and for calibration of peptide ion signal in label-free workflows. Data are available via ProteomeXchange with identifier PXD003472.

Wall-loss distribution of charge breeding ions in an electron cyclotron resonance ion source

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

Jeong, S. C.; Oyaizu, M.; Imai, N.

2012-02-15

We investigated the ion-loss distribution on the sidewall of an electron cyclotron resonance (ECR) plasma chamber using the 18-GHz ECR charge breeder at the Tokai Radioactive Ion Accelerator Complex (TRIAC). Similarities and differences between the ion-loss distributions (longitudinal and azimuthal) of different ion species (i.e., radioactive {sup 111}In{sup 1+} and {sup 140}Xe{sup 1+} ions that are typical volatile and nonvolatile elements) was qualitatively discussed to understand the element dependence of the charge breeding efficiency. Especially, the similarities represent universal ion loss characteristics in an ECR charge breeder, which are different from the loss patterns of electrons on the ECRIS wall.

Formation of stable inverse sheath in ion–ion plasma by strong negative ion emission

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Wu, Bang; Yang, Shali; Zhang, Ya; Chen, Dezhi; Fan, Mingwu; Jiang, Wei

2018-06-01

The effect of strong charged particle emission on plasma–wall interactions is a classical, yet unresolved question in plasma physics. Previous studies on secondary electron emission have shown that with different emission coefficients, there are classical, space-charge-limited, and inverse sheaths. In this letter, we demonstrate that a stable ion–ion inverse sheath and ion–ion plasma are formed with strong surface emission of negative ions. The continuous space-charge-limited to inverse ion–ion sheath transition is observed, and the plasma near the surface consequently transforms into pure ion–ion plasma. The results may explain the long-puzzled experimental observation that the density of negative ions depends on only charge not mass in negative ion sources.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

HITRAP: A Facility for Experiments with Trapped Highly Charged Ions

NASA Astrophysics Data System (ADS)

Quint, W.; Dilling, J.; Djekic, S.; Häffner, H.; Hermanspahn, N.; Kluge, H.-J.; Marx, G.; Moore, R.; Rodriguez, D.; Schönfelder, J.; Sikler, G.; Valenzuela, T.; Verdú, J.; Weber, C.; Werth, G.

2001-01-01

HITRAP is a planned ion trap facility for capturing and cooling of highly charged ions produced at GSI in the heavy-ion complex of the UNILAC-SIS accelerators and the ESR storage ring. In this facility heavy highly charged ions up to uranium will be available as bare nuclei, hydrogen-like ions or few-electron systems at low temperatures. The trap for receiving and studying these ions is designed for operation at extremely high vacuum by cooling to cryogenic temperatures. The stored highly charged ions can be investigated in the trap itself or can be extracted from the trap at energies up to about 10 keV/q. The proposed physics experiments are collision studies with highly charged ions at well-defined low energies (eV/u), high-accuracy measurements to determine the g-factor of the electron bound in a hydrogen-like heavy ion and the atomic binding energies of few-electron systems, laser spectroscopy of HFS transitions and X-ray spectroscopy.

The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films.

PubMed

Gudjonsdottir, Solrun; van der Stam, Ward; Kirkwood, Nicholas; Evers, Wiel H; Houtepen, Arjan J

2018-05-16

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li + and Na + the onset is at significantly less negative potentials. For larger ions (K + , quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li + and Na + . Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies.

The Role of Dopant Ions on Charge Injection and Transport in Electrochemically Doped Quantum Dot Films

PubMed Central

2018-01-01

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li+ and Na+ the onset is at significantly less negative potentials. For larger ions (K+, quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li+ and Na+. Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies. PMID:29718666

Mass spectrometer with electron source for reducing space charge effects in sample beam

DOEpatents

Houk, Robert S.; Praphairaksit, Narong

2003-10-14

A mass spectrometer includes an ion source which generates a beam including positive ions, a sampling interface which extracts a portion of the beam from the ion source to form a sample beam that travels along a path and has an excess of positive ions over at least part of the path, thereby causing space charge effects to occur in the sample beam due to the excess of positive ions in the sample beam, an electron source which adds electrons to the sample beam to reduce space charge repulsion between the positive ions in the sample beam, thereby reducing the space charge effects in the sample beam and producing a sample beam having reduced space charge effects, and a mass analyzer which analyzes the sample beam having reduced space charge effects.

Beam efflux measurements

NASA Technical Reports Server (NTRS)

Komatsu, G. K.; Stellen, J. M., Jr.

1976-01-01

Measurements have been made of the high energy thrust ions, (Group I), high angle/high energy ions (Group II), and high angle/low energy ions (Group IV) of a mercury electron bombardment thruster in the angular divergence range from 0 deg to greater than 90 deg. The measurements have been made as a function of thrust ion current, propellant utilization efficiency, bombardment discharge voltage, screen and accelerator grid potential (accel-decel ratio) and neutralizer keeper potential. The shape of the Group IV (charge exchange) ion plume has remained essentially fixed within the range of variation of the engine operation parameters. The magnitude of the charge exchange ion flux scales with thrust ion current, for good propellant utilization conditions. For fixed thrust ion current, charge exchange ion flux increases for diminishing propellant utilization efficiency. Facility effects influence experimental accuracies within the range of propellant utilization efficiency used in the experiments. The flux of high angle/high energy Group II ions is significantly diminished by the use of minimum decel voltages on the accelerator grid. A computer model of charge exchange ion production and motion has been developed. The program allows computation of charge exchange ion volume production rate, total production rate, and charge exchange ion trajectories for "genuine" and "facilities effects" particles. In the computed flux deposition patterns, the Group I and Group IV ion plumes exhibit a counter motion.

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

NASA Technical Reports Server (NTRS)

Thompson, David W.

1993-01-01

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Demonstration of charge breeding in a compact room temperature electron beam ion trap

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

Vorobjev, G.; Sokolov, A.; Herfurth, F.

2012-05-15

For the first time, a small room-temperature electron beam ion trap (EBIT), operated with permanent magnets, was successfully used for charge breeding experiments. The relatively low magnetic field of this EBIT does not contribute to the capture of the ions; single-charged ions are only caught by the space charge potential of the electron beam. An over-barrier injection method was used to fill the EBIT's electrostatic trap with externally produced, single-charged potassium ions. Charge states as high as K{sup 19+} were reached after about a 3 s breeding time. The capture and breeding efficiencies up to 0.016(4)% for K{sup 17+} havemore » been measured.« less

Charging of dust grains in a plasma with negative ions

NASA Astrophysics Data System (ADS)

Kim, Su-Hyun; Merlino, Robert L.

2006-05-01

The effect of negative ions on the charging of dust particles in a plasma is investigated experimentally. A plasma containing a very low percentage of electrons is formed in a single-ended SF6 is admitted into the vacuum system. The relatively cold (Te≈0.2eV ) readily attach to SF6 molecules to form SF6- negative ions. Calculations of the dust charge indicate that for electrons, negative ions, and positive ions of comparable temperatures, the charge (or surface potential) of the dust can be positive if the positive ion mass is smaller than the negative ion mass and if ɛ, the ratio of the electron to positive ion density, is sufficiently small. The K+ positive ions (mass 39amu) and SF6- negative ions (mass 146amu), and also utilizes a rotating cylinder to dispense dust into the plasma column. Analysis of the current-voltage characteristics of a Langmuir probe in the dusty plasma shows evidence for the reduction in the (magnitude) of the negative dust charge and the transition to positively charged dust as the relative concentration of the residual electrons is reduced. Some remarks are offered concerning experiments that could become possible in a dusty plasma with positive grains.

Moving Fe2+ from ferritin ion channels to catalytic OH centers depends on conserved protein cage carboxylates.

PubMed

Behera, Rabindra K; Theil, Elizabeth C

2014-06-03

Ferritin biominerals are protein-caged metabolic iron concentrates used for iron-protein cofactors and oxidant protection (Fe(2+) and O2 sequestration). Fe(2+) passage through ion channels in the protein cages, like membrane ion channels, required for ferritin biomineral synthesis, is followed by Fe(2+) substrate movement to ferritin enzyme (Fox) sites. Fe(2+) and O2 substrates are coupled via a diferric peroxo (DFP) intermediate, λmax 650 nm, which decays to [Fe(3+)-O-Fe(3+)] precursors of caged ferritin biominerals. Structural studies show multiple conformations for conserved, carboxylate residues E136 and E57, which are between ferritin ion channel exits and enzymatic sites, suggesting functional connections. Here we show that E136 and E57 are required for ferritin enzyme activity and thus are functional links between ferritin ion channels and enzymatic sites. DFP formation (Kcat and kcat/Km), DFP decay, and protein-caged hydrated ferric oxide accumulation decreased in ferritin E57A and E136A; saturation required higher Fe(2+) concentrations. Divalent cations (both ion channel and intracage binding) selectively inhibit ferritin enzyme activity (block Fe(2+) access), Mn(2+) < Co(2+) < Cu(2+) < Zn(2+), reflecting metal ion-protein binding stabilities. Fe(2+)-Cys126 binding in ferritin ion channels, observed as Cu(2+)-S-Cys126 charge-transfer bands in ferritin E130D UV-vis spectra and resistance to Cu(2+) inhibition in ferritin C126S, was unpredicted. Identifying E57 and E136 links in Fe(2+) movement from ferritin ion channels to ferritin enzyme sites completes a bucket brigade that moves external Fe(2+) into ferritin enzymatic sites. The results clarify Fe(2+) transport within ferritin and model molecular links between membrane ion channels and cytoplasmic destinations.

Characteristics of a large vacuum wave precursor on the SABRE voltage adder MITL and extraction ion diode

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

Cuneo, M.E.; Hanson, D.L.; Menge, P.R.

SABRE (Sandia Accelerator and Beam Research Experiment) is a ten-cavity linear induction magnetically insulated voltage adder (6 MV, 300 kA) operated in positive polarity to investigate issues relevant to ion beam production and propagation for inertial confinement fusion. The voltage adder section is coupled to an applied-B extraction ion diode via a long coaxial output transmission line. Observations indicate that the power propagates in a vacuum wave prior to electron emission. After the electron emission threshold is reached, power propagates in a magnetically insulated wave. The precursor is observed to have a dominant impact on he turn-on, impedance history, andmore » beam characteristics of applied-B ion diodes since the precursor voltage is large enough to cause electron emission at the diode from both the cathode feed and cathode tips. The amplitude of the precursor at the load (3--4.5 MV) is a significant fraction of the maximum load voltage (5--6 MV) because (1) the transmission line gaps ( {approx} 9 cm at output) and therefore impedances are relatively large, and hence the electric field threshold for electron emission (200 to 300 kV/cm) is not reached until well into the power pulse rise time; and (2) the rapidly falling forward wave and diode impedance reduces the ratio of main pulse voltage to precursor voltage. Experimental voltage and current data from the transmission line and the ion diode will be presented and compared with TWOQUICK (2-D electromagnetic PIC code) simulations and analytic models.« less

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

NASA Astrophysics Data System (ADS)

Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

2015-04-01

Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

Isobar Separation in a Multiple-Reflection Time-of-Flight Mass Spectrometer by Mass-Selective Re-Trapping.

PubMed

Dickel, Timo; Plaß, Wolfgang R; Lippert, Wayne; Lang, Johannes; Yavor, Mikhail I; Geissel, Hans; Scheidenberger, Christoph

2017-06-01

A novel method for (ultra-)high-resolution spatial mass separation in time-of-flight mass spectrometers is presented. Ions are injected into a time-of-flight analyzer from a radio frequency (rf) trap, dispersed in time-of-flight according to their mass-to-charge ratios and then re-trapped dynamically in the same rf trap. This re-trapping technique is highly mass-selective and after sufficiently long flight times can provide even isobaric separation. A theoretical treatment of the method is presented and the conditions for optimum performance of the method are derived. The method has been implemented in a multiple-reflection time-of-flight mass spectrometer and mass separation powers (FWHM) in excess of 70,000, and re-trapping efficiencies of up to 35% have been obtained for the protonated molecular ion of caffeine. The isobars glutamine and lysine (relative mass difference of 1/4000) have been separated after a flight time of 0.2 ms only. Higher mass separation powers can be achieved using longer flight times. The method will have important applications, including isobar separation in nuclear physics and (ultra-)high-resolution precursor ion selection in multiple-stage tandem mass spectrometry. Graphical Abstract ᅟ.

Isobar Separation in a Multiple-Reflection Time-of-Flight Mass Spectrometer by Mass-Selective Re-Trapping

NASA Astrophysics Data System (ADS)

Dickel, Timo; Plaß, Wolfgang R.; Lippert, Wayne; Lang, Johannes; Yavor, Mikhail I.; Geissel, Hans; Scheidenberger, Christoph

2017-06-01

A novel method for (ultra-)high-resolution spatial mass separation in time-of-flight mass spectrometers is presented. Ions are injected into a time-of-flight analyzer from a radio frequency (rf) trap, dispersed in time-of-flight according to their mass-to-charge ratios and then re-trapped dynamically in the same rf trap. This re-trapping technique is highly mass-selective and after sufficiently long flight times can provide even isobaric separation. A theoretical treatment of the method is presented and the conditions for optimum performance of the method are derived. The method has been implemented in a multiple-reflection time-of-flight mass spectrometer and mass separation powers (FWHM) in excess of 70,000, and re-trapping efficiencies of up to 35% have been obtained for the protonated molecular ion of caffeine. The isobars glutamine and lysine (relative mass difference of 1/4000) have been separated after a flight time of 0.2 ms only. Higher mass separation powers can be achieved using longer flight times. The method will have important applications, including isobar separation in nuclear physics and (ultra-)high-resolution precursor ion selection in multiple-stage tandem mass spectrometry. [Figure not available: see fulltext.

Highly charged ion based time of flight emission microscope

DOEpatents

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

2001-01-01

A highly charged ion based time-of-flight emission microscope has been designed, which improves the surface sensitivity of static SIMS measurements because of the higher ionization probability of highly charged ions. Slow, highly charged ions are produced in an electron beam ion trap and are directed to the sample surface. The sputtered secondary ions and electrons pass through a specially designed objective lens to a microchannel plate detector. This new instrument permits high surface sensitivity (10.sup.10 atoms/cm.sup.2), high spatial resolution (100 nm), and chemical structural information due to the high molecular ion yields. The high secondary ion yield permits coincidence counting, which can be used to enhance determination of chemical and topological structure and to correlate specific molecular species.

FAST TRACK COMMUNICATION: Inhomogeneous charge redistribution in Xe clusters exposed to an intense extreme ultraviolet free electron laser

NASA Astrophysics Data System (ADS)

Iwayama, H.; Sugishima, A.; Nagaya, K.; Yao, M.; Fukuzawa, H.; Motomura, K.; Liu, X.-J.; Yamada, A.; Wang, C.; Ueda, K.; Saito, N.; Nagasono, M.; Tono, K.; Yabashi, M.; Ishikawa, T.; Ohashi, H.; Kimura, H.; Togashi, T.

2010-08-01

The emission of highly charged ions from Xe clusters exposed to intense extreme ultraviolet laser pulses (λ ~ 52 nm) from the free electron laser in Japan was investigated using ion momentum spectroscopy. With increasing average cluster size, we observed multiply charged ions Xez + up to z = 3. From kinetic energy distributions, we found that multiply charged ions were generated near the cluster surface. Our results suggest that charges are inhomogeneously redistributed in the cluster to lower the total energy stored in the clusters.

The study towards high intensity high charge state laser ion sources.

PubMed

Zhao, H Y; Jin, Q Y; Sha, S; Zhang, J J; Li, Z M; Liu, W; Sun, L T; Zhang, X Z; Zhao, H W

2014-02-01

As one of the candidate ion sources for a planned project, the High Intensity heavy-ion Accelerator Facility, a laser ion source has been being intensively studied at the Institute of Modern Physics in the past two years. The charge state distributions of ions produced by irradiating a pulsed 3 J/8 ns Nd:YAG laser on solid targets of a wide range of elements (C, Al, Ti, Ni, Ag, Ta, and Pb) were measured with an electrostatic ion analyzer spectrometer, which indicates that highly charged ions could be generated from low-to-medium mass elements with the present laser system, while the charge state distributions for high mass elements were relatively low. The shot-to-shot stability of ion pulses was monitored with a Faraday cup for carbon target. The fluctuations within ±2.5% for the peak current and total charge and ±6% for pulse duration were demonstrated with the present setup of the laser ion source, the suppression of which is still possible.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Fu, Yongsheng; Hou, Yong; Kang, Dongdong; Gao, Cheng; Jin, Fengtao; Yuan, Jianmin

2018-01-01

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion-ion pair potentials are computed using the modified Gordon-Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green-Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Co@Carbon and Co 3 O4@Carbon nanocomposites derived from a single MOF for supercapacitors.

PubMed

Dai, Engao; Xu, Jiao; Qiu, Junjie; Liu, Shucheng; Chen, Ping; Liu, Yi

2017-10-03

Developing a composite electrode containing both carbon and transition metal/metal oxide as the supercapacitor electrode can combine the merits and mitigate the shortcomings of both the components. Herein, we report a simple strategy to prepare the hybrid nanostructure of Co@Carbon and Co 3 O 4 @Carbon by pyrolysis a single MOFs precursor. Co-based MOFs (Co-BDC) nanosheets with morphology of regular parallelogram slice have been prepared by a bottom-up synthesis strategy. One-step pyrolysis of Co-BDC, produces a porous carbon layer incorporating well-dispersed Co and Co 3 O 4 nanoparticles. The as-prepared cobalt-carbon composites exhibit the thin layer morphology and large specific surface area with hierarchical porosity. These features significantly improve the ion-accessible surface area for charge storage and shorten the ion transport length in thin dimension, thus contributing to a high specific capacitance. Improved capacitance performance was successfully realized for the asymmetric supercapacitors (ASCs) (Co@Carbon//Co 3 O 4 @Carbon), better than those of the symmetric supercapacitors (SSCs) based on Co@Carbon and Co 3 O 4 @Carbon materials (i.e., Co@Carbon//Co@Carbon and Co 3 O 4 @Carbon//Co 3 O 4 @Carbon). The working voltage of the ASCs can be extended to 1.5 V and show a remarkable high power capability in aqueous electrolyte. This work provides a controllable strategy for nanostructured carbon-metal and carbon-metal oxide composite electrodes from a single precursor.

Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

2015-10-01

Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

Spontaneous Mass and Charge Losses from Single Multi-Megadalton Ions Studied by Charge Detection Mass Spectrometry

NASA Astrophysics Data System (ADS)

Keifer, David Z.; Alexander, Andrew W.; Jarrold, Martin F.

2017-03-01

Spontaneous mass and charge losses from individual multi-megadalton ions have been observed with charge detection mass spectrometry (CDMS) by trapping single hepatitis B virus (HBV) capsids for 3 s. Gradual increases in the oscillation frequency of single ions in the ion trap are attributed mainly to mass loss (probably solvent, water, and/or salt). The total mass lost during the 3 s trapping period peaks at around 20 kDa for 4 MDa HBV T = 4 capsids. Discrete frequency drops punctuate the gradual increases in the oscillation frequencies. The drops are attributed to a sudden loss of charge. In most cases a single positive charge is lost along with some mass (on average around 1000 Da). Charge loss occurs for over 40% of the trapped ions. It usually occurs near the beginning of the trapping event, and it occurs preferentially in regions of the trap with strong electric fields, indicating that external electric fields promote charge loss. This process may contribute to the decrease in m/ z resolution that often occurs with megadalton ions.

Synthesis and extreme rate capability of Si-Al-C-N functionalized carbon nanotube spray-on coatings as Li-ion battery electrode.

PubMed

David, Lamuel; Asok, Deepu; Singh, Gurpreet

2014-09-24

Silicon-based precursor derived glass-ceramics or PDCs have proven to be an attractive alternative anode material for Li ion batteries. Main challenges associated with PDC anodes are their low electrical conductivity, first cycle loss, and meager C-rate performance. Here, we show that thermal conversion of single source aluminum-modified polysilazane on the surfaces of carbon nanotubes (CNTs) results in a robust Si-Al-C-N/CNT shell/core composite that offers extreme C-rate capability as battery electrode. Addition of Al to the molecular network of Si-C-N improved electrical conductivity of Si-C-N by 4 orders of magnitude, while interfacing with CNTs showed 7-fold enhancement. Further, we present a convenient spray-coating technique for PDC composite electrode preparation that eliminates polymeric binder and conductive agent there-by reducing processing steps and eradicating foreign material in the electrode. The Si-Al-C-N/CNT electrode showed stable charge capacity of 577 mAh g(-1) at 100 mA g(-1) and a remarkable 400 mAh g(-1) at 10,000 mA g(-1), which is the highest reported value for a silazane derived glass-ceramic or nanocomposite electrode. Under symmetric cycling conditions, a high charge capacity of ∼350 mA g(-1) at 1600 mA g(-1) was continuously observed for over 1000 cycles.

Atomic charges of sulfur in ionic liquids: experiments and calculations.

PubMed

Fogarty, Richard M; Rowe, Rebecca; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Smith, Emily F; Bourne, Richard A; Chamberlain, Thomas W; Thompson, Paul B J; Hunt, Patricia A; Lovelock, Kevin R J

2017-12-14

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra, X-ray photoelectron (XP) spectra and Auger electron spectra are reported for sulfur in ionic liquids (ILs) with a range of chemical structures. These values provide experimental measures of the atomic charge in each IL and enable the evaluation of the suitability of NEXAFS spectroscopy and XPS for probing the relative atomic charge of sulfur. In addition, we use Auger electron spectroscopy to show that when XPS binding energies differ by less than 0.5 eV, conclusions on atomic charge should be treated with caution. Our experimental data provides a benchmark for calculations of the atomic charge of sulfur obtained using different methods. Atomic charges were computed for lone ions and ion pairs, both in the gas phase (GP) and in a solvation model (SMD), with a wide range of ion pair conformers considered. Three methods were used to compute the atomic charges: charges from the electrostatic potential using a grid based method (ChelpG), natural bond orbital (NBO) population analysis and Bader's atoms in molecules (AIM) approach. By comparing the experimental and calculated measures of the atomic charge of sulfur, we provide an order for the sulfur atoms, ranging from the most negative to the most positive atomic charge. Furthermore, we show that both ChelpG and NBO are reasonable methods for calculating the atomic charge of sulfur in ILs, based on the agreement with both the XPS and NEXAFS spectroscopy results. However, the atomic charges of sulfur derived from ChelpG are found to display significant, non-physical conformational dependence. Only small differences in individual atomic charge of sulfur were observed between lone ion (GP) and ion pair IL(SMD) model systems, indicating that ion-ion interactions do not strongly influence individual atomic charges.

Dielectric boundary force and its crucial role in gramicidin

NASA Astrophysics Data System (ADS)

Nadler, Boaz; Hollerbach, Uwe; Eisenberg, R. S.

2003-08-01

In an electrostatic problem with nonuniform geometry, a charge Q in one region induces surface charges [called dielectric boundary charges (DBC)] at boundaries between different dielectrics. These induced surface charges, in return, exert a force [called dielectric boundary force (DBF)] on the charge Q that induced them. The DBF is often overlooked. It is not present in standard continuum theories of (point) ions in or near membranes and proteins, such as Gouy-Chapman, Debye-Huckel, Poisson-Boltzmann or Poisson-Nernst- Planck. The DBF is important when a charge Q is near dielectric interfaces, for example, when ions permeate through protein channels embedded in biological membranes. In this paper, we define the DBF and calculate it explicitly for a planar dielectric wall and for a tunnel geometry resembling the ionic channel gramicidin. In general, we formulate the DBF in a form useful for continuum theories, namely, as a solution of a partial differential equation with boundary conditions. The DBF plays a crucial role in the permeation of ions through the gramicidin channel. A positive ion in the channel produces a DBF of opposite sign to that of the fixed charge force (FCF) produced by the permanent charge of the gramicidin polypeptide, and so the net force on the positive ion is reduced. A negative ion creates a DBF of the same sign as the FCF and so the net (repulsive) force on the negative ion is increased. Thus, a positive ion can permeate the channel, while a negative ion is excluded from it. In gramicidin, it is this balance between the FCF and DBF that allows only singly charged positive ions to move into and through the channel. The DBF is not directly responsible, however, for selectivity between the alkali metal ions (e.g., Li+, Na+, K+): we prove that the DBF on a mobile spherical ion is independent of the ion’s radius.

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.

The charge spectrum of positive ions in a hydrogen aurora

NASA Technical Reports Server (NTRS)

Lynch, J.; Pulliam, D.; Leach, R.; Scherb, F.

1976-01-01

An auroral ion charge spectrometer was flown into a hydrogen aurora on a Javelin sounding rocket launched from Churchill, Manitoba. The instrument contained an electrostatic analyzer which selected particles with incident energy per unit charge up to 20 keV/charge and an 80-kV power supply which accelerated these ions onto an array of solid state detectors. Ions tentatively identified as H(+), He(+2), and O(+) were detected from 225 to 820 km in altitude. The experiment did not discriminate between H(+) and He(+), or between O(+), N(+), and C(+). Upper limits of highly charged heavy ion abundances have been set at 20% of the He(+2) and 0.15% of the H(+). It is concluded that both terrestrial and solar wind sources play significant roles in auroral ion precipitation.

Numerical experiments on charging of a spherical body in a plasma with Maxwellian distributions of charged particles

NASA Astrophysics Data System (ADS)

Krasovsky, Victor L.; Kiselyov, Alexander A.

2017-12-01

New results of numerical simulation of collisionless plasma perturbation caused by a sphere absorbing electrons and ions are presented. Consideration is given to nonstationary phenomena accompanying the process of charging as well as to plasma steady state reached at long times. Corresponding asymptotic values of charges of the sphere and trapped-ion cloud around it have been found along with self-consistent electric field pattern depending on parameters of the unperturbed plasma. It is established that contribution of the trapped ions to screening of the charged sphere can be quite significant, so that the screening becomes essentially nonlinear in nature. A simple interconnection between the sphere radius, electron and ion Debye lengths has been revealed as the condition for maximum trapped-ion effect. Kinetic structure of the space charge induced in the plasma is discussed with relation to the specific form of the unperturbed charged particle distribution functions.

Expected charge states of energetic ions in the magnetosphere

NASA Technical Reports Server (NTRS)

Spjeldvik, W. N.

1979-01-01

Major developments in magnetospheric heavy ion physics during the period 1974-1977 are reviewed with emphasis on charge state aspects. Particular attention is given to the high energy component at energies above tens of keV per ion. Also considered are charge exchange processes with application to the inner magnetosphere, a comparison between theory and measurements, and a survey of heavy ion and charge state observations in the outer magnetosphere, magnetosheath and the surrounding space.

Holographic heavy ion collisions with baryon charge

DOE PAGES

Casalderrey-Solana, Jorge; Mateos, David; van der Schee, Wilke; ...

2016-09-19

We numerically simulate collisions of charged shockwaves in Einstein-Maxwell theory in anti-de Sitter space as a toy model of heavy ion collisions with non-zero baryon charge. The stress tensor and the baryon current become well described by charged hydrodynamics at roughly the same time. The effect of the charge density on generic observables is typically no larger than 15%. Finally, we find significant stopping of the baryon charge and compare our results with those in heavy ion collision experiments.

Colloidal Stability in Asymmetric Electrolytes: Modifications of the Schulze-Hardy Rule.

PubMed

Trefalt, Gregor; Szilagyi, Istvan; Téllez, Gabriel; Borkovec, Michal

2017-02-21

The Schulze-Hardy rule suggests a strong dependence of the critical coagulation concentration (CCC) on the ionic valence. This rule is addressed theoretically and confronted with recent experimental results. The commonly presented derivation of this rule assumes symmetric electrolytes and highly charged particles. Both assumptions are incorrect. Symmetric electrolytes containing multivalent ions are hardly soluble, and experiments are normally carried out with the well-soluble salts of asymmetric electrolytes containing monovalent and multivalent ions. In this situation, however, the behavior is completely different whether the multivalent ions represent the counterions or co-ions. When these ions represent the counterions, meaning that the multivalent ions have the opposite sign than the charge of the particle, they adsorb strongly to the particles. Thereby, they progressively reduce the magnitude of the surface charge with increasing valence. In fact, this dependence of the charge density on the counterion valence is mainly responsible for the decrease of the CCC with the valence. In the co-ion case, where the multivalent ions have the same sign as the charge of the particle, the multivalent ions are repelled from the particles, and the surfaces remain highly charged. In this case, the inverse Schulze-Hardy rule normally applies, whereby the CCC varies inversely proportional to the co-ion valence.

New development of laser ion source for highly charged ion beam production at Institute of Modern Physics (invited).

PubMed

Zhao, H Y; Zhang, J J; Jin, Q Y; Liu, W; Wang, G C; Sun, L T; Zhang, X Z; Zhao, H W

2016-02-01

A laser ion source based on Nd:YAG laser has been being studied at the Institute of Modern Physics for the production of high intensity high charge state heavy ion beams in the past ten years, for possible applications both in a future accelerator complex and in heavy ion cancer therapy facilities. Based on the previous results for the production of multiple-charged ions from a wide range of heavy elements with a 3 J/8 ns Nd:YAG laser [Zhao et al., Rev. Sci. Instrum. 85, 02B910 (2014)], higher laser energy and intensity in the focal spot are necessary for the production of highly charged ions from the elements heavier than aluminum. Therefore, the laser ion source was upgraded with a new Nd:YAG laser, the maximum energy of which is 8 J and the pulse duration can be adjusted from 8 to 18 ns. Since then, the charge state distributions of ions from various elements generated by the 8 J Nd:YAG laser were investigated for different experimental conditions, such as laser energy, pulse duration, power density in the focal spot, and incidence angle. It was shown that the incidence angle is one of the most important parameters for the production of highly charged ions. The capability of producing highly charged ions from the elements lighter than silver was demonstrated with the incidence angle of 10° and laser power density of 8 × 10(13) W cm(-2) in the focal spot, which makes a laser ion source complementary to the superconducting electron cyclotron resonance ion source for the future accelerator complex especially in terms of the ion beam production from some refractory elements. Nevertheless, great efforts with regard to the extraction of intense ion beams, modification of the ion beam pulse duration, and reliability of the ion source still need to be made for practical applications.

New development of laser ion source for highly charged ion beam production at Institute of Modern Physics (invited)

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

Zhao, H. Y., E-mail: zhaohy@impcas.ac.cn; Zhang, J. J.; Jin, Q. Y.

2016-02-15

A laser ion source based on Nd:YAG laser has been being studied at the Institute of Modern Physics for the production of high intensity high charge state heavy ion beams in the past ten years, for possible applications both in a future accelerator complex and in heavy ion cancer therapy facilities. Based on the previous results for the production of multiple-charged ions from a wide range of heavy elements with a 3 J/8 ns Nd:YAG laser [Zhao et al., Rev. Sci. Instrum. 85, 02B910 (2014)], higher laser energy and intensity in the focal spot are necessary for the production ofmore » highly charged ions from the elements heavier than aluminum. Therefore, the laser ion source was upgraded with a new Nd:YAG laser, the maximum energy of which is 8 J and the pulse duration can be adjusted from 8 to 18 ns. Since then, the charge state distributions of ions from various elements generated by the 8 J Nd:YAG laser were investigated for different experimental conditions, such as laser energy, pulse duration, power density in the focal spot, and incidence angle. It was shown that the incidence angle is one of the most important parameters for the production of highly charged ions. The capability of producing highly charged ions from the elements lighter than silver was demonstrated with the incidence angle of 10° and laser power density of 8 × 10{sup 13} W cm{sup −2} in the focal spot, which makes a laser ion source complementary to the superconducting electron cyclotron resonance ion source for the future accelerator complex especially in terms of the ion beam production from some refractory elements. Nevertheless, great efforts with regard to the extraction of intense ion beams, modification of the ion beam pulse duration, and reliability of the ion source still need to be made for practical applications.« less

An electron beam ion trap and source for re-acceleration of rare-isotope ion beams at TRIUMF

NASA Astrophysics Data System (ADS)

Blessenohl, M. A.; Dobrodey, S.; Warnecke, C.; Rosner, M. K.; Graham, L.; Paul, S.; Baumann, T. M.; Hockenbery, Z.; Hubele, R.; Pfeifer, T.; Ames, F.; Dilling, J.; Crespo López-Urrutia, J. R.

2018-05-01

Electron beam driven ionization can produce highly charged ions (HCIs) in a few well-defined charge states. Ideal conditions for this are maximally focused electron beams and an extremely clean vacuum environment. A cryogenic electron beam ion trap fulfills these prerequisites and delivers very pure HCI beams. The Canadian rare isotope facility with electron beam ion source-electron beam ion sources developed at the Max-Planck-Institut für Kernphysik (MPIK) reaches already for a 5 keV electron beam and a current of 1 A with a density in excess of 5000 A/cm2 by means of a 6 T axial magnetic field. Within the trap, the beam quickly generates a dense HCI population, tightly confined by a space-charge potential of the order of 1 keV times the ionic charge state. Emitting HCI bunches of ≈107 ions at up to 100 Hz repetition rate, the device will charge-breed rare-isotope beams with the mass-over-charge ratio required for re-acceleration at the Advanced Rare IsotopE Laboratory (ARIEL) facility at TRIUMF. We present here its design and results from commissioning runs at MPIK, including X-ray diagnostics of the electron beam and charge-breeding process, as well as ion injection and HCI-extraction measurements.

Performance on the low charge state laser ion source in BNL

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

Okamura, M.; Alessi, J.; Beebe, E.

On March 2014, a Laser Ion Source (LIS) was commissioned which delivers high-brightness, low-charge-state heavy ions for the hadron accelerator complex in Brookhaven National Laboratory (BNL). Since then, the LIS has provided many heavy ion species successfully. The low-charge-state (mostly singly charged) beams are injected to the Electron Beam Ion Source (EBIS), where ions are then highly ionized to fit to the following accelerator’s Q/M acceptance, like Au 32+. Recently we upgraded the LIS to be able to provide two different beams into EBIS on a pulse-to-pulse basis. Now the LIS is simultaneously providing beams for both the Relativistic Heavymore » Ion Collider (RHIC) and NASA Space Radiation Laboratory (NSRL).« less

Effective Electrostatic Interactions Between Two Overall Neutral Surfaces with Quenched Charge Heterogeneity Over Atomic Length Scale

NASA Astrophysics Data System (ADS)

Zhou, S.

2017-12-01

Using Monte Carlo results as a reference, a classical density functional theory ( CDFT) is shown to reliably predict the forces between two heterogeneously charged surfaces immersed in an electrolyte solution, whereas the Poisson-Boltzmann ( PB) theory is demonstrated to deteriorate obviously for the same system even if the system parameters considered fall within the validity range of the PB theory in the homogeneously charged surfaces. By applying the tested CDFT, we study the effective electrostatic potential of mean force ( EPMF) between two face-face planar and hard surfaces of zero net charge on which positive and negative charges are separated and considered to present as discontinuous spots on the inside edges of the two surfaces. Main conclusions are summarized as follows: (i) strength of the EPMF in the surface charge separation case is very sensitively and positively correlated with the surface charge separation level and valency of the salt ion. Particularly, the charge separation level and the salt ion valency have a synergistic effect, which makes high limit of the EPMF strength in the surface charge separation case significantly go beyond that of the ideal homogeneously charged surface counterpart at average surface charge density similar to the average surface positive or negative charge density in the charge separation case. (ii) The surface charge distribution patterns mainly influence sign of the EPMF: symmetrical and asymmetrical patterns induce repulsive and attractive (at small distances) EPMF, respectively; but with low valency salt ions and low charge separation level the opposite may be the case. With simultaneous presence of both higher valency cation and anion, the EPMF can be repulsive at intermediate distances for asymmetrical patterns. (iii) Salt ion size has a significant impact, which makes the EPMF tend to become more and more repulsive with the ion diameter regardless of the surface charge distribution patterns and the valency of the salt ion; whereas if the 1:1 type electrolyte and the symmetrical patterns are considered, then the opposite may be the case. All of these findings can be explained self-consistently from several perspectives: an excess adsorption of the salt ions (induced by the surface charge separation) serving to raise the osmotic pressure between the plates, configuration fine-tuning in the thinner ion adsorption layer driven by the energy decrease principle, direct Coulombic interactions operating between charged objects on the two face-to-face plates involved, and net charge strength in the ion adsorption layer responsible for the net electrostatic repulsion.

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

PubMed Central

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

2009-01-01

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

Generation of multicomponent ion beams by a vacuum arc ion source with compound cathode.

PubMed

Savkin, K P; Yushkov, Yu G; Nikolaev, A G; Oks, E M; Yushkov, G Yu

2010-02-01

This paper presents the results of time-of-flight mass spectrometry studies of the elemental and mass-to-charge state compositions of metal ion beams produced by a vacuum arc ion source with compound cathode (WC-Co(0.5), Cu-Cr(0.25), Ti-Cu(0.1)). We found that the ion beam composition agrees well with the stoichiometric composition of the cathode material from which the beam is derived, and the maximum ion charge state of the different plasma components is determined by the ionization capability of electrons within the cathode spot plasma, which is common to all components. The beam mass-to-charge state spectrum from a compound cathode features a greater fraction of multiply charged ions for those materials with lower electron temperature in the vacuum arc cathode spot, and a smaller fraction for those with higher electron temperature within the spot. We propose a potential diagram method for determination of attainable ion charge states for all components of the compound cathodes.

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.

Halogeno-substituted 2-aminobenzoic acid derivatives for negative ion fragmentation studies of N-linked carbohydrates.

PubMed

Harvey, David J

2005-01-01

Negative ion electrospray mass spectra of high-mannose N-linked glycans derivatised with 2-aminobenzoic acids and ionised from solutions containing ammonium hydroxide gave prominent [M-H](-) ions accompanied by weaker [M-2H](2-) ions. Fragmentation of both types of ions gave prominent singly charged glycosidic cleavage ions containing the derivatised reducing terminus and ions from the non-reducing terminus that appeared to be products of cross-ring cleavages. Differentiation of these two groups of ions was conveniently achieved in a single spectrum by use of chloro- or bromo-substituted benzoic acids in order to label ions containing the derivative with an atom with a distinctive isotope pattern. Fragmentation of the doubly charged ions gave more abundant fragments, both singly and doubly charged, than did fragmentation of the singly charged ions, but information of chain branching was masked by the appearance of prominent ions produced by internal cleavages. Copyright (c) 2005 John Wiley & Sons, Ltd.

High responsivity secondary ion energy analyzer

NASA Astrophysics Data System (ADS)

Belov, A. S.; Chermoshentsev, D. A.; Gavrilov, S. A.; Frolov, O. T.; Netchaeva, L. P.; Nikulin, E. S.; Zubets, V. N.

2018-05-01

The degree of space charge compensation of a 70 mA, 400 keV pulsed hydrogen ion beam has been measured with the use of an electrostatic energy analyzer of secondary ions. The large azimuthal angle of the analyzer enables a high responsivity, defined as the ratio of the slow secondary ion current emerging from the partially-compensated ion beam to the fast ion beam current. We measured 84% space charge compensation of the ion beam. The current from the slow ions and the rise time from the degree of space charge compensation were measured and compared with expected values.

PECAN: Library Free Peptide Detection for Data-Independent Acquisition Tandem Mass Spectrometry Data

PubMed Central

Ting, Ying S.; Egertson, Jarrett D.; Bollinger, James G.; Searle, Brian C.; Payne, Samuel H.; Noble, William Stafford; MacCoss, Michael J.

2017-01-01

In mass spectrometry-based shogun proteomics, data-independent acquisition (DIA) is an emerging technique for unbiased and reproducible measurement of protein mixtures. Without targeting a specific precursor ion, DIA MS/MS spectra are often highly multiplexed, containing product ions from multiple co-fragmenting precursors. Thus, detecting peptides directly from DIA data is challenging; most DIA data analyses require spectral libraries. Here we present a new library-free, peptide-centric tool PECAN that detects peptides directly from DIA data. PECAN reports evidence of detection based on product ion scoring, enabling detection of low abundance analytes with poor precursor ion signal. We benchmarked PECAN with chromatographic peak picking accuracy and peptide detection capability. We further validated PECAN detection with data-dependent acquisition and targeted analyses. Last, we used PECAN to build a library from DIA data and to query sequence variants. Together, these results show that PECAN detects peptides robustly and accurately from DIA data without using a library. PMID:28783153

SPM observation of nano-dots induced by slow highly charged ions

NASA Astrophysics Data System (ADS)

Nakamura, Nobuyuki; Terada, Masashi; Nakai, Yoichi; Kanai, Yasuyuki; Ohtani, Shunsuke; Komaki, Ken-ichiro; Yamazaki, Yasunori

2005-05-01

We have observed nano-dots on a highly oriented pyrolytic graphite (HOPG) surface produced by highly charged ion impacts with a scanning probe microscope. In order to clarify the role of potential and kinetic energies in surface modification, we have measured the kinetic energy and incident ion charge dependences of the dot size. The results showed that the potential energy or the incident ion charge has strong influence on the surface modification rather than the kinetic energy.

Steady-State Ion Beam Modeling with MICHELLE

NASA Astrophysics Data System (ADS)

Petillo, John

2003-10-01

There is a need to efficiently model ion beam physics for ion implantation, chemical vapor deposition, and ion thrusters. Common to all is the need for three-dimensional (3D) simulation of volumetric ion sources, ion acceleration, and optics, with the ability to model charge exchange of the ion beam with a background neutral gas. The two pieces of physics stand out as significant are the modeling of the volumetric source and charge exchange. In the MICHELLE code, the method for modeling the plasma sheath in ion sources assumes that the electron distribution function is a Maxwellian function of electrostatic potential over electron temperature. Charge exchange is the process by which a neutral background gas with a "fast" charged particle streaming through exchanges its electron with the charged particle. An efficient method for capturing this is essential, and the model presented is based on semi-empirical collision cross section functions. This appears to be the first steady-state 3D algorithm of its type to contain multiple generations of charge exchange, work with multiple species and multiple charge state beam/source particles simultaneously, take into account the self-consistent space charge effects, and track the subsequent fast neutral particles. The solution used by MICHELLE is to combine finite element analysis with particle-in-cell (PIC) methods. The basic physics model is based on the equilibrium steady-state application of the electrostatic particle-in-cell (PIC) approximation employing a conformal computational mesh. The foundation stems from the same basic model introduced in codes such as EGUN. Here, Poisson's equation is used to self-consistently include the effects of space charge on the fields, and the relativistic Lorentz equation is used to integrate the particle trajectories through those fields. The presentation will consider the complexity of modeling ion thrusters.

Adding high time resolution to charge-state-specific ion energy measurements for pulsed copper vacuum arc plasmas

NASA Astrophysics Data System (ADS)

Tanaka, Koichi; Han, Liang; Zhou, Xue; Anders, André

2015-08-01

Charge-state-resolved ion energy-time distributions of pulsed Cu arc plasma were obtained by using direct (time-dependent) acquisition of the ion detection signal from a commercial ion mass-per-charge and energy-per-charge analyzer. We find a shift of energies of Cu2+, Cu3+ and Cu4+ ions to lower values during the first few hundred microseconds after arc ignition, which is evidence for particle collisions in the plasma. The generation of Cu+ ions in the later part of the pulse, measured by the increase of Cu+ signal intensity and an associated slight reduction of the mean charge state, points to charge exchange reactions between ions and neutrals. At the very beginning of the pulse, when the plasma expands into vacuum and the plasma potential strongly fluctuates, ions with much higher energy (over 200 eV) are observed. Early in the pulse, the ion energies observed are approximately proportional to the ion charge state, and we conclude that the acceleration mechanism is primarily based on acceleration in an electric field. This field is directed away from the cathode, indicative of a potential hump. Measurements by a floating probe suggest that potential structures travel, and ions moving in the traveling field can gain high energies up to a few hundred electron-volts. Later in the pulse, the approximate proportionality is lost, which is related to increased smearing out of different energies due to collisions with neutrals, and/or to a change of the acceleration character from electrostatic to ‘gas-dynamic’, i.e. dominated by pressure gradient.

Polymer/Nanocrystal Hybrid Solar Cells: Influence of Molecular Precursor Design on Film Nanomorphology, Charge Generation and Device Performance

PubMed Central

MacLachlan, Andrew J; Rath, Thomas; Cappel, Ute B; Dowland, Simon A; Amenitsch, Heinz; Knall, Astrid-Caroline; Buchmaier, Christine; Trimmel, Gregor; Nelson, Jenny; Haque, Saif A

2015-01-01

In this work, molecular tuning of metal xanthate precursors is shown to have a marked effect on the heterojunction morphology of hybrid poly(3-hexylthiophene-2,5-diyl) (P3HT)/CdS blends and, as a result, the photochemical processes and overall performance of in situ fabricated hybrid solar cells. A series of cadmium xanthate complexes is synthesized for use as in situ precursors to cadmium sulfide nanoparticles in hybrid P3HT/CdS solar cells. The formation of CdS domains is studied by simultaneous GIWAXS (grazing incidence wide-angle X-ray scattering) and GISAXS (grazing incidence small-angle X-ray scattering), revealing knowledge about crystal growth and the formation of different morphologies observed using TEM (transmission electron microscopy). These measurements show that there is a strong relationship between precursor structure and heterojunction nanomorphology. A combination of TAS (transient absorption spectroscopy) and photovoltaic device performance measurements is used to show the intricate balance required between charge photogeneration and percolated domains in order to effectively extract charges to maximize device power conversion efficiencies. This study presents a strong case for xanthate complexes as a useful route to designing optimal heterojunction morphologies for use in the emerging field of hybrid organic/inorganic solar cells, due to the fact that the nanomorphology can be tuned via careful design of these precursor materials. PMID:25866496

CALUTRON

DOEpatents

Kamen, M.D.

1958-02-25

This patent describes an improved ion source for a calutron which is designed to eliminate the necessity of opening the evacuated calutron tank to permit entrance into the tank to place a further charge in thc ion source. The improved ion source comprises a charge reservoir positioned exerior to the calutron tank and connected to an ionizing device located within the tank by a channeled member. A section cf the tank wall supports the ion source structure and Is removable to allow withdrawal of the composite assembly. Heat is applied to the charge reservoir to vaporize the charge and force the charge to the ionizing device, and heat is also furnished along the connecting channel to prevent condensation of the vapor, a valve structure at the exit from the charge reservoir controls the amount of charge received by the ionizing device.

Relationships between structure, ionization profile and sensitivity of exogenous anabolic steroids under electrospray ionization and analysis in human urine using liquid chromatography-tandem mass spectrometry.

PubMed

Cha, Eunju; Kim, Sohee; Kim, Hee Won; Lee, Kang Mi; Kim, Ho Jun; Kwon, Oh-Seung; Lee, Jaeick

2016-04-01

The relationships between the ionization profile, sensitivity, and structures of 64 exogenous anabolic steroids (groups I-IV) was investigated under electrospray ionization (ESI) conditions. The target analytes were ionized as [M + H](+) or [M + H-nH2 O](+) in the positive mode, and these ions were used as precursor ions for selected reaction monitoring analysis. The collision energy and Q3 ions were optimized based on the sensitivity and selectivity. The limits of detection (LODs) were 0.05-20 ng/mL for the 64 steroids. The LODs for 38 compounds, 14 compounds and 12 compounds were in the range of 0.05-1, 2-5 and 10-20 ng/mL, respectively. Steroids including the conjugated keto-functional group at C3 showed good proton affinity and stability, and generated the [M + H](+) ion as the most abundant precursor ion. In addition, the LODs of steroids using the [M + H](+) ion as the precursor ion were mostly distributed at low concentrations. In contrast, steroids containing conjugated/unconjugated hydroxyl functional groups at C3 generated [M + H - H2 O](+) or [M + H - 2H2 O](+) ions, and these steroids showed relatively high LODs owing to poor stability and multiple ion formation. An LC-MS/MS method based on the present ionization profile was developed and validated for the determination of 78 steroids (groups I-V) in human urine. Copyright © 2015 John Wiley & Sons, Ltd.

The ion dependent change in the mechanism of charge storage of chemically preintercalated bilayered vanadium oxide electrodes

NASA Astrophysics Data System (ADS)

Clites, Mallory; Pomerantseva, Ekaterina

2017-08-01

Chemical pre-intercalation is a soft chemistry synthesis approach that allows for the insertion of inorganic ions into the interlayer space of layered battery electrode materials prior to electrochemical cycling. Previously, we have demonstrated that chemical pre-intercalation of Na+ ions into the structure of bilayered vanadium oxide (δ-V2O5) results in record high initial capacities above 350 mAh g-1 in Na-ion cells. This performance is attributed to the expanded interlayer spacing and predefined diffusion pathways achieved by the insertion of charge-carrying ions. However, the effect of chemical pre-intercalation of δ-V2O5 has not been studied for other ion-based systems beyond sodium. In this work, we report the effect of the chemically preintercalated alkali ion size on the mechanism of charge storage of δ- MxV2O5 (M = Li, Na, K) in Li-ion, Na-ion, and K-ion batteries, respectively. The interlayer spacing of the δ-MxV2O5 varied depending on inserted ion, with 11.1 Å achieved for Li-preintercalated δ-V2O5, 11.4 Å for Na-preintercalated δ- V2O5, and 9.6 Å for K-preintercalated δ-V2O5. Electrochemical performance of each material has been studied in its respective ion-based system (δ-LixV2O5 in Li-ion cells, δ-NaxV2O5 in Na-ion cells, and δ-KxV2O5 in K-ion cells). All materials demonstrated high initial capacities above 200 mAh g-1. However, the mechanism of charge storage differed depending on the charge-carrying ion, with Li-ion cells demonstrating predominantly pseudocapacitive behavior and Naion and K-ion cells demonstrating a significant portion of capacity from diffusion-limited intercalation processes. In this study, the combination of increased ionic radii of the charge-carrying ions and decreased synthesized interlayer spacing of the bilayered vanadium oxide phase correlates to an increase in the portion of capacity attributed diffusion-limited charge-storage processes.

Efficiently accounting for ion correlations in electrokinetic nanofluidic devices using density functional theory.

PubMed

Gillespie, Dirk; Khair, Aditya S; Bardhan, Jaydeep P; Pennathur, Sumita

2011-07-15

The electrokinetic behavior of nanofluidic devices is dominated by the electrical double layers at the device walls. Therefore, accurate, predictive models of double layers are essential for device design and optimization. In this paper, we demonstrate that density functional theory (DFT) of electrolytes is an accurate and computationally efficient method for computing finite ion size effects and the resulting ion-ion correlations that are neglected in classical double layer theories such as Poisson-Boltzmann. Because DFT is derived from liquid-theory thermodynamic principles, it is ideal for nanofluidic systems with small spatial dimensions, high surface charge densities, high ion concentrations, and/or large ions. Ion-ion correlations are expected to be important in these regimes, leading to nonlinear phenomena such as charge inversion, wherein more counterions adsorb at the wall than is necessary to neutralize its surface charge, leading to a second layer of co-ions. We show that DFT, unlike other theories that do not include ion-ion correlations, can predict charge inversion and other nonlinear phenomena that lead to qualitatively different current densities and ion velocities for both pressure-driven and electro-osmotic flows. We therefore propose that DFT can be a valuable modeling and design tool for nanofluidic devices as they become smaller and more highly charged. Copyright © 2011 Elsevier Inc. All rights reserved.

Extraction of highly charged ions from the Berlin Electron Beam Ion Trap for interactions with a gas target

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

Allen, F.I.; Biedermann, C.; Radtke, R.

2006-03-15

Highly charged ions are extracted from the Berlin Electron Beam Ion Trap for investigations of charge exchange with a gas target. The classical over-the-barrier model for slow highly charged ions describes this process, whereby one or more electrons are captured from the target into Rydberg states of the ion. The excited state relaxes via a radiative cascade of the electron to ground energy. The cascade spectra are characteristic of the capture state. We investigate x-ray photons emitted as a result of interactions between Ar{sup 17+} ions at energies {<=}5q keV with Ar atoms. Of particular interest is the velocity dependencemore » of the angular momentum capture state l{sub c}.« less

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Production of soft X-ray emitting slow multiply charged ions - Recoil ion spectroscopy

NASA Technical Reports Server (NTRS)

Sellin, I. A.; Elston, S. B.; Forester, J. P.; Griffin, P. M.; Pegg, D. J.; Peterson, R. S.; Thoe, R. S.; Vane, C. R.; Wright, J. J.; Groeneveld, K.-O.

1977-01-01

S ions with a mean charge state of about 14+ and Cl ions with a mean charge state of 12+ were used to study Ne L-shell vacancy production. The ions caused copious production of NeII-NeVIII excited states with approximately 10 to the minus 18 sq cm cross sections. The induced recoil velocities might have application to a significantly higher resolution spectroscopy than is possible with beam-foil methods.

Collision-induced fragmentation of negative ions from N-linked glycans derivatized with 2-aminobenzoic acid.

PubMed

Harvey, David J

2005-05-01

N-Linked glycans from bovine ribonuclease B, chicken ovalbumin, bovine fetuin, porcine thyroglobulin and human alpha(1)-acid glycoprotein were derivatized with 2-aminobenzoic acid by reductive amination and their tandem mass spectra were recorded by negative ion electrospray ionization with a quadrupole time-of-flight mass spectrometer. Derivatives were also prepared from 2-amino-5-methyl- and 2-amino-4,5-dimethoxybenzoic acid in order to confirm the identity of fragment ions containing the reducing terminus. Major fragments from the [M - H](-) ions from the neutral glycans retained the derivative (Y-type cleavages) and provided information on sequence and branching. Other major fragments were products of A-type cross-ring cleavages giving information on antenna structure. Singly doubly and triply charged ions were formed from sialylated glycans. They produced major fragments by loss of sialic acid and a series of singly charged ions that were similar to those from the neutral analogues. Doubly charge ions were also produced by the neutral glycans and were fragmented to form product ions with one and two charges. Again, the fragment ions with a single charge were similar to those from the singly charged parents, but branching information was less obvious because of the occurrence of more abundant ions produced by multiple cleavages. Detection limits were around 200 fmol (3 : 1 signal-to-noise ratio). Copyright 2005 John Wiley & Sons, Ltd.

Dressed ion theory of size-asymmetric electrolytes: effective ionic charges and the decay length of screened Coulomb potential and pair correlations.

PubMed

Forsberg, Björn; Ulander, Johan; Kjellander, Roland

2005-02-08

The effects of ionic size asymmetry on long-range electrostatic interactions in electrolyte solutions are investigated within the primitive model. Using the formalism of dressed ion theory we analyze correlation functions from Monte Carlo simulations and the hypernetted chain approximation for size asymmetric 1:1 electrolytes. We obtain decay lengths of the screened Coulomb potential, effective charges of ions, and effective permittivity of the solution. It is found that the variation of these quantities with the degree of size asymmetry depends in a quite intricate manner on the interplay between the electrostatic coupling and excluded volume effects. In most cases the magnitude of the effective charge of the small ion species is larger than that of the large species; the difference increases with increasing size asymmetry. The effective charges of both species are larger (in absolute value) than the bare ionic charge, except for high asymmetry where the effective charge of the large ions can become smaller than the bare charge.

Van Allen Probe Charging During the St. Patrick's Day Event

NASA Technical Reports Server (NTRS)

Parker, L. Neergaard; Minow, J. I.

2015-01-01

The geomagnetic storms on and around March 17, 2015 marked the largest storms seen in the declining phase of the solar cycle to date. We use the Helium Oxygen Proton Electron (HOPE) mass spectrometer on board the Van Allen Probe - A and B satellites to study in detail the charging effects seen on these spacecraft during this time. Ion particle flux data provides information on the magnitude of the charging events using the ion line charging signature due to low energy ions accelerated by the spacecraft potential. Electron flux observations are used to correlate the charging environment with variations in spacecraft potential through the event. We also investigate the density and temperature of ions and electrons during the time of the charging event.

Anatomy of charge-exchange straggling

NASA Astrophysics Data System (ADS)

Sigmund, P.; Osmani, O.; Schinner, A.

2014-11-01

We have studied charge-exchange straggling theoretically for swift krypton and silicon ions and five target gases in the MeV/u energy regime. We find a pronounced two-peak structure for all ion-target combinations. The peak at the highest energy appears around the velocity where the bare ion and the one-electron ion are equally abundant in the equilibrium charge distribution. Correspondingly, the low-energy peak appears near the cross-over between the charge fractions of the two- and the three-electron ion. The possibility of further peaks at lower energies is discussed. Our findings are compared with recent experimental results on straggling of krypton beams.

Studies on the primary structure of short polysaccharides using SEC MALDI mass spectroscopy.

PubMed

Garozzo, D; Spina, E; Cozzolino, R; Cescutti, P; Fett, W F

2000-01-12

The introduction of size-exclusion chromatography (SEC) analysis of polysaccharides prior to MALDI mass spectroscopy accounts for the determination of the molecular mass of the repeating unit when neutral homopolymers are investigated. In the case of natural polysaccharides characterised by more complicated structural features (presence of non-carbohydrate substituents, charged groups, etc.), this mass value usually is in agreement with more than one sugar composition. Therefore, it is not sufficient to give the correct monosaccharidic composition of the polysaccharide investigated. To solve this problem, MALDI spectra were recorded on the permethylated sample and post-source decay experiments were performed on precursor ions. In this way, the composition (in terms of Hex, HexNAc, etc.), size and sequence of the repeating unit were determined.

In situ synthesis of TiO2(B) nanotube/nanoparticle composite anode materials for lithium ion batteries.

PubMed

Liu, Xiang; Sun, Qian; Ng, Alan M C; Djurišić, Aleksandra B; Xie, Maohai; Liao, Changzhong; Shih, Kaimin; Vranješ, Mila; Nedeljković, Jovan M; Deng, Zhaofeng

2015-10-23

Titania nanotubes were prepared by a simple hydrothermal route. Their electrochemical performance has been examined in detail and compared to TiO2(B) nanoparticles, TiO2 anatase and P25 titania nanoparticles. The cycling and rate performance of TiO2 nanotubes is superior to both types of nanoparticles, and it can be further improved by an in situ titanium precursor treatment, which results in the formation of TiO2 nanoparticles on/between the nanotubes. The obtained specific capacity after 200 cycles at 0.2 A g(-1) charge/discharge rate remained above 130 mAh g(-1). The enhanced lithium storage properties of these samples can be attributed to their unique morphology and crystal structure.

Characterization of the internal ion environment of biofilms based on charge density and shape of ion.

PubMed

Kurniawan, Andi; Tsuchiya, Yuki; Eda, Shima; Morisaki, Hisao

2015-12-01

Biofilm polymers contain both electrically positively and negatively charged sites. These charged sites enable the biofilm to trap and retain ions leading to an important role of biofilm such as nutrient recycling and pollutant purification. Much work has focused on the ion-exchange capacity of biofilms, and they are known to adsorb ions through an exchange mechanism between the ions in solution and the ions adsorbed to the charged sites on the biofilm polymer. However, recent studies suggest that the adsorption/desorption behavior of ions in a biofilm cannot be explained solely by this ion exchange mechanism. To examine the possibility that a substantial amount of ions are held in the interstitial region of the biofilm polymer by an electrostatic interaction, intact biofilms formed in a natural environment were immersed in distilled water and ion desorption was investigated. All of the detected ion species were released from the biofilms over a short period of time, and very few ions were subsequently released over more time, indicating that the interstitial region of biofilm polymers is another ion reserve. The extent of ion retention in the interstitial region of biofilms for each ion can be determined largely by charge density, |Z|/r, where |Z| is the ion valence as absolute value and r is the ion radius. The higher |Z|/r value an ion has, the stronger it is retained in the interstitial region of biofilms. Ion shape is also a key determinant of ion retention. Spherical and non-spherical ions have different correlations between the condensation ratio and |Z|/r. The generality of these findings were assured by various biofilm samples. Thus, the internal regions of biofilms exchange ions dynamically with the outside environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Efficiently photo-charging lithium-ion battery by perovskite solar cell

NASA Astrophysics Data System (ADS)

Xu, Jiantie; Chen, Yonghua; Dai, Liming

2015-08-01

Electric vehicles using lithium-ion battery pack(s) for propulsion have recently attracted a great deal of interest. The large-scale practical application of battery electric vehicles may not be realized unless lithium-ion batteries with self-charging suppliers will be developed. Solar cells offer an attractive option for directly photo-charging lithium-ion batteries. Here we demonstrate the use of perovskite solar cell packs with four single CH3NH3PbI3 based solar cells connected in series for directly photo-charging lithium-ion batteries assembled with a LiFePO4 cathode and a Li4Ti5O12 anode. Our device shows a high overall photo-electric conversion and storage efficiency of 7.80% and excellent cycling stability, which outperforms other reported lithium-ion batteries, lithium-air batteries, flow batteries and super-capacitors integrated with a photo-charging component. The newly developed self-chargeable units based on integrated perovskite solar cells and lithium-ion batteries hold promise for various potential applications.

Efficiently photo-charging lithium-ion battery by perovskite solar cell

PubMed Central

Xu, Jiantie; Chen, Yonghua; Dai, Liming

2015-01-01

Electric vehicles using lithium-ion battery pack(s) for propulsion have recently attracted a great deal of interest. The large-scale practical application of battery electric vehicles may not be realized unless lithium-ion batteries with self-charging suppliers will be developed. Solar cells offer an attractive option for directly photo-charging lithium-ion batteries. Here we demonstrate the use of perovskite solar cell packs with four single CH3NH3PbI3 based solar cells connected in series for directly photo-charging lithium-ion batteries assembled with a LiFePO4 cathode and a Li4Ti5O12 anode. Our device shows a high overall photo-electric conversion and storage efficiency of 7.80% and excellent cycling stability, which outperforms other reported lithium-ion batteries, lithium–air batteries, flow batteries and super-capacitors integrated with a photo-charging component. The newly developed self-chargeable units based on integrated perovskite solar cells and lithium-ion batteries hold promise for various potential applications. PMID:26311589

Attraction between like-charged monovalent ions.

PubMed

Zangi, Ronen

2012-05-14

Ions with like-charges repel each other with a magnitude given by the Coulomb law. The repulsion is also known to persist in aqueous solutions albeit factored by the medium's dielectric constant. In this paper, we report results from molecular dynamics simulations of alkali halides salt solutions indicating an effective attraction between some of the like-charged monovalent ions. The attraction is observed between anions, as well as between cations, leading to the formation of dimers with lifetimes on the order of few picoseconds. Two mechanisms have been identified to drive this counterintuitive attraction. The first is exhibited by high-charge density ions, such as fluoride, at low salt concentrations, yielding effective attractions with magnitude up to the order of 1-2 kT. In this case, the stronger local electric field generated when the two ions are in contact augments the alignment of neighboring waters toward the ions. This results in a gain of substantial favorable ion-water interaction energy. For fluorides, this interaction constitutes the major change among the different energy components compensating for the anion-anion repulsion, and therefore, rendering like-charge association possible. The second mechanism involves mediation by counterions, the attractions increase with salt concentration and are characterized by small magnitudes. In particular, clusters of ion triplets, in which a counterion is either bridging the two like-charged ions or is paired to only one of them, are formed. Although these two mechanisms may not yield net attractions in many cases, they might still be operational and significant, explaining effective repulsions between like-charged ions with magnitudes much smaller than expected based on continuum electrostatics.

High-energy and low-energy collision-induced dissociation of protonated flavonoids generated by MALDI and by electrospray ionization

NASA Astrophysics Data System (ADS)

March, Raymond E.; Li, Hongxia; Belgacem, Omar; Papanastasiou, Dimitris

2007-04-01

Product ion mass spectra of a series of nine protonated flavonoids have been observed by electrospray ionization combined with quadrupole/time-of-flight (ESI QTOF), and matrix-assisted laser desorption ionization combined either with quadrupole ion trap (MALDI QIT) tandem mass spectrometry or time-of-flight tandem mass spectrometry (MALDI TOF ReTOF). The compounds examined are 3,6-, 3,2'-, and 3,3'-dihydoxyflavone, apigenin (5,7,4'-trihydroxyflavone), luteolin (5,7,3',4'-tetrahydroxyflavone), apigenin-7-O-glucoside, hesperidin (5,7,3'-trihydroxy-4'-methoxyflavanone), daidzen (7,4'-dihydroxyisoflavone), and rutin (quercitin-3-O-rutinoside) where quercitin is 3,5,7,3',4'-pentahydroxyflavone; sodiated rutin was examined also. The center-of-mass energies in ESI QTOF and MALDI QIT are similar (1-4 eV) and their product ion mass spectra are virtually identical. In the MALDI TOF ReTOF instrument, center-of-mass energies range from 126-309 eV for sodiated rutin to protonated dihydroxyflavones, respectively. Due to the high center-of-mass energies available with the MALDI TOF ReTOF instrument, some useful structural information may be obtained; however, with increasing precursor mass/charge ratio, product ion mass spectra become simplified so as to be of limited structural value. Electronic excitation of the protonated (and sodiated) species examined here offers an explanation for the very simple product ion mass spectra observed particularly for glycosylated flavonoids.

Neutralized ion beam modification of cellulose membranes for study of ion charge effect on ion-beam-induced DNA transfer

NASA Astrophysics Data System (ADS)

Prakrajang, K.; Sangwijit, K.; Anuntalabhochai, S.; Wanichapichart, P.; Yu, L. D.

2012-02-01

Low-energy ion beam biotechnology (IBBT) has recently been rapidly developed worldwide. Ion-beam-induced DNA transfer is one of the important applications of IBBT. However, mechanisms involved in this application are not yet well understood. In this study plasma-neutralized ion beam was applied to investigate ion charge effect on induction of DNA transfer. Argon ion beam at 7.5 keV was neutralized by RF-driven plasma in the beam path and then bombarded cellulose membranes which were used as the mimetic plant cell envelope. Electrical properties such as impedance and capacitance of the membranes were measured after the bombardment. An in vitro experiment on plasmid DNA transfer through the cellulose membrane was followed up. The results showed that the ion charge input played an important role in the impedance and capacitance changes which would affect DNA transfer. Generally speaking, neutral particle beam bombardment of biologic cells was more effective in inducing DNA transfer than charged ion beam bombardment.

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode

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

Huang, J Y; Zhong, L; Wang, C M

2010-12-09

We report the creation of a nanoscale electrochemical device inside a transmission electron microscope—consisting of a single tin dioxide (SnO{sub 2}) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO{sub 2}) cathode—and the in situ observation of the lithiation of the SnO{sub 2} nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a “Medusa zone” containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfitmore » stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.« less

The SMILETRAP facility

NASA Astrophysics Data System (ADS)

Carlberg, C.; Borgenstrand, H.; Rouleau, G.; Schuch, R.; Söderberg, F.; Bergström, I.; Jertz, R.; Schwarz, T.; Stein, J.; Bollen, G.; Kluge, H.-J.; Mann, R.

1995-01-01

The SMILETRAP experimental set-up, a Penning trap mass spectrometer for highly charged ions, is described. Capture and observation of cyclotron frequencies of externally produced highly charged ions, rapid interchange of investigated and reference ions and measurements of the rotational kinetic energies are demonstrated. Mass measurements utilizing different charge states and species to verify the consistency of the measurements are presented. A relative uncertainty of about 10-9 is attained in comparisons between highly charged carbon, nitrogen, oxygen, neon and the singly charged hydrogen molecule.

Dissociation reactions of protonated anthracycline antibiotics following electrospray ionization-tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Sleno, Lekha; Campagna-Slater, Valerie; Volmer, Dietrich A.

2006-09-01

Fragmentation pathways of doxorubicin, a common cancer therapy agent, and three closely related analogs (epirubicin, daunorubicin, idarubicin) were compared using electrospray ionization with tandem mass spectrometry. This class of antibiotics with anti-tumour activity has important structural features, with a tetracyclic aromatic, polyketide portion, which is glycosylated with an amino sugar in order to exhibit its biological activity. Collision-induced dissociation spectra revealed very similar product ions for each analog, however, important differences were seen in the relative abundances and the ease at which certain fragments were formed. Fragment ions observed included those from cleavage of the glycosidic bond, loss of the side chain from the aglycone moiety, water losses and loss of a methyl radical. Following cleavage of the glycosidic bond, the charge can either reside on the aglycone portion or the sugar moiety, and each of these primary fragments undergoes several secondary dissociation pathways, depending on the collision energy. By ramping the collision voltage, we were able to correlate the changes in fragmentation behavior with small alterations in the structure of the precursor ion. The detailed study of the fragmentation behavior of doxorubicin was supported by accurate mass measurements, using an electrospray-time of flight instrument, as well as MS3 data from a quadrupole-linear ion trap mass spectrometer. Computational studies were also performed to help explain the role of certain functional groups in the fragmentation reactions.

Self-Supported CoP Nanorod Arrays Grafted on Stainless Steel as an Advanced Integrated Anode for Stable and Long-Life Lithium-Ion Batteries.

PubMed

Xu, Xijun; Liu, Jun; Hu, Renzong; Liu, Jiangwen; Ouyang, Liuzhang; Zhu, Min

2017-04-19

To alleviate the capacity degradation of anode materials for Li-ion batteries, caused by serious volume expansion and particle aggregation, intensive attention has been devoted to the rational design and fabrication of novel anode architectures. Herein, self-supported CoP nanorod arrays have been facilely synthesized using hydrothemally deposited Co(CO 3 ) 0.5 (OH)⋅0.11 H 2 O nanorod arrays as the precursor, through a gas-phase phosphidation method. As the anode for Li-ion batteries, such 3D interconnected CoP nanorod arrays show an initial discharge capacity of 1067 mAh g -1 and a high reversible charge capacity of 737 mAh g -1 at 0.4 Ag -1 . After 400 cycles, their specific capacity can reach 510 mAh g -1 ; even after 900 cycles, they can still deliver a specific capacity of 390 mAh g -1 . CoP//LiCoO 2 full-cells also exhibit a high reversible capacity of 400 mAh g -1 after 50 cycles. These unique 3D interconnected CoP nanorod arrays also show ultrastable cycling performance over 500 cycles when used as the anode in a Na-ion battery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-mediated ion-ion interactions are enhanced at the water vapor-liquid interface.

PubMed

Venkateshwaran, Vasudevan; Vembanur, Srivathsan; Garde, Shekhar

2014-06-17

There is overwhelming evidence that ions are present near the vapor-liquid interface of aqueous salt solutions. Charged groups can also be driven to interfaces by attaching them to hydrophobic moieties. Despite their importance in many self-assembly phenomena, how ion-ion interactions are affected by interfaces is not understood. We use molecular simulations to show that the effective forces between small ions change character dramatically near the water vapor-liquid interface. Specifically, the water-mediated attraction between oppositely charged ions is enhanced relative to that in bulk water. Further, the repulsion between like-charged ions is weaker than that expected from a continuum dielectric description and can even become attractive as the ions are drawn to the vapor side. We show that thermodynamics of ion association are governed by a delicate balance of ion hydration, interfacial tension, and restriction of capillary fluctuations at the interface, leading to nonintuitive phenomena, such as water-mediated like charge attraction. "Sticky" electrostatic interactions may have important consequences on biomolecular structure, assembly, and aggregation at soft liquid interfaces. We demonstrate this by studying an interfacially active model peptide that changes its structure from α-helical to a hairpin-turn-like one in response to charging of its ends.

Li-Ion Battery and Supercapacitor Hybrid Design for Long Extravehicular Activities

NASA Technical Reports Server (NTRS)

Jeevarajan, Judith

2013-01-01

With the need for long periods of extravehicular activities (EVAs) on the Moon or Mars or a near-asteroid, the need for long-performance batteries has increased significantly. The energy requirements for the EVA suit, as well as surface systems such as rovers, have increased significantly due to the number of applications they need to power at the same time. However, even with the best state-of-the-art Li-ion batteries, it is not possible to power the suit or the rovers for the extended period of performance. Carrying a charging system along with the batteries makes it cumbersome and requires a self-contained power source for the charging system that is usually not possible. An innovative method to charge and use the Li-ion batteries for long periods seems to be necessary and hence, with the advent of the Li-ion supercapacitors, a method has been developed to extend the performance period of the Li-ion power system for future exploration applications. The Li-ion supercapacitors have a working voltage range of 3.8 to 2.5 V, and are different from a traditional supercapacitor that typically has a working voltage of 1 V. The innovation is to use this Li-ion supercapacitor to charge Liion battery systems on an as-needed basis. The supercapacitors are charged using solar arrays and have battery systems of low capacity in parallel to be able to charge any one battery system while they provide power to the application. Supercapacitors can safely take up fast charge since the electrochemical process involved is still based on charge separation rather than the intercalation process seen in Li-ion batteries, thus preventing lithium metal deposition on the anodes. The lack of intercalation and eliminating wear of the supercapacitors allows for them to be charged and discharged safely for a few tens of thousands of cycles. The Li-ion supercapacitors can be charged from the solar cells during the day during an extended EVA. The Liion battery used can be half the capacity required for a nominal EVA. The small Li-ion battery can be divided into two parallel modules with independent charging ports that would allow the supercapacitors to charge one battery while the other is providing power to the rover or suit.

Ultrathin TiO2 layer coated-CdS spheres core-shell nanocomposite with enhanced visible-light photoactivity.

PubMed

Chen, Zhang; Xu, Yi-Jun

2013-12-26

Development of various strategies for controllable fabrication of core-shell nanocomposites (CSNs) with highly active photocatalytic performance has been attracting ever-increasing research attention. In particular, control of the ultrathin layer TiO2 shell in constructing CSNs in an aqueous phase is a significant but technologically challenging issue. Here, this paper demonstrates the interface assembly synthesis of CdS nanospheres@TiO2 core-shell photocatalyst via the electrostatic interaction of negatively charged water-stable titania precursor with positively charged CdS nanospheres (CdS NSPs), followed by the formation of the ultrathin-layer TiO2 shell through a facile refluxing process in aqueous phase. The as-formed CdS NSPs@TiO2 core-shell nanohybrid exhibits a high visible-light-driven photoactivity for selective transformation and reduction of heavy metal ions. The ultrathin TiO2 layer coated on CdS NSPs results in excellent light transmission property, enhanced adsorption capacity, and improved transfer of charge carriers and lifespan of photoinduced electron-hole pairs, which would prominently contribute to the significant photoactivity enhancement. It is anticipated that this facile aqueous-phase synthesis strategy could be extended to design a variety of more efficient CSN photocatalysts with controllable morphology toward target applications in diverse photoredox processes.

Boron Nitride Nanoporous Membranes with High Surface Charge by Atomic Layer Deposition.

PubMed

Weber, Matthieu; Koonkaew, Boonprakrong; Balme, Sebastien; Utke, Ivo; Picaud, Fabien; Iatsunskyi, Igor; Coy, Emerson; Miele, Philippe; Bechelany, Mikhael

2017-05-17

In this work, we report the design and the fine-tuning of boron nitride single nanopore and nanoporous membranes by atomic layer deposition (ALD). First, we developed an ALD process based on the use of BBr 3 and NH 3 as precursors in order to synthesize BN thin films. The deposited films were characterized in terms of thickness, composition, and microstructure. Next, we used the newly developed process to grow BN films on anodic aluminum oxide nanoporous templates, demonstrating the conformality benefit of BN prepared by ALD, and its scalability for the manufacturing of membranes. For the first time, the ALD process was then used to tune the diameter of fabricated single transmembrane nanopores by adjusting the BN thickness and to enable studies of the fundamental aspects of ionic transport on a single nanopore. At pH = 7, we estimated a surface charge density of 0.16 C·m -2 without slip and 0.07 C·m -2 considering a reasonable slip length of 3 nm. Molecular dynamics simulations performed with experimental conditions confirmed the conductivities and the sign of surface charges measured. The high ion transport results obtained and the ability to fine-tune nanoporous membranes by such a scalable method pave the way toward applications such as ionic separation, energy harvesting, and ultrafiltration devices.

Current-voltage characteristics influenced by the nanochannel diameter and surface charge density in a fluidic field-effect-transistor.

PubMed

Singh, Kunwar Pal; Guo, Chunlei

2017-06-21

The nanochannel diameter and surface charge density have a significant impact on current-voltage characteristics in a nanofluidic transistor. We have simulated the effect of the channel diameter and surface charge density on current-voltage characteristics of a fluidic nanochannel with positive surface charge on its walls and a gate electrode on its surface. Anion depletion/enrichment leads to a decrease/increase in ion current with gate potential. The ion current tends to increase linearly with gate potential for narrow channels at high surface charge densities and narrow channels are more effective to control the ion current at high surface charge densities. The current-voltage characteristics are highly nonlinear for wide channels at low surface charge densities and they show different regions of current change with gate potential. The ion current decreases with gate potential after attaining a peak value for wide channels at low values of surface charge densities. At low surface charge densities, the ion current can be controlled by a narrow range of gate potentials for wide channels. The current change with source drain voltage shows ohmic, limiting and overlimiting regions.

Focused helium-ion-beam-induced deposition

NASA Astrophysics Data System (ADS)

Alkemade, P. F. A.; Miro, H.

2014-12-01

The recent introduction of the helium ion microscope (HIM) offers new possibilities for materials modification and fabrication with spatial resolution below 10 nm. In particular, the specific interaction of He+ ions in the tens of keV energy range with materials—i.e., minimal deflection and mainly energy loss via electronic excitations—renders the HIM a special tool for ion-beam-induced deposition. In this work, an overview is given of all studies of helium-ion-beam-induced deposition (He-IBID) that appeared in the literature before summer 2014. Continuum models that describe the deposition processes are presented in detail, with emphasis on precursor depletion and replenishment. In addition, a Monte Carlo model is discussed. Basic experimental He-IBID studies are critically examined. They show deposition rates of up to 0.1 nm3/ion. Analysis by means of a continuum model yields the precursor diffusion constant and the cross sections for beam-induced precursor decomposition and beam-induced desorption. Moreover, it is shown that deposition takes place only in a small zone around the beam impact point. Furthermore, the characterization of deposited materials is discussed in terms of microstructure and resistivity. It is shown that He-IBID material resembles more electron-beam-induced-deposition (EBID) material than Ga-ion-beam-induced-deposition (Ga-IBID) material. Nevertheless, the spatial resolution for He-IBID is in general better than for EBID and Ga-IBID; in particular, proximity effects are minimal.

Determining Energies and Cross Sections of Individual Ions Using Higher-Order Harmonics in Fourier Transform Charge Detection Mass Spectrometry (FT-CDMS)

NASA Astrophysics Data System (ADS)

Harper, Conner C.; Elliott, Andrew G.; Lin, Haw-Wei; Williams, Evan R.

2018-06-01

A general method for in situ measurements of the energy of individual ions trapped and weighed using charge detection mass spectrometry (CDMS) is described. Highly charged (> 300 e), individual polyethylene glycol (PEG) ions are trapped and oscillate within an electrostatic trap, producing a time domain signal. A segmented Fourier transform (FT) of this signal yields the temporal evolution of the fundamental and harmonic frequencies of ion motion throughout the 500-ms trap time. The ratio of the fundamental frequency and second harmonic (HAR) depends on the ion energy, which is an essential parameter for measuring ion mass in CDMS. This relationship is calibrated using simulated ion signals, and the calibration is compared to the HAR values measured for PEG ion signals where the ion energy was also determined using an independent method that requires that the ions be highly charged (> 300 e). The mean error of 0.6% between the two measurements indicates that the HAR method is an accurate means of ion energy determination that does not depend on ion size or charge. The HAR is determined dynamically over the entire trapping period, making it possible to observe the change in ion energy that takes place as solvent evaporates from the ion and collisions with background gas occur. This method makes it possible to measure mass changes, either from solvent evaporation or from molecular fragmentation (MSn), as well as the cross sections of ions measured using CDMS.

Global Profiling and Novel Structure Discovery Using Multiple Neutral Loss/Precursor Ion Scanning Combined with Substructure Recognition and Statistical Analysis (MNPSS): Characterization of Terpene-Conjugated Curcuminoids in Curcuma longa as a Case Study.

PubMed

Qiao, Xue; Lin, Xiong-hao; Ji, Shuai; Zhang, Zheng-xiang; Bo, Tao; Guo, De-an; Ye, Min

2016-01-05

To fully understand the chemical diversity of an herbal medicine is challenging. In this work, we describe a new approach to globally profile and discover novel compounds from an herbal extract using multiple neutral loss/precursor ion scanning combined with substructure recognition and statistical analysis. Turmeric (the rhizomes of Curcuma longa L.) was used as an example. This approach consists of three steps: (i) multiple neutral loss/precursor ion scanning to obtain substructure information; (ii) targeted identification of new compounds by extracted ion current and substructure recognition; and (iii) untargeted identification using total ion current and multivariate statistical analysis to discover novel structures. Using this approach, 846 terpecurcumins (terpene-conjugated curcuminoids) were discovered from turmeric, including a number of potentially novel compounds. Furthermore, two unprecedented compounds (terpecurcumins X and Y) were purified, and their structures were identified by NMR spectroscopy. This study extended the application of mass spectrometry to global profiling of natural products in herbal medicines and could help chemists to rapidly discover novel compounds from a complex matrix.

Analysis of spectra of 3s-3p and 3p-3d transitions of highly-charged copper ions

NASA Astrophysics Data System (ADS)

Su, M. G.; Min, Q.; He, S. Q.; Wu, L.; Sun, R.; Ding, X. B.; Sun, D. X.

2017-08-01

Beam-foil excited spectra in the range of 160-360 Å from highly charged copper ions were identified with the aid of the National Institute of Standards and Technology Atomic Spectra Database and theoretical calculations with Cowan and Flexible Atomic Code (FAC) calculations. Spectra arising from 3s-3p and 3p-3d transitions of Cu13+-Cu22+ ions were considered. The ion fraction at an ion beam energy of 110 MeV was estimated from the equilibrium charge distribution of the fast ion beams after passing through the solid. The corresponding simulated spectra were in good agreement with the experimental result. Our Cowan and FAC calculation results should be useful for further spectral identification and lifetime measurements of highly charged copper ions.

Recent charge-breeding developments with EBIS/T devices (invited).

PubMed

Schwarz, S; Lapierre, A

2016-02-01

Short breeding times, narrow charge state distributions, low background, high efficiency, and the flexible time structure of the ejected low-emittance ion pulses are among the most attractive features of electron beam ion source or trap (EBIS/T) based charge breeders. Significant progress has been made to further improve these properties: Several groups are working to increase current densities towards 10(3) or even 10(4) A/cm(2). These current densities will become necessary to deliver high charge states of heavy nuclei in a short time and/or provide sufficient space-charge capacity to handle high-current ion beams in next-generation rare-isotope beam (RIB) facilities. Efficient capture of continuous beams, attractive because of its potential of handling highest-current ion beams, has become possible with the development of high-density electron beams of >1 A. Requests for the time structure of the charge bred ion pulse range from ultra-short pulses to quasi-continuous beams. Progress is being made on both ends of this spectrum, by either dividing the extracted charge in many pulse-lets, adjusting the extraction potential for a near-uniform long pulse, or adding dedicated devices to spread the ion bunches delivered from the EBIS/T in time. Advances in EBIS/T charge state breeding are summarized, including recent results with NSCL's ReA EBIS/T charge breeder.

Recent charge-breeding developments with EBIS/T devices (invited)

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

Schwarz, S., E-mail: schwarz@nscl.msu.edu; Lapierre, A.

Short breeding times, narrow charge state distributions, low background, high efficiency, and the flexible time structure of the ejected low-emittance ion pulses are among the most attractive features of electron beam ion source or trap (EBIS/T) based charge breeders. Significant progress has been made to further improve these properties: Several groups are working to increase current densities towards 10{sup 3} or even 10{sup 4} A/cm{sup 2}. These current densities will become necessary to deliver high charge states of heavy nuclei in a short time and/or provide sufficient space-charge capacity to handle high-current ion beams in next-generation rare-isotope beam (RIB) facilities.more » Efficient capture of continuous beams, attractive because of its potential of handling highest-current ion beams, has become possible with the development of high-density electron beams of >1 A. Requests for the time structure of the charge bred ion pulse range from ultra-short pulses to quasi-continuous beams. Progress is being made on both ends of this spectrum, by either dividing the extracted charge in many pulse-lets, adjusting the extraction potential for a near-uniform long pulse, or adding dedicated devices to spread the ion bunches delivered from the EBIS/T in time. Advances in EBIS/T charge state breeding are summarized, including recent results with NSCL’s ReA EBIS/T charge breeder.« less

Characterization of Boron Contamination in Fluorine Implantation using Boron Trifluoride as a Source Material

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

Schmeide, Matthias; Kondratenko, Serguei

2011-01-07

Fluorine implantation process purity was considered on different types of high current implanters. It was found that implanters equipped with an indirectly heated cathode ion source show an enhanced deep boron contamination compared to a high current implanter using a cold RF-driven multicusp ion source when boron trifluoride is used for fluorine implantations. This contamination is directly related to the source technology and thus, should be considered potentially for any implanter design using hot cathode/hot filament ion source, independently of the manufacturer.The boron contamination results from the generation of double charged boron ions in the arc chamber and the subsequentmore » charge exchange reaction to single charged boron ions taking place between the arc chamber and the extraction electrode. The generation of the double charged boron ions depends mostly on the source parameters, whereas the pressure in the region between the arc chamber and the extraction electrode is mostly responsible for the charge exchange from double charged to single charged ions. The apparent mass covers a wide range, starting at mass 11. A portion of boron ions with energies of (19/11) times higher than fluorine energy has the same magnetic rigidity as fluorine beam and cannot be separated by the analyzer magnet. The earlier described charge exchange effects between the extraction electrode and the entrance to the analyzer magnet, however, generates boron beam with a higher magnetic rigidity compared to fluorine beam and cannot cause boron contamination after mass-separation.The energetic boron contamination was studied as a function of the ion source parameters, such as gas flow, arc voltage, and source magnet settings, as well as analyzing magnet aperture resolution. This allows process optimization reducing boron contamination to the level acceptable for device performance.« less

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2014-05-13

The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

A DIM model for sodium cluster-ions interacting with a charged conducting sphere

NASA Astrophysics Data System (ADS)

Kuntz, P. J.

A diatomics-in-molecules (DIM) model for the energy, shape and charge distribution of metal cluster ions in the presence of a charged insulated conducting sphere is presented. The electrostatic interaction between the sphere and the cluster-ion is introduced in a self-consistent manner which allows the sphere to be polarized by the ion and the ion by the sphere. This interaction appears in the diagonal elements of the model Hamiltonian matrix in such a way that the lowest eigenvalue includes the correct electrostatic energy for the charge distribution in the ground state. The model is applied to the calculation of fusion barriers for Na+2 and Na+3 ions. When both the charge distribution and the geometric configuration of the cluster-ion are allowed to relax freely, the energy as a function of distance from the sphere is nearly the same as that calculated from the electrostatic energy alone, which implies that details of the molecular structure of the cluster-ion can be neglected in calculating fusion barriers from charge polarization alone. That the fusion barriers lie sufficiently far away from the sphere so that the molecule does not dissociate under the influence of the Coulomb interaction confirms that it is meaningful to speak of two separate entities at the barrier position.

Solar Wind Charge Exchange Studies Of Highly Charged Ions On Atomic Hydrogen

NASA Astrophysics Data System (ADS)

Draganić, I. N.; Seely, D. G.; McCammon, D.; Havener, C. C.

2011-06-01

Accurate studies of low-energy charge exchange (CX) are critical to understanding underlying soft X-ray radiation processes in the interaction of highly charged ions from the solar wind with the neutral atoms and molecules in the heliosphere, cometary comas, planetary atmospheres, interstellar winds, etc.. Particularly important are the CX cross sections for bare, H-like, and He-like ions of C, N, O and Ne, which are the dominant charge states for these heavier elements in the solar wind. Absolute total cross sections for single electron capture by H-like ions of C, N, O and fully-stripped O ions from atomic hydrogen have been measured in an expanded range of relative collision energies (5 eV/u-20 keV/u) and compared to previous H-oven measurements. The present measurements are performed using a merged-beams technique with intense highly charged ion beams extracted from a 14.5 GHz ECR ion source installed on a high voltage platform at the Oak Ridge National Laboratory. For the collision energy range of 0.3 keV/u-3.3 keV/u, which corresponds to typical ion velocities in the solar wind, the new measurements are in good agreement with previous H-oven measurements. The experimental results are discussed in detail and compared with theoretical calculations where available.

A new battery-charging method suggested by molecular dynamics simulations.

PubMed

Abou Hamad, Ibrahim; Novotny, M A; Wipf, D O; Rikvold, P A

2010-03-20

Based on large-scale molecular dynamics simulations, we propose a new charging method that should be capable of charging a lithium-ion battery in a fraction of the time needed when using traditional methods. This charging method uses an additional applied oscillatory electric field. Our simulation results show that this charging method offers a great reduction in the average intercalation time for Li(+) ions, which dominates the charging time. The oscillating field not only increases the diffusion rate of Li(+) ions in the electrolyte but, more importantly, also enhances intercalation by lowering the corresponding overall energy barrier.

Design and application of a data-independent precursor and product ion repository.

PubMed

Thalassinos, Konstantinos; Vissers, Johannes P C; Tenzer, Stefan; Levin, Yishai; Thompson, J Will; Daniel, David; Mann, Darrin; DeLong, Mark R; Moseley, M Arthur; America, Antoine H; Ottens, Andrew K; Cavey, Greg S; Efstathiou, Georgios; Scrivens, James H; Langridge, James I; Geromanos, Scott J

2012-10-01

The functional design and application of a data-independent LC-MS precursor and product ion repository for protein identification, quantification, and validation is conceptually described. The ion repository was constructed from the sequence search results of a broad range of discovery experiments investigating various tissue types of two closely related mammalian species. The relative high degree of similarity in protein complement, ion detection, and peptide and protein identification allows for the analysis of normalized precursor and product ion intensity values, as well as standardized retention times, creating a multidimensional/orthogonal queryable, qualitative, and quantitative space. Peptide ion map selection for identification and quantification is primarily based on replication and limited variation. The information is stored in a relational database and is used to create peptide- and protein-specific fragment ion maps that can be queried in a targeted fashion against the raw or time aligned ion detections. These queries can be conducted either individually or as groups, where the latter affords pathway and molecular machinery analysis of the protein complement. The presented results also suggest that peptide ionization and fragmentation efficiencies are highly conserved between experiments and practically independent of the analyzed biological sample when using similar instrumentation. Moreover, the data illustrate only minor variation in ionization efficiency with amino acid sequence substitutions occurring between species. Finally, the data and the presented results illustrate how LC-MS performance metrics can be extracted and utilized to ensure optimal performance of the employed analytical workflows.

Optical properties of β-Ga2O3 nanorods synthesized by a simple and cost-effective method using egg white solution

NASA Astrophysics Data System (ADS)

Phumying, Santi; Labauyai, Sarawut; Chareonboon, Wirat; Phokha, Sumalin; Maensiri, Santi

2015-06-01

In this paper, we report on the optical properties of gallium oxide (β-Ga2O3) nanorods synthesized by a simple, cost-effective and environment-friendly method using gallium(III) nitrate hydrate and freshly extracted egg white (ovalbumin) in an aqueous medium. The extracted egg white acted as a matrix for the entrapment of gallium ions to generate a gelled precursor. The structure of the prepared samples was studied by X-ray diffraction and Raman spectroscopy to confirm the formation of β-Ga2O3 with a monoclinic structure after calcination of the precursor in air at 750, 850, and 950 °C for 3 h. Scanning electron microscopy images revealed the morphology and formation of nanorods with different sizes and shapes in the samples, resulting from the effect of the calcination temperature. All the samples showed a strong UV absorption with the band gap in the range of 3.87-3.97 eV. Room-temperature photoluminescence spectra of all the samples also showed a strong UV emission. The UV emission results were discussed based on the basis of charge recombination.

Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Hsu, Chun-Tsung; Hu, Chi-Chang

2013-11-01

A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

Poly (acrylic acid sodium) grafted carboxymethyl cellulose as a high performance polymer binder for silicon anode in lithium ion batteries

PubMed Central

Wei, Liangming; Chen, Changxin; Hou, Zhongyu; Wei, Hao

2016-01-01

The design of novel binder systems is required for the high capacity silicon (Si) anodes which usually undergo huge volume change during the charge/discharge cycling. Here, we introduce a poly (acrylic acid sodium)-grafted-carboxymethyl cellulose (NaPAA-g-CMC) copolymer as an excellent binder for Si anode in lithium ion batteries (LIBs). The NaPAA-g-CMC copolymer was prepared via a free radical graft polymerization method by using CMC and acrylic acid as precursors. Unlike the linear, one-dimensional binders, the NaPAA-g-CMC copolymer binder is expected to present multi-point interaction with Si surface, resulting in enhanced binding ability with Si particles as well as with the copper (Cu) current collectors, and building a stable solid electrolyte interface (SEI) layer on the Si surface. The NaPAA-g-CMC based Si anode shows much better cycle stability and higher coulombic efficiency than those made with the well-known linear polymeric binders such as CMC and NaPPA. PMID:26786315

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

NASA Technical Reports Server (NTRS)

Pitsch, S.; Krishnamurthy, R.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

2000-01-01

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

Korteweg-deVries-Burgers (KdVB) equation in a five component cometary plasma with kappa described electrons and ions

NASA Astrophysics Data System (ADS)

Michael, Manesh; Willington, Neethu T.; Jayakumar, Neethu; Sebastian, Sijo; Sreekala, G.; Venugopal, Chandu

2016-12-01

We investigate the existence of ion-acoustic shock waves in a five component cometary plasma consisting of positively and negatively charged oxygen ions, kappa described hydrogen ions, hot solar electrons, and slightly colder cometary electrons. The KdVB equation has been derived for the system, and its solution plotted for different kappa values, oxygen ion densities, as well as the temperature ratios for the ions. It is found that the amplitude of the shock wave decreases with increasing kappa values. The strength of the shock profile decreases with increasing temperatures of the positively charged oxygen ions and densities of negatively charged oxygen ions.

Electron cyclotron resonance sources: Historical review and future prospects (invited)

NASA Astrophysics Data System (ADS)

Geller, R.

1998-03-01

Low charge state electron cyclotron resonance ion source (ECRIS) work since 1965 and high charge state ECRIS since 1974. These ECR sources are categorized into three main sections: (1) Low charged ion (ECRIS) inside simple magnetic mirror or Bucket configurations. (2) High charged ion ECRIS inside min-B mirror configurations. (3) Short pulsed ECRIS with highly charged ions where the ion confinement is disturbed for a short while, which allows the extraction of intense ion pulses. Future prospects are based on rational scaling of the magnetic confinement including high B modes, by increasing the radio frequency (rf) frequency and ECR magnetic field. In this case, charge exchange has to be minimized and plasma instabilities have to be avoided. However, clever empirical tricks lead also to outstanding not always predicted improvements. Let us cite: optimized rf plasma coupling, electron guns, gas mixing, wall coating, biased electrodes, and more recently multiple ECR frequency heating. ECRIS have not yet achieved their optimal possibilities. Let us wait for the next generation of superconducting ECRIS and the possible use of subcentimeter waves.

Electron cyclotron resonance sources: Historical review and future prospects (invited)

NASA Astrophysics Data System (ADS)

Geller, R.

1998-02-01

Low charge state electron cyclotron resonance ion source (ECRIS) work since 1965 and high charge state ECRIS since 1974. These ECR sources are categorized into three main sections: (1) Low charged ion (ECRIS) inside simple magnetic mirror or Bucket configurations. (2) High charged ion ECRIS inside min-B mirror configurations. (3) Short pulsed ECRIS with highly charged ions where the ion confinement is disturbed for a short while, which allows the extraction of intense ion pulses. Future prospects are based on rational scaling of the magnetic confinement including high B modes, by increasing the radio frequency (rf) frequency and ECR magnetic field. In this case, charge exchange has to be minimized and plasma instabilities have to be avoided. However, clever empirical tricks lead also to outstanding not always predicted improvements. Let us cite: optimized rf plasma coupling, electron guns, gas mixing, wall coating, biased electrodes, and more recently multiple ECR frequency heating. ECRIS have not yet achieved their optimal possibilities. Let us wait for the next generation of superconducting ECRIS and the possible use of subcentimeter waves.

Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.

1997-01-01

The laser ablation/ion storage facility at the UNLV Physics Department is dedicated to the study of atomic processes in low temperature plasmas. Our current program is directed to the study of charge transfer of multiply charged ions and neutrals that are of importance to astrophysics at energies less than 1 eV (about 10(exp 4) K). Specifically, we measure the charge transfer rate coefficient of ions such as N(2+), Si(3+), Si(3+), with helium and Fe(2+) with molecular and atomic hydrogen. All these ions are found in a variety of astrophysical plasmas. Their electron transfer reactions with neutral atoms can affect the ionization equilibrium of the plasma.

Metrology and Transport of Multiply Charged Ions

NASA Astrophysics Data System (ADS)

Kulkarni, Dhruva

The transport and interaction of singly- and multiply-charged ions with matter has been studied. The experiments were performed in an ultra-high vacuum environment. The low- and hyperthermal-energy ion beamline was used as a source of singly charged ions, while the CUEBIT facility was used as a source of multiply charged ions. The kinetic energy of the ion beam obtained from the CUEBIT is offset from the nominal value expected from the applied electrostatic potentials. These offsets were studied by measuring the kinetic energy of the beam using a retarding field analyzer (RFA). The offset was attributed to the space charge of the electron beam that is used to create the multiply charged ions. The charge density of the electron beam was varied by changing operational parameters of the electron beam, namely the electron beam current and the energy of the electron beam. Ion beams of Ar4+ and Ar8+ were extracted from the source and the offsets observed in the kinetic energy were related to the variation in the space charge potential of the electron beam. Measurements of these offsets, ranging from 100 eV/Q to 300 eV/Q, are significant and important for experiments that aim to utilize the potential energy of slow multiply charged ions. The transport of ions using capillaries has been studied to investigate the viability of ion-guiding as a means for a novel ion delivery mechanism. Results on transport through large bore capillaries (macrocapillaries) that probe both the geometric and ionguided mechanisms are presented. The angle- and position-dependent transport properties were found to depend on the material of the capillary (specifically, whether metal or insulator) and the geometry of the capillary. Rb+ ions at a kinetic energy of 1 keV were transmitted through metal and glass capillaries that were a few centimeters in length and a few millimeters in diameter. Oscillations were observed in the capillaries made of glass which were absent in the metal capillaries. Calculations based on the geometry of the experimental setup and kinematics of the ions showed that these oscillations could be attributed to the charge patches formed on the capillary walls. Electronic excitations in solids due to energetic ions at low kinetic energy were measured by using Schottky diodes. Hot electron currents measured at the backside of an Ag/n-Si Schottky diode due to ion bombardment on the frontside were found to depend on the kinetic energy (500 eV to 1500 eV) and angle of incidence (+/-30°) of the ion (Rb+) beam. A sharp upturn in the energy dependent yield is consistent with a kinetic emission model for electronic excitations utilizing the device Schottky barrier as determined from current-voltage characteristics. Backside currents measured for ion incident angle are strongly peaked about normal incidence. Accounting for the increased transport distance for excited charges at non-normal incidence, the mean free path for electrons in silver was found to be 5.2 +/- 1.4 nm, which is consistent with values reported in the literature.

The role of amorphous precursors in the crystallization of La and Nd carbonates

NASA Astrophysics Data System (ADS)

Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

2015-07-01

Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01497b

ION PRODUCING MECHANISM (CHARGE CUPS)

DOEpatents

Brobeck, W.W.

1959-04-21

The problems of confining a charge material in a calutron and uniformly distributing heat to the charge is described. The charge is held in a cup of thermally conductive material removably disposed within the charge chamber of the ion source block. A central thermally conducting stem is incorporated within the cup for conducting heat to the central portion of the charge contained within the cup.

Dynamics of ions in a water drop using the AMOEBA polarizable force field

NASA Astrophysics Data System (ADS)

Thaunay, Florian; Ohanessian, Gilles; Clavaguéra, Carine

2017-03-01

Various ions carrying a charge from -2 to +3 were confined in a drop of 100 water molecules as a way to model coordination properties inside the cluster and at the interface. The behavior of the ions has been followed by molecular dynamics with the AMOEBA polarizable force field. Multiply charged ions and small singly charged ions are found to lie inside the droplet, while bigger monovalent ions sit near the surface. The results provide a coherent picture of average structural properties as well as residence times for which a general trend is proposed, especially for the anions.

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.

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

Meusel, O., E-mail: o.meusel@iap.uni-frankfurt.de; Droba, M.; Noll, D.

The transport of intense ion beams is affected by the collective behavior of this kind of multi-particle and multi-species system. The space charge expressed by the generalized perveance dominates the dynamical process of thermalisation, which leads to emittance growth. To prevent changes of intrinsic beam properties and to reduce the intensity dependent focusing forces, space charge compensation seems to be an adequate solution. In the case of positively charged ion beams, electrons produced by residual gas ionization and secondary electrons provide the space charge compensation. The influence of the compensation particles on the beam transport and the local degree ofmore » space charge compensation is given by different beam properties as well as the ion beam optics. Especially for highly charged ion beams, space charge compensation in combination with poor vacuum conditions leads to recombination processes and therefore increased beam losses. Strategies for providing a compensation-electron reservoir at very low residual gas pressures will be discussed.« less

Heavy ion therapy: Bevalac epoch

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

Castro, J.R.

1993-10-01

An overview of heavy ion therapy at the Bevelac complex (SuperHILac linear accelerator + Bevatron) is given. Treatment planning, clinical results with helium ions on the skull base and uveal melanoma, clinical results with high-LET charged particles, neon radiotherapy of prostate cancer, heavy charged particle irradiation for unfavorable soft tissue sarcoma, preliminary results in heavy charged particle irradiation of bone sarcoma, and irradiation of bile duct carcinoma with charged particles and-or photons are all covered. (GHH)

Photodegradation of dissolved organic matter in ice under solar irradiation.

PubMed

Xue, Shuang; Wang, Chao; Zhang, Zhaohong; Song, Youtao; Liu, Qiang

2016-02-01

The photodegradation behavior of dissolved organic matter (DOM) with different origins in ice under solar irradiation was investigated. Exposure to sunlight at 2.7 × 10(5) J m(-2) resulted in dissolved organic carbon (DOC) reductions of 22.1-36.5% in ice. The naturally occurring DOM had higher photodegradation potentials than the wastewater-derived DOM in ice. Ultraviolet (UV)-absorbing compounds in DOM, regardless of DOM origin, had much higher photodegradation potentials than gross DOC in ice. The susceptibility of UV-absorbing compounds with natural origin to sunlight exposure in ice was higher than those derived from wastewater. Trihalomethane (THM) precursors were more susceptible to photochemical reactions than gross DOC and haloacetic acid (HAA) precursors in ice. THM precursors in naturally occurring DOM were more photoreactive than those in wastewater-derived DOM in ice, while the photoreactivity of HAA precursors in ice was independent of DOM origin. In ice, the photoreactivity of humic-like fluorescent materials, regardless of DOM origin, was higher than that of gross DOC and protein-like fluorescent materials. DOC reductions caused by sunlight irradiation were found to be negatively correlated to DOC levels, and positively correlated to the aromaticity of DOM. The photodegradation of both wastewater-derived and naturally occurring DOM in ice was significantly facilitated at both acid and alkaline pH, as compared to neutral pH. The photodegradation of DOM in ice, regardless of the origin, was facilitated by nitrate ion [Formula: see text] , nitrite ion [Formula: see text] , ferric ion (Fe(3+)) and ferrous ion (Fe(2+)), and on the other hand, was inhibited by chloridion ion (Cl(-)) and copper ion (Cu(2+)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions

NASA Astrophysics Data System (ADS)

Guerrero-García, Guillermo Iván; González-Tovar, Enrique; Olvera de la Cruz, Mónica

2011-08-01

The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-elec-trolytes with different ion sizes.

Complexation of Polyelectrolyte Micelles with Oppositely Charged Linear Chains.

PubMed

Kalogirou, Andreas; Gergidis, Leonidas N; Miliou, Kalliopi; Vlahos, Costas

2017-03-02

The formation of interpolyelectrolyte complexes (IPECs) from linear AB diblock copolymer precursor micelles and oppositely charged linear homopolymers is studied by means of molecular dynamics simulations. All beads of the linear polyelectrolyte (C) are charged with elementary quenched charge +1e, whereas in the diblock copolymer only the solvophilic (A) type beads have quenched charge -1e. For the same Bjerrum length, the ratio of positive to negative charges, Z +/- , of the mixture and the relative length of charged moieties r determine the size of IPECs. We found a nonmonotonic variation of the size of the IPECs with Z +/- . For small Z +/- values, the IPECs retain the size of the precursor micelle, whereas at larger Z +/- values the IPECs decrease in size due to the contraction of the corona and then increase as the aggregation number of the micelle increases. The minimum size of the IPECs is obtained at lower Z +/- values when the length of the hydrophilic block of the linear diblock copolymer decreases. The aforementioned findings are in agreement with experimental results. At a smaller Bjerrum length, we obtain the same trends but at even smaller Z +/- values. The linear homopolymer charged units are distributed throughout the corona.

Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

PubMed

Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

2015-11-15

The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long-lived intermediates formed by electron capture/transfer in which a labile hydrogen atom is present and plays a key role with low energy processes leading to c and z ion formation. Ab initio and density functional calculations are performed to support our conclusion, which depends most importantly on the proton affinity, electron affinity and hydrogen atom affinity of the TEMPO moiety.

First charge breeding results at CARIBU EBIS

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

Kondrashev, S., E-mail: kondrashev@anl.gov; Barcikowski, A., E-mail: kondrashev@anl.gov; Dickerson, C., E-mail: kondrashev@anl.gov

The Electron Beam Ion Source (EBIS) developed to breed CARIBU radioactive beams at ATLAS is currently in the off-line commissioning stage. The beam commissioning is being performed using a low emittance surface ionization source producing singly-charged cesium ions. The primary goal of the off-line commissioning is the demonstration of high-efficiency charge breeding in the pulsed injection mode. An overview of the final design of the CARIBU EBIS charge breeder, the off-line commissioning installation and the first results on charge breeding of stable cesium ions are presented and discussed.

Conversion of multiple analyte cation types to a single analyte anion type via ion/ion charge inversion.

PubMed

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

2009-11-01

Charge inversion ion/ion reactions can convert several cation types associated with a single analyte molecule to a single anion type for subsequent mass analysis. Specifically, analyte ions present with one of a variety of cationizing agents, such as an excess proton, excess sodium ion, or excess potassium ion, can all be converted to the deprotonated molecule, provided that a stable anion can be generated for the analyte. Multiply deprotonated species that are capable of exchanging a proton for a metal ion serve as the reagent anions for the reaction. This process is demonstrated here for warfarin and for a glutathione conjugate. Examples for several other glutathione conjugates are provided as supplementary material to demonstrate the generality of the reaction. In the case of glutathione conjugates, multiple metal ions can be associated with the singly-charged analyte due to the presence of two carboxylate groups. The charge inversion reaction involves the removal of the excess cationizing agent, as well as any metal ions associated with anionic groups to yield a singly deprotonated analyte molecule. The ability to convert multiple cation types to a single anion type is analytically desirable in cases in which the analyte signal is distributed among several cation types, as is common in the electrospray ionization of solutions with relatively high salt contents. For analyte species that undergo efficient charge inversion, such as glutathione conjugates, there is the additional potential advantage for significantly improved signal-to-noise ratios when species that give rise to 'chemical noise' in the positive ion spectrum do not undergo efficient charge inversion.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-12-07

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1990-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, S.F.; Rauh, R.D.

1990-07-03

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counter electrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films. 4 figs.

Properties of Minor Ions in the Solar Wind and Implications for the Background Solar Wind Plasma

NASA Technical Reports Server (NTRS)

Esser, Ruth; Ling, James (Technical Monitor)

2001-01-01

Ion charge states measured in situ in interplanetary space carry information on the properties of the solar wind plasma in the inner corona where these ion charge states are formed. The goal of the proposed research was to determine solar wind models and coronal observations that are necessary tools for the interpretation of the ion charge state observations made in situ in the solar wind.

Lithium-Ion Battery Failure: Effects of State of Charge and Packing Configuration

DTIC Science & Technology

2016-08-22

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6180--16-9689 Lithium - Ion Battery Failure: Effects of State of Charge and Packing...PAGES 17. LIMITATION OF ABSTRACT Lithium - Ion Battery Failure: Effects of State of Charge and Packing Configuration Neil S. Spinner,* Katherine M. Hinnant...Steven G. Tuttle (202) 404-3419 Lithium - ion battery safety remains a significant concern, as battery failure leads to ejection of hazardous materials

New precursors for direct synthesis of single phase Na- and K-{beta}{double_prime}-aluminas for use in AMTEC systems

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

Cook, R.L.; MacQueen, D.B.; Bader, K.E.

1997-12-31

Alkali Metal Thermoelectric Converters (AMTEC) are efficient direct energy conversion devices that depend on the use of highly conductive beta-alumina membranes for their operation. The key component of the AMTEC system is a highly conductive Na-{beta}{double_prime}-alumina solid electrolyte which conducts sodium ions from the high to low temperature zone, thereby generating electricity. AMTEC cells convert thermal to electrical energy by using heat to produce and maintain an alkali metal concentration gradient across the ion transporting BASE membrane. They have developed a method for producing pure phase Na-{beta}{double_prime}-alumina and K-{beta}{double_prime}-alumina powders from single phase nano-sized carboxylato-alumoxanes precursors. Sodium or potassium ionsmore » (the mobile ions) and either Mg{sup 2+} or Li{sup +} ions (which stabilize the {beta}{double_prime}-alumina structure) can be atomically dispersed into the carboxylato-alumoxane lattice at low (< 100 C) temperature. Calculation of the carboxylato-alumoxane precursors at 1,200--1,500 C produces pure phase {beta}{double_prime}-alumina powders.« less

Sodium modified molybdenum sulfide via molten salt electrolysis as an anode material for high performance sodium-ion batteries.

PubMed

Wang, Shuai; Tu, Jiguo; Yuan, Yan; Ma, Rui; Jiao, Shuqiang

2016-01-28

The paper reports a facile and cost effective method for fabricating sodium molybdenum sulfide nanoparticles through using MoS2 sheets as the precursor by sodium-modification. The electrochemical performances of sodium molybdenum sulfide nanoparticles are studied as anode materials for sodium-ion batteries. The galvanostatic charge-discharge measurements have been performed in a voltage range of 0.01-2.6 V vs. Na(+)/Na under different current densities, using the as-prepared sodium molybdenum sulfide nanoparticles as a working electrode. Typically, the initial discharge and charge capacities of sodium molybdenum sulfide nanoparticles are 475 and 380 mA h g(-1), respectively, at a current density of 20 mA g(-1). The sodium molybdenum sulfide nanoparticles exhibit high capacity with a reversible discharge capacity of about 190 mA h g(-1) after 100 cycles. It should be emphasized that the discharge reaction consists of two steps which correspond to voltage plateaus of 0.93 V and 0.85 V vs. Na(+)/Na in the first discharge curve of the Na/MoS2 battery, respectively. But there is only one apparent voltage plateau in the Na/Na-Mo-S battery, and it reduces to below 0.5 V vs. Na(+)/Na, which can enhance the power density. All of the findings demonstrate that sodium molybdenum sulfide nanoparticles have steady cycling performance and environmental and cost friendliness as next generation secondary batteries.

Three-dimensionally interconnected Si frameworks derived from natural halloysite clay: a high-capacity anode material for lithium-ion batteries.

PubMed

Wan, Hao; Xiong, Hao; Liu, Xiaohe; Chen, Gen; Zhang, Ning; Wang, Haidong; Ma, Renzhi; Qiu, Guanzhou

2018-05-23

On account of its high theoretical capacity, silicon (Si) has been regarded as a promising anode material for Li-ion batteries. Extracting Si content from earth-abundant and low-cost aluminosilicate minerals, rather than from artificial silica (SiO2) precursors, is a more favorable and practical method for the large-scale application of Si anodes. In this work, three-dimensionally interconnected (3D-interconnected) Si frameworks with a branch diameter of ∼15 nm are prepared by the reduction of amorphous SiO2 nanotubes derived from natural halloysite clay. Benefiting from their nanostructure, the as-prepared 3D-interconnected Si frameworks yield high reversible capacities of 2.54 A h g-1 at 0.1 A g-1 after 50 cycles, 1.87 A h g-1 at 0.5 A g-1 after 200 cycles, and 0.97 A h g-1 at 2 A g-1 after a long-term charge-discharge process of 500 cycles, remarkably outperforming the commercial Si material. Further, when the as-prepared Si frameworks and commercial LiCoO2 cathodes are paired in full cells, a high anode capacity of 0.98 A h g-1 is achieved after 100 cycles of rapid charge/discharge at 2 A g-1. This work provides a new strategy for the synthesis of high-capacity Si anodes derived from natural aluminosilicate clay.

Apparatus and method of determining molecular weight of large molecules

DOEpatents

Fuerstenau, S.; Benner, W.H.; Madden, N.M.; Searles, W.

1998-06-23

A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e{sup {minus}} are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation. 14 figs.

Apparatus and method of determining molecular weight of large molecules

DOEpatents

Fuerstenau, Stephen; Benner, W. Henry; Madden, Norman; Searles, William

1998-01-01

A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e.sup.- are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation.

Coulomb clusters in RETRAP

NASA Astrophysics Data System (ADS)

Steiger, J.; Beck, B. R.; Gruber, L.; Church, D. A.; Holder, J. P.; Schneider, D.

1999-01-01

Storage rings and Penning traps are being used to study ions in their highest charge states. Both devices must have the capability for ion cooling in order to perform high precision measurements such as mass spectrometry and laser spectroscopy. This is accomplished in storage rings in a merged beam arrangement where a cold electron beam moves at the speed of the ions. In RETRAP, a Penning trap located at Lawrence Livermore National Laboratory, a sympathetic laser/ion cooling scheme has been implemented. In a first step, singly charged beryllium ions are cooled electronically by a tuned circuit and optically by a laser. Then hot, highly charged ions are merged into the cold Be plasma. By collisions, their kinetic energy is reduced to the temperature of the Be plasma. First experiments indicate that the highly charged ions form a strongly coupled plasma with a Coulomb coupling parameter exceeding 1000.

Electrode materials for rechargeable battery

DOEpatents

Johnson, Christopher; Kang, Sun-Ho

2015-09-08

A positive electrode is disclosed for a non-aqueous electrolyte lithium rechargeable cell or battery. The electrode comprises a lithium containing material of the formula Na.sub.yLi.sub.xNi.sub.zMn.sub.1-z-z'M.sub.z'O.sub.d, wherein M is a metal cation, x+y>1, 0

Overcharging below the nanoscale: Multivalent cations reverse the ion selectivity of a biological channel

NASA Astrophysics Data System (ADS)

García-Giménez, Elena; Alcaraz, Antonio; Aguilella, Vicente M.

2010-02-01

We report charge inversion within a nanoscopic biological protein ion channel in salts of multivalent ions. The presence of positive divalent and trivalent counterions reverses the cationic selectivity of the OmpF channel, a general diffusion porin located in the outer membrane of E. coli. We discuss the conditions under which charge inversion can be inferred from the change in sign of the measured quantity, the channel zero current potential. By comparing experimental results in protein channels whose charge has been modified after site-directed mutagenesis, the predictions of current theories of charge inversion are critically examined. It is emphasized that charge inversion does not necessarily increase with the bare surface charge density of the interface and that even this concept of surface charge density may become meaningless in some biological ion channels. Thus, any theory based on electrostatic correlations or chemical binding should explicitly take into account the particular structure of the charged interface.

An omnipotent Li-ion battery charger with multimode control and polarity reversible techniques

NASA Astrophysics Data System (ADS)

Chen, Jiann-Jong; Ku, Yi-Tsen; Yang, Hong-Yi; Hwang, Yuh-Shyan; Yu, Cheng-Chieh

2016-07-01

The omnipotent Li-ion battery charger with multimode control and polarity reversible techniques is presented in this article. The proposed chip is fabricated with TSMC 0.35μm 2P4M complementary metal-oxide- semiconductor processes, and the chip area including pads is 1.5 × 1.5 mm2. The structure of the omnipotent charger combines three charging modes and polarity reversible techniques, which adapt to any Li-ion batteries. The three reversible Li-ion battery charging modes, including trickle-current charging, large-current charging and constant-voltage charging, can charge in matching polarities or opposite polarities. The proposed circuit has a maximum charging current of 300 mA and the input voltage of the proposed circuit is set to 4.5 V. The maximum efficiency of the proposed charger is about 91% and its average efficiency is 74.8%. The omnipotent charger can precisely provide the charging current to the battery.

Carbon Mineralization Using Phosphate and Silicate Ions

NASA Astrophysics Data System (ADS)

Gokturk, H.

2013-12-01

Carbon dioxide (CO2) reduction from combustion of fossil fuels has become an urgent concern for the society due to marked increase in weather related natural disasters and other negative consequences of global warming. CO2 is a highly stable molecule which does not readily interact with other neutral molecules. However it is more responsive to ions due to charge versus quadrupole interaction [1-2]. Ions can be created by dissolving a salt in water and then aerosolizing the solution. This approach gives CO2 molecules a chance to interact with the hydrated salt ions over the large surface area of the aerosol. Ion containing aerosols exist in nature, an example being sea spray particles generated by breaking waves. Such particles contain singly and doubly charged salt ions including Na+, Cl-, Mg++ and SO4--. Depending on the proximity of CO2 to the ion, interaction energy can be significantly higher than the thermal energy of the aerosol. For example, an interaction energy of 0.6 eV is obtained with the sulfate (SO4--) ion when CO2 is the nearest neighbor [2]. In this research interaction between CO2 and ions which carry higher charges are investigated. The molecules selected for the study are triply charged phosphate (PO4---) ions and quadruply charged silicate (SiO4----) ions. Examples of salts which contain such molecules are potassium phosphate (K3PO4) and sodium orthosilicate (Na4SiO4). The research has been carried out with first principle quantum mechanical calculations using the Density Functional Theory method with B3LYP functional and Pople type basis sets augmented with polarization and diffuse functions. Atomic models consist of the selected ions surrounded by water and CO2 molecules. Similar to the results obtained with singly and doubly charged ions [1-2], phosphate and silicate ions attract CO2 molecules. Energy of interaction between the ion and CO2 is 1.6 eV for the phosphate ion and 3.3 eV for the silicate ion. Hence one can expect that the selected ions would enhance the absorption of CO2 into the aerosol even more than the singly or doubly charged ions. Ion containing aerosols also help to catalyze reactions between water and CO2. Hydrated phosphate and silicate ions tend to attract hydrogen atoms from neighboring water molecules to reduce the charged state. When there is CO2 in the vicinity of the ion, the remainder of the water molecule which loses the hydrogen(s) reacts with CO2 to form carbonates. (PO4---) + H2O + CO2 -> (HPO3--) + (HCO3-) (SiO4----) + H2O + CO2 -> (HSiO4---) + (HCO3-) (SiO4----) + H2O + CO2 -> (H2SiO4--) + (CO3--) In conclusion, highly charged phosphate and silicate ions dissolved in water and aerosolized into small droplets can facilitate both the capture and the mineralization of CO2. This method would be especially effective in a CO2 rich environment such as the exhaust gas of a combustion process. [1] H. Gokturk, "Geoengineering with Charged Droplets," AGU Fall Meeting, San Francisco 2011 [2] H. Gokturk, "Atomistic Simulation of Sea Spray Particles," AGU Fall Meeting, San Francisco 2012

Determining Energies and Cross Sections of Individual Ions Using Higher-Order Harmonics in Fourier Transform Charge Detection Mass Spectrometry (FT-CDMS).

PubMed

Harper, Conner C; Elliott, Andrew G; Lin, Haw-Wei; Williams, Evan R

2018-06-02

A general method for in situ measurements of the energy of individual ions trapped and weighed using charge detection mass spectrometry (CDMS) is described. Highly charged (> 300 e), individual polyethylene glycol (PEG) ions are trapped and oscillate within an electrostatic trap, producing a time domain signal. A segmented Fourier transform (FT) of this signal yields the temporal evolution of the fundamental and harmonic frequencies of ion motion throughout the 500-ms trap time. The ratio of the fundamental frequency and second harmonic (HAR) depends on the ion energy, which is an essential parameter for measuring ion mass in CDMS. This relationship is calibrated using simulated ion signals, and the calibration is compared to the HAR values measured for PEG ion signals where the ion energy was also determined using an independent method that requires that the ions be highly charged (> 300 e). The mean error of 0.6% between the two measurements indicates that the HAR method is an accurate means of ion energy determination that does not depend on ion size or charge. The HAR is determined dynamically over the entire trapping period, making it possible to observe the change in ion energy that takes place as solvent evaporates from the ion and collisions with background gas occur. This method makes it possible to measure mass changes, either from solvent evaporation or from molecular fragmentation (MS n ), as well as the cross sections of ions measured using CDMS. Graphical Abstract.

Double ion production in mercury thrusters. M.S. Thesis

NASA Technical Reports Server (NTRS)

Peters, R. R.

1976-01-01

The development of a model which predicts doubly charged ion density is discussed. The accuracy of the model is shown to be good for two different thruster sizes and a total of 11 different cases. The model indicates that in most cases more than 80% of the doubly charged ions are produced from singly charged ions. This result can be used to develop a much simpler model which, along with correlations of the average plasma properties, can be used to determine the doubly charged ion density in ion thrusters with acceptable accuracy. Two different techniques which can be used to reduce the doubly charged ion density while maintaining good thruster operation, are identified as a result of an examination of the simple model. First, the electron density can be reduced and the thruster size then increased to maintain the same propellant utilization. Second, at a fixed thruster size, the plasma density, temperature and energy can be reduced and then to maintain a constant propellant utilization the open area of the grids to neutral propellant loss can be reduced through the use of a small hole accelerator grid.

Ultra-high-mass mass spectrometry with charge discrimination using cryogenic detectors

DOEpatents

Frank, Matthias; Mears, Carl A.; Labov, Simon E.; Benner, W. Henry

1999-01-01

An ultra-high-mass time-of-flight mass spectrometer using a cryogenic particle detector as an ion detector with charge discriminating capabilities. Cryogenic detectors have the potential for significantly improving the performance and sensitivity of time-of-flight mass spectrometers, and compared to ion multipliers they exhibit superior sensitivity for high-mass, slow-moving macromolecular ions and can be used as "stop" detectors in time-of-flight applications. In addition, their energy resolving capability can be used to measure the charge state of the ions. Charge discrimination is very valuable in all time-of-flight mass spectrometers. Using a cryogenically-cooled Nb-Al.sub.2 O.sub.3 -Nb superconductor-insulator-superconductor (SIS) tunnel junction (STJ) detector operating at 1.3 K as an ion detector in a time-of-flight mass spectrometer for large biomolecules it was found that the STJ detector has charge discrimination capabilities. Since the cryogenic STJ detector responds to ion energy and does not rely on secondary electron production, as in the conventionally used microchannel plate (MCP) detectors, the cryogenic detector therefore detects large molecular ions with a velocity-independent efficiency approaching 100%.

Kinetic energy offsets for multicharged ions from an electron beam ion source.

PubMed

Kulkarni, D D; Ahl, C D; Shore, A M; Miller, A J; Harriss, J E; Sosolik, C E; Marler, J P

2017-08-01

Using a retarding field analyzer, we have measured offsets between the nominal and measured kinetic energy of multicharged ions extracted from an electron beam ion source (EBIS). By varying source parameters, a shift in ion kinetic energy was attributed to the trapping potential produced by the space charge of the electron beam within the EBIS. The space charge of the electron beam depends on its charge density, which in turn depends on the amount of negative charge (electron beam current) and its velocity (electron beam energy). The electron beam current and electron beam energy were both varied to obtain electron beams of varying space charge and these were related to the observed kinetic energy offsets for Ar 4+ and Ar 8+ ion beams. Knowledge of these offsets is important for studies that seek to utilize slow, i.e., low kinetic energy, multicharged ions to exploit their high potential energies for processes such as surface modification. In addition, we show that these offsets can be utilized to estimate the effective radius of the electron beam inside the trap.

Single ion induced surface nanostructures: a comparison between slow highly charged and swift heavy ions.

PubMed

Aumayr, Friedrich; Facsko, Stefan; El-Said, Ayman S; Trautmann, Christina; Schleberger, Marika

2011-10-05

This topical review focuses on recent advances in the understanding of the formation of surface nanostructures, an intriguing phenomenon in ion-surface interaction due to the impact of individual ions. In many solid targets, swift heavy ions produce narrow cylindrical tracks accompanied by the formation of a surface nanostructure. More recently, a similar nanometric surface effect has been revealed for the impact of individual, very slow but highly charged ions. While swift ions transfer their large kinetic energy to the target via ionization and electronic excitation processes (electronic stopping), slow highly charged ions produce surface structures due to potential energy deposited at the top surface layers. Despite the differences in primary excitation, the similarity between the nanostructures is striking and strongly points to a common mechanism related to the energy transfer from the electronic to the lattice system of the target. A comparison of surface structures induced by swift heavy ions and slow highly charged ions provides a valuable insight to better understand the formation mechanisms. © 2011 IOP Publishing Ltd

How ions affect the structure of water.

PubMed

Hribar, Barbara; Southall, Noel T; Vlachy, Vojko; Dill, Ken A

2002-10-16

We model ion solvation in water. We use the MB model of water, a simple two-dimensional statistical mechanical model in which waters are represented as Lennard-Jones disks having Gaussian hydrogen-bonding arms. We introduce a charge dipole into MB waters. We perform (NPT) Monte Carlo simulations to explore how water molecules are organized around ions and around nonpolar solutes in salt solutions. The model gives good qualitative agreement with experiments, including Jones-Dole viscosity B coefficients, Samoilov and Hirata ion hydration activation energies, ion solvation thermodynamics, and Setschenow coefficients for Hofmeister series ions, which describe the salt concentration dependence of the solubilities of hydrophobic solutes. The two main ideas captured here are (1) that charge densities govern the interactions of ions with water, and (2) that a balance of forces determines water structure: electrostatics (water's dipole interacting with ions) and hydrogen bonding (water interacting with neighboring waters). Small ions (kosmotropes) have high charge densities so they cause strong electrostatic ordering of nearby waters, breaking hydrogen bonds. In contrast, large ions (chaotropes) have low charge densities, and surrounding water molecules are largely hydrogen bonded.

Charge-exchange plasma environment for an ion drive spacecraft. [a model for describing mercury ion engines and its effect on spacecraft subsystems

NASA Technical Reports Server (NTRS)

Kaufman, H. R.; Carruth, M. R., Jr.

1979-01-01

The charge exchange plasma environment around a spacecraft that uses mercury ion thrusters for propulsion is described. The interactions between the plasma environment and the spacecraft are determined and a model which describes the propagation of the mercury charge exchange plasma is discussed. The model is extended to describe the flow of the molybdenum component of the charge exchange plasma. The uncertainties in the models for various conditions are discussed and current drain to the solar array, charge exchange plasma material deposition, and the effects of space plasma on the charge exchange plasma propagation are addressed.

Influence of argon and oxygen on charge-state-resolved ion energy distributions of filtered aluminum arcs

NASA Astrophysics Data System (ADS)

Rosén, Johanna; Anders, André; Mráz, Stanislav; Atiser, Adil; Schneider, Jochen M.

2006-06-01

The charge-state-resolved ion energy distributions (IEDs) in filtered aluminum vacuum arc plasmas were measured and analyzed at different oxygen and argon pressures in the range of 0.5-8.0 mTorr. A significant reduction of the ion energy was detected as the pressure was increased, most pronounced in an argon environment and for the higher charge states. The corresponding average charge state decreased from 1.87 to 1.0 with increasing pressure. The IEDs of all metal ions in oxygen were fitted with shifted Maxwellian distributions. The results show that it is possible to obtain a plasma composition with a narrow charge-state distribution as well as a narrow IED. These data may enable tailoring thin film properties through selecting growth conditions that are characterized by predefined charge state and energy distributions.

Quantum dynamics of charge state in silicon field evaporation

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

Silaeva, Elena P.; Uchida, Kazuki; Watanabe, Kazuyuki, E-mail: kazuyuki@rs.kagu.tus.ac.jp

2016-08-15

The charge state of an ion field-evaporating from a silicon-atom cluster is analyzed using time-dependent density functional theory coupled to molecular dynamics. The final charge state of the ion is shown to increase gradually with increasing external electrostatic field in agreement with the average charge state of silicon ions detected experimentally. When field evaporation is triggered by laser-induced electronic excitations the charge state also increases with increasing intensity of the laser pulse. At the evaporation threshold, the charge state of the evaporating ion does not depend on the electrostatic field due to the strong contribution of laser excitations to themore » ionization process both at low and high laser energies. A neutral silicon atom escaping the cluster due to its high initial kinetic energy is shown to be eventually ionized by external electrostatic field.« less

Particle accelerator employing transient space charge potentials

DOEpatents

Post, Richard F.

1990-01-01

The invention provides an accelerator for ions and charged particles. The plasma is generated and confined in a magnetic mirror field. The electrons of the plasma are heated to high temperatures. A series of local coils are placed along the axis of the magnetic mirror field. As an ion or particle beam is directed along the axis in sequence the coils are rapidly pulsed creating a space charge to accelerate and focus the beam of ions or charged particles.

Calculations of heavy ion charge state distributions for nonequilibrium conditions

NASA Technical Reports Server (NTRS)

Luhn, A.; Hovestadt, D.

1985-01-01

Numerical calculations of the charge state distributions of test ions in a hot plasma under nonequilibrium conditions are presented. The mean ionic charges of heavy ions for finite residence times in an instantaneously heated plasma and for a non-Maxwellian electron distribution function are derived. The results are compared with measurements of the charge states of solar energetic particles, and it is found that neither of the two simple cases considered can explain the observations.

Relationship between ion pair geometries and electrostatic strengths in proteins.

PubMed Central

Kumar, Sandeep; Nussinov, Ruth

2002-01-01

The electrostatic free energy contribution of an ion pair in a protein depends on two factors, geometrical orientation of the side-chain charged groups with respect to each other and the structural context of the ion pair in the protein. Conformers in NMR ensembles enable studies of the relationship between geometry and electrostatic strengths of ion pairs, because the protein structural contexts are highly similar across different conformers. We have studied this relationship using a dataset of 22 unique ion pairs in 14 NMR conformer ensembles for 11 nonhomologous proteins. In different NMR conformers, the ion pairs are classified as salt bridges, nitrogen-oxygen (N-O) bridges and longer-range ion pairs on the basis of geometrical criteria. In salt bridges, centroids of the side-chain charged groups and at least a pair of side-chain nitrogen and oxygen atoms of the ion-pairing residues are within a 4 A distance. In N-O bridges, at least a pair of the side-chain nitrogen and oxygen atoms of the ion-pairing residues are within 4 A distance, but the distance between the side-chain charged group centroids is greater than 4 A. In the longer-range ion pairs, the side-chain charged group centroids as well as the side-chain nitrogen and oxygen atoms are more than 4 A apart. Continuum electrostatic calculations indicate that most of the ion pairs have stabilizing electrostatic contributions when their side-chain charged group centroids are within 5 A distance. Hence, most (approximately 92%) of the salt bridges and a majority (68%) of the N-O bridges are stabilizing. Most (approximately 89%) of the destabilizing ion pairs are the longer-range ion pairs. In the NMR conformer ensembles, the electrostatic interaction between side-chain charged groups of the ion-pairing residues is the strongest for salt bridges, considerably weaker for N-O bridges, and the weakest for longer-range ion pairs. These results suggest empirical rules for stabilizing electrostatic interactions in proteins. PMID:12202384

High charge state carbon and oxygen ions in Earth's equatorial quasi-trapping region

NASA Technical Reports Server (NTRS)

Christon, S. P.; Hamilton, D. C.; Gloeckler, G.; Eastmann, T. E.

1994-01-01

Observations of energetic (1.5 - 300 keV/e) medium-to-high charge state (+3 less than or equal to Q less than or equal to +7) solar wind origin C and O ions made in the quasi-trapping region (QTR) of Earth's magnetosphere are compared to ion trajectories calculated in model equatorial magnetospheric magnetic and electric fields. These comparisons indicate that solar wind ions entering the QTR on the nightside as an energetic component of the plasma sheet exit the region on the dayside, experiencing little or no charge exchange on the way. Measurements made by the CHarge Energy Mass (CHEM) ion spectrometer on board the Active Magnetospheric Particle Tracer Explorer/Charge Composition Explorer (AMPTE/CCE) spacecraft at 7 less than L less than 9 from September 1984 to January 1989 are the source of the new results contained herein: quantitative long-term determination of number densities, average energies, energy spectra, local time distributions, and their variation with geomagnetic disturbance level as indexed by Kp. Solar wind primaries (ions with charge states unchanged) and their secondaries (ions with generally lower charge states produced from primaries in the magnetosphere via charge exchange)are observed throughout the QTR and have distinctly different local time variations that persist over the entire 4-year analysis interval. During Kp larger than or equal to 3 deg intervals, primary ion (e.g., O(+6)) densities exhibit a pronounced predawn maximum with average energy minimum and a broad near-local-noon density minimum with average energy maximum. Secondary ion (e.g., O(+5)) densities do not have an identifiable predawn peak, rather they have a broad dayside maximum peaked in local morning and a nightside minimum. During Kp less than or equal to 2(-) intervals, primary ion density peaks are less intense, broader in local time extent, and centered near midnight, while secondary ion density local time variations diminish. The long-time-interval baseline helps to refine and extend previous observations; for example, we show that ionospheric contribution to O(+3)) is negligible. Through comparison with model ion trajectories, we interpret the lack of pronounced secondary ion density peaks colocated with the primary density peaks to indicate that: (1) negligible charge exchange occurs at L greater than 7, that is, solar wind secondaries are produced at L less than 7, and (2) solar wind secondaries do not form a significant portion of the plasma sheet population injected into the QTR. We conclude that little of the energetic solar wind secondary ion population is recirculated through the magnetosphere.

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L.; Aines, Roger D.; Haslam, Jeffery J.; Schaldach, Charlene M.; O& #x27; Brien, Kevin C.; Cussler, Edward

2013-06-11

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L [Livermore, CA; Aines, Roger D [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Schaldach, Charlene M [Pleasanton, CA; O'Brien, Kevin C [San Ramon, CA; Cussler, Edward [Edina, MN

2011-07-19

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

High sensitivity charge amplifier for ion beam uniformity monitor

DOEpatents

Johnson, Gary W.

2001-01-01

An ion beam uniformity monitor for very low beam currents using a high-sensitivity charge amplifier with bias compensation. The ion beam monitor is used to assess the uniformity of a raster-scanned ion beam, such as used in an ion implanter, and utilizes four Faraday cups placed in the geometric corners of the target area. Current from each cup is integrated with respect to time, thus measuring accumulated dose, or charge, in Coulombs. By comparing the dose at each corner, a qualitative assessment of ion beam uniformity is made possible. With knowledge of the relative area of the Faraday cups, the ion flux and areal dose can also be obtained.

Development of electron beam ion source for nanoprocess using highly charged ions

NASA Astrophysics Data System (ADS)

Sakurai, Makoto; Nakajima, Fumiharu; Fukumoto, Takunori; Nakamura, Nobuyuki; Ohtani, Shunsuke; Mashiko, Shinro; Sakaue, Hiroyuki

2005-07-01

Highly charged ion is useful to produce nanostructure on various materials, and is key tool to realize single ion implantation technique. On such demands for the application to nanotechnology, we have designed an electron bean ion source. The design stresses on the volume of drift tubes where highly charged ions are confined and the efficiency of ion extraction from the drift tube through collector electrode in order to obtain intense ion beam as much as possible. The ion source uses a discrete superconducting magnet cooled by a closed-cycle refrigerator in order to reduce the running costs and to simplify the operating procedures. The electrodes of electron gun, drift tubes, and collector are enclosed in ultrahigh vacuum tube that is inserted into the bore of the magnet system.

Charge-Transfer Processes in Warm Dense Matter: Selective Spectral Filtering for Laser-Accelerated Ion Beams

NASA Astrophysics Data System (ADS)

Braenzel, J.; Barriga-Carrasco, M. D.; Morales, R.; Schnürer, M.

2018-05-01

We investigate, both experimentally and theoretically, how the spectral distribution of laser accelerated carbon ions can be filtered by charge exchange processes in a double foil target setup. Carbon ions at multiple charge states with an initially wide kinetic energy spectrum, from 0.1 to 18 MeV, were detected with a remarkably narrow spectral bandwidth after they had passed through an ultrathin and partially ionized foil. With our theoretical calculations, we demonstrate that this process is a consequence of the evolution of the carbon ion charge states in the second foil. We calculated the resulting spectral distribution separately for each ion species by solving the rate equations for electron loss and capture processes within a collisional radiative model. We determine how the efficiency of charge transfer processes can be manipulated by controlling the ionization degree of the transfer matter.

The effects of vortex like distributed electron in magnetized multi-ion dusty plasmas

NASA Astrophysics Data System (ADS)

Haider, Md. Masum; Ferdous, Tahmina; Duha, Syed S.

2014-09-01

The nonlinear propagation of small but finite amplitude dust-ion-acoustic solitary waves in a magnetized, collisionless dusty plasma is investigated theoretically. It has been assumed that the electrons are trapped following the vortex-like distribution and that the negatively and positively charged ions are mobile with the presence of charge fluctuating stationary dusts, where ions mass provide the inertia and restoring forces are provided by the thermal pressure of hot electrons. A reductive perturbation method was employed to obtain a modified Korteweg-de Vries (mK-dV) equation for the first-order potential and a stationary solution is obtained. The effect of the presence of trapped electrons, negatively and positively charged ions and arbitrary charged dust grains are discussed.

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

Magnetic and electric deflector spectrometers for ion emission analysis from laser generated plasma

NASA Astrophysics Data System (ADS)

Torrisi, Lorenzo; Costa, Giuseppe; Ceccio, Giovanni; Cannavò, Antonino; Restuccia, Nancy; Cutroneo, Mariapompea

2018-01-01

The pulsed laser-generated plasma in vacuum and at low and high intensities can be characterized using different physical diagnostics. The charge particles emission can be characterized using magnetic, electric and magnet-electrical spectrometers. Such on-line techniques are often based on time-of-flight (TOF) measurements. A 90° electric deflection system is employed as ion energy analyzer (IEA) acting as a filter of the mass-to-charge ratio of emitted ions towards a secondary electron multiplier. It determines the ion energy and charge state distributions. The measure of the ion and electron currents as a function of the mass-to-charge ratio can be also determined by a magnetic deflector spectrometer, using a magnetic field of the order of 0.35 T, orthogonal to the ion incident direction, and an array of little ion collectors (IC) at different angles. A Thomson parabola spectrometer, employing gaf-chromix as detector, permits to be employed for ion mass, energy and charge state recognition. Mass quadrupole spectrometry, based on radiofrequency electric field oscillations, can be employed to characterize the plasma ion emission. Measurements performed on plasma produced by different lasers, irradiation conditions and targets are presented and discussed. Complementary measurements, based on mass and optical spectroscopy, semiconductor detectors, fast CCD camera and Langmuir probes are also employed for the full plasma characterization. Simulation programs, such as SRIM, SREM, and COMSOL are employed for the charge particle recognition.

Electron-beam-ion-source (EBIS) modeling progress at FAR-TECH, Inc

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

Kim, J. S., E-mail: kim@far-tech.com; Zhao, L., E-mail: kim@far-tech.com; Spencer, J. A., E-mail: kim@far-tech.com

FAR-TECH, Inc. has been developing a numerical modeling tool for Electron-Beam-Ion-Sources (EBISs). The tool consists of two codes. One is the Particle-Beam-Gun-Simulation (PBGUNS) code to simulate a steady state electron beam and the other is the EBIS-Particle-In-Cell (EBIS-PIC) code to simulate ion charge breeding with the electron beam. PBGUNS, a 2D (r,z) electron gun and ion source simulation code, has been extended for efficient modeling of EBISs and the work was presented previously. EBIS-PIC is a space charge self-consistent PIC code and is written to simulate charge breeding in an axisymmetric 2D (r,z) device allowing for full three-dimensional ion dynamics.more » This 2D code has been successfully benchmarked with Test-EBIS measurements at Brookhaven National Laboratory. For long timescale (< tens of ms) ion charge breeding, the 2D EBIS-PIC simulations take a long computational time making the simulation less practical. Most of the EBIS charge breeding, however, may be modeled in 1D (r) as the axial dependence of the ion dynamics may be ignored in the trap. Where 1D approximations are valid, simulations of charge breeding in an EBIS over long time scales become possible, using EBIS-PIC together with PBGUNS. Initial 1D results are presented. The significance of the magnetic field to ion dynamics, ion cooling effects due to collisions with neutral gas, and the role of Coulomb collisions are presented.« less

Water-mediated ion–ion interactions are enhanced at the water vapor–liquid interface

PubMed Central

Venkateshwaran, Vasudevan; Vembanur, Srivathsan; Garde, Shekhar

2014-01-01

There is overwhelming evidence that ions are present near the vapor–liquid interface of aqueous salt solutions. Charged groups can also be driven to interfaces by attaching them to hydrophobic moieties. Despite their importance in many self-assembly phenomena, how ion–ion interactions are affected by interfaces is not understood. We use molecular simulations to show that the effective forces between small ions change character dramatically near the water vapor–liquid interface. Specifically, the water-mediated attraction between oppositely charged ions is enhanced relative to that in bulk water. Further, the repulsion between like-charged ions is weaker than that expected from a continuum dielectric description and can even become attractive as the ions are drawn to the vapor side. We show that thermodynamics of ion association are governed by a delicate balance of ion hydration, interfacial tension, and restriction of capillary fluctuations at the interface, leading to nonintuitive phenomena, such as water-mediated like charge attraction. “Sticky” electrostatic interactions may have important consequences on biomolecular structure, assembly, and aggregation at soft liquid interfaces. We demonstrate this by studying an interfacially active model peptide that changes its structure from α-helical to a hairpin-turn–like one in response to charging of its ends. PMID:24889634

An analytic expression for the sheath criterion in magnetized plasmas with multi-charged ion species

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

Hatami, M. M., E-mail: m-hatami@kntu.ac.ir

2015-04-15

The generalized Bohm criterion in magnetized multi-component plasmas consisting of multi-charged positive and negative ion species and electrons is analytically investigated by using the hydrodynamic model. It is assumed that the electrons and negative ion density distributions are the Boltzmann distribution with different temperatures and the positive ions enter into the sheath region obliquely. Our results show that the positive and negative ion temperatures, the orientation of the applied magnetic field and the charge number of positive and negative ions strongly affect the Bohm criterion in these multi-component plasmas. To determine the validity of our derived generalized Bohm criterion, itmore » reduced to some familiar physical condition and it is shown that monotonically reduction of the positive ion density distribution leading to the sheath formation occurs only when entrance velocity of ion into the sheath satisfies the obtained Bohm criterion. Also, as a practical application of the obtained Bohm criterion, effects of the ionic temperature and concentration as well as magnetic field on the behavior of the charged particle density distributions and so the sheath thickness of a magnetized plasma consisting of electrons and singly charged positive and negative ion species are studied numerically.« less

Measurements of charge state breeding efficiency at BNL test EBIS

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

Kondrashev, S.; Alessi, J.; Beebe, E.N.

Charge breeding of singly charged ions is required to efficiently accelerate rare isotope ion beams for nuclear and astrophysics experiments, and to enhance the accuracy of low-energy Penning trap-assisted spectroscopy. An efficient charge breeder for the Californium Rare Isotope Breeder Upgrade (CARIBU) to the ANL Tandem Linear Accelerator System (ATLAS) facility is being developed using the BNL Test Electron Beam Ion Source (Test EBIS) as a prototype. Parameters of the CARIBU EBIS charge breeder are similar to those of the BNL Test EBIS except the electron beam current will be adjustable in the range from 1 to 2 {angstrom}. Themore » electron beam current density in the CARIBU EBIS trap will be significantly higher than in existing operational charge state breeders based on the EBIS concept. The charge state breeding efficiency is expected to be about 25% for the isotope ions extracted from the CARIBU. For the success of our EBIS project, it is essential to demonstrate high breeding efficiency at the BNL Test EBIS tuned to the regime close to the parameters of the CARIBU EBIS at ANL. The breeding efficiency optimization and measurements have been successfully carried out using a Cs{sup +} surface ionization ion source for externally pulsed injection into the BNL Test EBIS. A Cs{sup +} ion beam with a total number of ions of 5 x 10{sup 8} and optimized pulse length of 70 {mu}s has been injected into the Test EBIS and charge-bred for 5.3 ms for two different electron beam currents 1 and 1.5 {angstrom}. In these experiments we have achieved 70% injection/extraction efficiency and breeding efficiency into the most abundant charge state 17%.« less

Responses of the Jovian Atmosphere to Cometary Particles and Photon Impacts

NASA Technical Reports Server (NTRS)

Dalgarno, A.

1998-01-01

Spectra of soft x-ray and EUV emissions of oxygen ions, precipitating into the Jovian atmosphere, are calculated, taking into account the dynamical character of the energy and charge distributions of the ions as they propagate. Monte-Carlo simulations are performed using experimental and theoretical cross sections of ion collisions with the atmospheric gases. The numbers of x-ray and EUV photons produced per precipitating oxygen ion are calculated as functions of the initial ion energy and charge. The energy and charge distribution functions are used to evaluate the intensities of characteristic x-ray and EUV spectral emission lines of oxygen ions in the Jovian aurora.

Charge amplifier with bias compensation

DOEpatents

Johnson, Gary W.

2002-01-01

An ion beam uniformity monitor for very low beam currents using a high-sensitivity charge amplifier with bias compensation. The ion beam monitor is used to assess the uniformity of a raster-scanned ion beam, such as used in an ion implanter, and utilizes four Faraday cups placed in the geometric corners of the target area. Current from each cup is integrated with respect to time, thus measuring accumulated dose, or charge, in Coulombs. By comparing the dose at each corner, a qualitative assessment of ion beam uniformity is made possible. With knowledge of the relative area of the Faraday cups, the ion flux and areal dose can also be obtained.

Thin HTSC films produced by a polymer metal precursor technique

NASA Astrophysics Data System (ADS)

Lampe, L. v.; Zygalsky, F.; Hinrichsen, G.

In precursors the metal ions are combined with acid groups of polymethacrylic acid (PMAA), polyacrylic acid (PAA) or novolac. Compared to thermal degradation temperature of pure polymers those of precursors are low. Precursors films were patterned by UV lithography. Diffractometric investigations showed that the c-axis oriented epitaxial films of YBa 2Cu 3O x and Bi 2Sr 2CaCu 2O x originated from amorphous metal oxide films, which were received after thermal degradation of the precursor. Transition temperatures and current densities were determined by electric resistivity measurements.

Mesoporous metal oxides and processes for preparation thereof

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

Suib, Steven L.; Poyraz, Altug Suleyman

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

Modeling secondary electron emission from nanostructured materials in helium ion microscope

NASA Astrophysics Data System (ADS)

Ohya, K.; Yamanaka, T.

2013-11-01

Charging of a SiO2 layer on a Si substrate during helium (He) beam irradiation is investigated at an energy range relevant to a He ion microscope (HIM). A self-consistent calculation is performed to model the transport of the ions and secondary electrons (SEs), the charge accumulation in the layer, and the electric field below and above the surface. The calculated results are compared with those for gallium (Ga) ions at the same energy and 1 keV electrons corresponding to a low-voltage scanning electron microscope (SEM). The charging of thin layers (<250 nm) is strongly suppressed due to wide depth and lateral distributions of the He ions in the layer, the voltage of which is much lower than that for the Ga ions and the electrons, where the distributions are much more localized. When the irradiation approaches the edge of a 100-nm-high SiO2 step formed on a Si substrate, a sharp increase in the number of SEs is observed, irrespective of whether a material is charged or not. When the He ions are incident on the bottom of the step, the re-entrance of SEs emitted from the substrate into the sidewall is clearly observed, but it causes the sidewall to be charged negatively. At the positions on the SiO2 layer away from the step edge, the charging voltage becomes positive with increasing number of Ga ions and electrons. However, He ions do not induce such a voltage due to strong relaxation of positive and negative charges in the Si substrate and their recombination in the SiO2 layer.

Target Plate Material Influence on Fullerene-C60 Laser Desorption/Ionization Efficiency

NASA Astrophysics Data System (ADS)

Zeegers, Guido P.; Günthardt, Barbara F.; Zenobi, Renato

2016-04-01

Systematic laser desorption/ionization (LDI) experiments of fullerene-C60 on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0-3.53 Jcm-2) and the ion extraction delay time (0-950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C60 precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C60 cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements.

Ion-source modeling and improved performance of the CAMS high-intensity Cs-sputter ion source

NASA Astrophysics Data System (ADS)

Brown, T. A.; Roberts, M. L.; Southon, J. R.

2000-10-01

The interior of the high-intensity Cs-sputter source used in routine operations at the Center for Accelerator Mass Spectrometry (CAMS) has been computer modeled using the program NEDLab, with the aim of improving negative ion output. Space charge effects on ion trajectories within the source were modeled through a successive iteration process involving the calculation of ion trajectories through Poisson-equation-determined electric fields, followed by calculation of modified electric fields incorporating the charge distribution from the previously calculated ion trajectories. The program has several additional features that are useful in ion source modeling: (1) averaging of space charge distributions over successive iterations to suppress instabilities, (2) Child's Law modeling of space charge limited ion emission from surfaces, and (3) emission of particular ion groups with a thermal energy distribution and at randomized angles. The results of the modeling effort indicated that significant modification of the interior geometry of the source would double Cs + ion production from our spherical ionizer and produce a significant increase in negative ion output from the source. The results of the implementation of the new geometry were found to be consistent with the model results.

Structural and electrochemical properties of iron- and nickel-substituted Li2MnO3 cathodes in charged and discharged states

NASA Astrophysics Data System (ADS)

Yuge, Ryota; Kuroshima, Sadanori; Toda, Akio; Miyazaki, Takashi; Tabuchi, Mitsuharu; Doumae, Kyosuke; Shibuya, Hideka; Tamura, Noriyuki

2017-10-01

Structural change and the charge compensation mechanism of lithium-rich layered cathode (Li1.23Fe0.15Ni0.15Mn0.46O2) in charged and discharged states were investigated. Selected area electron diffraction analysis revealed that in discharged state, an initial structure composed of a single phase of monoclinic layered rock-salt changed to a mixture of hexagonal layered rock-salt and spinel-like structures. In charged state, the spinel-like phase became dominant as transition-metal ions migrate. 57Fe Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), and Soft-XAS showed that the valence of Fe and Ni ions approximately changed from Fe3+ to Fe3.2+ and Ni2+ to Ni3.5+ during charge-discharge, although Mn ions remained as Mn4+. Various oxidation states of oxide ions such as superoxide, peroxide, and hole states have also been detected in charged state. Considering that actual discharge capacity was 255 mAh/g, the contribution to charge compensation from the valence change of Fe and Ni ions was extremely small, and it only contributed to about one-third of total capacity. Therefore, the mechanism to yield high capacity of the Li1.23Fe0.15Ni0.15Mn0.46O2 cathode relates strongly to the redox reaction of oxide ions. Moreover, the decrease in capacity during charge-discharge cycling was mainly due to the irreversible redox reaction of Mn, Fe, and oxide ions.

ION SOURCE WITH SPACE CHARGE NEUTRALIZATION

DOEpatents

Flowers, J.W.; Luce, J.S.; Stirling, W.L.

1963-01-22

This patent relates to a space charge neutralized ion source in which a refluxing gas-fed arc discharge is provided between a cathode and a gas-fed anode to provide ions. An electron gun directs a controlled, monoenergetic electron beam through the discharge. A space charge neutralization is effected in the ion source and accelerating gap by oscillating low energy electrons, and a space charge neutralization of the source exit beam is effected by the monoenergetic electron beam beyond the source exit end. The neutralized beam may be accelerated to any desired energy at densities well above the limitation imposed by Langmuir-Child' s law. (AEC)

Rectification of Ion Current in Nanopipettes by External Substrates

PubMed Central

Shi, Wenqing; Baker, Lane A.

2014-01-01

We describe ion distribution and the current-voltage (i-V) response of nanopipettes at different probe-to-substrate distances (Dps) as simulated by finite-element methods. Results suggest electrostatic interactions between a charged substrate and the nanopipette dominate electrophoretic ion transport through the nanopipette when Dps is within one order of magnitude of the Debye length (~10 nm for a 1 mM solution as employed in the simulation). Ion current rectification (ICR) and permselectivity associated with a neutral or charged nanopipette can be reversibly enhanced or reduced dependent on Dps, charge polarity and charge density (σ) of the substrate. Regulation of nanopipette current is a consequence of the enrichment or depletion of ions within the nanopipette interior which influences conductivity of the nanopipette. When the external substrate is less negatively charged than the nanopipette, the substrate first reduces, and then enhances the ICR as Dps decreases. Surprisingly, both experimental and simulated data show that a neutral substrate was also able to reduce and reverse the ICR of a slightly negatively charged nanopipette. Simulated results ascribe such effects to the elimination of ion depletion within the nanopipette at positive potentials. PMID:24200344

Rectification of ion current in nanopipettes by external substrates.

PubMed

Sa, Niya; Lan, Wen-Jie; Shi, Wenqing; Baker, Lane A

2013-12-23

We describe ion distribution and the current-voltage (i-V) response of nanopipettes at different probe-to-substrate distances (Dps) as simulated by finite-element methods. Results suggest electrostatic interactions between a charged substrate and the nanopipette dominate electrophoretic ion transport through the nanopipette when Dps is within 1 order of magnitude of the Debye length (∼10 nm for a 1 mM solution as employed in the simulation). Ion current rectification (ICR) and permselectivity associated with a neutral or charged nanopipette can be reversibly enhanced or reduced dependent on Dps, charge polarity, and charge density (σ) of the substrate. Regulation of nanopipette current is a consequence of the enrichment or depletion of ions within the nanopipette interior, which influences conductivity of the nanopipette. When the external substrate is less negatively charged than the nanopipette, the substrate first reduces, and then enhances the ICR as Dps decreases. Surprisingly, both experimental and simulated data show that a neutral substrate was also able to reduce and reverse the ICR of a slightly negatively charged nanopipette. Simulated results ascribe such effects to the elimination of ion depletion within the nanopipette at positive potentials.

Charge exchange of highly charged argon ions as a function of projectile energy

NASA Astrophysics Data System (ADS)

Allen, F. I.; Biedermann, C.; Radtke, R.; Fussmann, G.

2007-03-01

X-ray emission of highly charged argon ions following charge exchange collisions with argon atoms has been measured as a function of projectile energy. The ions are extracted from the Electron Beam Ion Trap (EBIT) in Berlin and selected according to their massto-charge ratios. Experiments focussed on hydrogen-like and bare argon ions which were decelerated from 125q eV/amu to below 0.25q eV/amu prior to interaction with an argon gas target. The x-ray spectra recorded probe the cascading transitions resulting from electron capture into Rydberg states and are found to vary significantly with collision velocity. This indicates a shift in the orbital angular momentum of the capture state. Hardness ratios are observed to increase with decreasing projectile energy though at a rate which differs from the results of simulations. For comparison, measurements of the x-ray emission following charge exchange within the trap were carried out and are in agreement with the findings of the EBIT group at LLNL. Both of these in situ measurements, however, are in discrepancy with the results of the experiments using extracted ions.

Controlling Gas-Phase Reactions for Efficient Charge Reduction Electrospray Mass Spectrometry of Intact Proteins

PubMed Central

Frey, Brian L.; Lin, Yuan; Westphall, Michael S.; Smith, Lloyd M.

2006-01-01

Charge reduction electrospray mass spectrometry (CREMS) reduces the charge states of electrospray-generated ions, which concentrates the ions from a protein into fewer peaks spread over a larger m/z range, thereby increasing peak separation and decreasing spectral congestion. An optimized design for a CREMS source is described that provides an order-of-magnitude increase in sensitivity compared to previous designs and provides control over the extent of charge reduction. Either a corona discharge or an α-particle source was employed to generate anions that abstract protons from electrosprayed protein cations. These desired ion/ion proton transfer reactions predominated, but some oxidation and ion-attachment reactions also occurred leading to new peaks or mass-shifted broader peaks while decreasing signal intensity. The species producing these deleterious side-reactions were identified, and conditions were found that prevented their formation. Spectrometer m/z biases were examined because of their effect upon the signal intensity of higher m/z charge-reduced protein ions. The utility of this atmospheric pressure CREMS was demonstrated using a cell lysate fraction from E. coli. The spectral simplification afforded by CREMS reveals more proteins than are observed without charge reduction. PMID:16198118

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

Depth profile of halide anions under highly charged biological membrane

NASA Astrophysics Data System (ADS)

Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

2015-03-01

Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

A particle accelerator employing transient space charge potentials

DOEpatents

Post, R.F.

1988-02-25

The invention provides an accelerator for ions and charged particles. The plasma is generated and confined in a magnetic mirror field. The electrons of the plasma are heated to high temperatures. A series of local coils are placed along the axis of the magnetic mirror field. As an ion or particle beam is directed along the axis in sequence the coils are rapidly pulsed creating a space charge to accelerate and focus the beam of ions or charged particles. 3 figs.

Characterization of an Atomic Hydrogen Source for Charge Exchange Experiments

NASA Technical Reports Server (NTRS)

Leutenegger, M. A.; Beierdorfer, P.; Betancourt-Martinez, G. L.; Brown, G. V.; Hell, N; Kelley, R. L.; Kilbourne, C. A.; Magee, E. W.; Porter, F. S.

2016-01-01

We characterized the dissociation fraction of a thermal dissociation atomic hydrogen source byinjecting the mixed atomic and molecular output of the source into an electron beam ion trapcontaining highly charged ions and recording the x-ray spectrum generated by charge exchangeusing a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchangestate-selective capture cross sections are very different for atomic and molecular hydrogen incidenton the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

Extreme ultraviolet spectra of multiply charged tungsten ions

NASA Astrophysics Data System (ADS)

Mita, Momoe; Sakaue, Hiroyuki A.; Kato, Daiji; Murakami, Izumi; Nakamura, Nobuyuki

2017-11-01

We present extreme ultraviolet spectra of multiply charged tungsten ions observed with an electron beam ion trap. The observed spectra are compared with previous experimental results and theoretical spectra obtained with a collisional radiative model.

LC/QTOF-MS fragmentation of N-nitrosodimethylamine precursors in drinking water supplies is predictable and aids their identification.

PubMed

Hanigan, David; Ferrer, Imma; Thurman, E Michael; Herckes, Pierre; Westerhoff, Paul

2017-02-05

N-Nitrosodimethylamine (NDMA) is carcinogenic in rodents and occurs in chloraminated drinking water and wastewater effluents. NDMA forms via reactions between chloramines and mostly unidentified, N-containing organic matter. We developed a mass spectrometry technique to identify NDMA precursors by analyzing 25 model compounds with LC/QTOF-MS. We searched isolates of 11 drinking water sources and 1 wastewater using a custom MATLAB ® program and extracted ion chromatograms for two fragmentation patterns that were specific to the model compounds. Once a diagnostic fragment was discovered, we conducted MS/MS during a subsequent injection to confirm the precursor ion. Using non-target searches and two diagnostic fragmentation patterns, we discovered 158 potential NDMA precursors. Of these, 16 were identified using accurate mass combined with fragment and retention time matches of analytical standards when available. Five of these sixteen NDMA precursors were previously unidentified in the literature, three of which were metabolites of pharmaceuticals. Except methadone, the newly identified precursors all had NDMA molar yields of less than 5%, indicating that NDMA formation could be additive from multiple compounds, each with low yield. We demonstrate that the method is applicable to other disinfection by-product precursors by predicting and verifying the fragmentation patterns for one nitrosodiethylamine precursor. Copyright © 2016. Published by Elsevier B.V.

Probing Interactions at the Nanoscale by Ion Current through Nanopores and Nanovoids

NASA Astrophysics Data System (ADS)

Gamble, Trevor Patrick

Polymer nanopores offer themselves as excellent test beds for study of phenomena that occur on the nano-scale, such as Debye layer formation, surface charge modulation, current saturation, and rectification. Studying ions interactions within the Debye layer, for example, is not possible on the micro-scale, where the pore diameter can be 100 times the size of the zone where interactions of interest occur. However, in our nanopores with an opening diameter less than 10 nm, a slight change of the Debye length can lead to drastic changes of the recorded ion current. Here we present our nanopores' use as a tool to study geometrical and electrochemical properties of porous manganese oxide. There is great value in studying nano-scale properties of this material because of its importance in lithium ion batteries and newly developed nano-architectures within supercapacitors. We electrodeposited manganese oxide wires into our cylindrical nanopores, filling them completely. In this use, nanopores became a template to probe properties of the embedded material such as surface charge, ion selectivity, and porosity. This information was then reported to the Energy Frontier Research Center (EFRC) collaboration, so that other groups can incorporate these recently discovered characteristics into future their nano-architecture design. Additionally, we constructed conical nanopores to study interactions between the surface charges found on the walls and alkali metal ions. In particular we looked at lithium, as it is the electrochemically active ion during charge cycling in EFRC energy storage devices. We attempted to reveal lithium ion's affinity to bind to surface charges. We found this binding led to lowering of the effective surface charge of the pore walls, while also decreasing lithium's ability to move through channels or voids that have charged walls. In connection to manganese oxide, a porous, charged material with voids, information on lithium's interaction with these charges is paramount.

Influence of Coulombic repulsion on the dissociation pathways and energetics of multiprotein complexes in the gas phase.

PubMed

Sinelnikov, Igor; Kitova, Elena N; Klassen, John S

2007-04-01

Thermal dissociation experiments, implemented with blackbody infrared radiative dissociation and Fourier-transform ion cyclotron resonance mass spectrometry, are performed on gaseous protonated and deprotonated ions of the homopentameric B subunits of Shiga toxin 1 (Stx1 B5) and Shiga toxin 2 (Stx2 B5) and the homotetramer streptavidin (S4). Dissociation of the gaseous, multisubunit complexes proceeds predominantly by the loss of a single subunit. Notably, the fractional partitioning of charge between the product ions, i.e., the leaving subunit and the resulting multimer, for a given complex is, within error, constant over the range of charge states investigated. The Arrhenius activation parameters (E(a), A) measured for the loss of subunit decrease with increasing charge state of the complex. However, the parameters for the protonated and deprotonated ions, with the same number of charges, are indistinguishable. The influence of the complex charge state on the dissociation pathways and the magnitude of the dissociation E(a) are modeled theoretically with the discrete charge droplet model (DCDM) and the protein structure model (PSM), wherein the structure of the subunits is considered. Importantly, the major subunit charge states observed experimentally for the Stx1 B5(n+/-) ions correspond to the minimum energy charge distribution predicted by DCDM and PSM assuming a late dissociative transition-state (TS); while for structurally-related Stx2 B5(n+) ions, the experimental charge distribution corresponds to an early TS. It is proposed that the lateness of the TS is related, in part, to the degree of unfolding of the leaving subunit, with Stx1 B being more unfolded than Stx2 B. PSM, incorporating significant subunit unfolding is necessary to account for the product ions observed for the S4(n+) ions. The contribution of Coulombic repulsion to the dissociation E(a) is quantified and the intrinsic activation energy is estimated for the first time.

Control and Signal Conditioning Circuits for E.I.R.M.A (Energetic Ion Retarding Mass Analyzer),

DTIC Science & Technology

1984-10-01

electrically isolated segment of the vehicle with respect to the main body of the vehicle containing the mass analyzer and other instruments. The...ambient plasma. The vehicle was to be charged positive by the ejection of electrons and negative by the positive ion ejection. Also, the operation of...ambient ions and the ener- getic ions emitted and created during the vehicle charging and dis- charging experiments. It also was intended to survey the

Development of a pepper pot emittance probe and its application for ECR ion beam studies.

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

Kondrashev, S.; Barcikowski, A.; Mustapha, B.

2009-07-21

A pepper pot-scintillator screen system has been developed and used to measure the emittance of DC ion beams extracted from a high-intensity permanent magnet ECR ion source. The system includes a fast beam shutter with a minimum dwell time of 18 ms to reduce the degradation of the CsI(Tl) scintillator by DC ion beam irradiation and a CCD camera with a variable shutter speed in the range of 1 {micro}s-65 s. On-line emittance measurements are performed by an application code developed on a LabVIEW platform. The sensitivity of the device is sufficient to measure the emittance of DC ion beamsmore » with current densities down to about 100 nA/cm{sup 2}. The emittance of all ion species extracted from the ECR ion source and post-accelerated to an energy of 75-90 keV/charge have been measured downstream of the LEBT. As the mass-to-charge ratio of ion species increases, the normalized RMS emittances in both transverse phase planes decrease from 0.5-1.0 {pi} mm mrad for light ions to 0.05-0.09 {pi} mm mrad for highly charged {sup 209}Bi ions. The dependence of the emittance on ion's mass-to-charge ratio follows very well the dependence expected from beam rotation induced by decreasing ECR axial magnetic field. The measured emittance values cannot be explained by only ion beam rotation for all ion species and the contribution to emittance of ion temperature in plasma, non-linear electric fields and non-linear space charge is comparable or even higher than the contribution of ion beam rotation.« less

Influence of argon and oxygen on charge-state-resolved ion energydistributions of filtered aluminum arcs

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

Rosen, Johanna; Anders, Andre; Mraz, Stanislav

2006-03-23

The charge-state-resolved ion energy distributions (IEDs) in filtered aluminum vacuum arc plasmas were measured and analyzed at different oxygen and argon pressures in the range 0.5 8.0 mTorr. A significant reduction of the ion energy was detected as the pressure was increased, most pronounced in an argon environment and for the higher charge states. The corresponding average charge state decreased from 1.87 to 1.0 with increasing pressure. The IEDs of all metal ions in oxygen were fitted with shifted Maxwellian distributions. The results show that it is possible to obtain a plasma composition with a narrow charge-state distribution as wellmore » as a narrow IED. These data may enable tailoring thin-film properties through selecting growth conditions that are characterized by predefined charge state and energy distributions.« less

Easy synthesis of hierarchical carbon spheres with superior capacitive performance in supercapacitors.

PubMed

Huang, Xinhua; Kim, Seok; Heo, Min Seon; Kim, Ji Eun; Suh, Hongsuk; Kim, Il

2013-10-01

An easy template-free approach to the fabrication of pure carbon microspheres has been achieved via direct pyrolysis of as-prepared polyaromatic hydrocarbons including polynaphthalene and polypyrene. The polyaromatics were synthesized from aromatic hydrocarbons (AHCs) using anhydrous zinc chloride as the Friedel-Crafts catalyst and chloromethyl methyl ether as a cross-linker. The experimental results show that the methylene bridges between phenyl rings generate a hierarchical porous polyaromatic precursor to form three-dimensionally (3D) interconnected micro-, meso-, and macroporous networks during carbonization. These hierarchical porous carbon aggregates of spherical carbon spheres exhibit faster ion transport/diffusion behavior and increased surface area usage in electric double-layer capacitors. Furthermore, micropores are present in the 3D interconnected network inside the cross-linked AHC-based carbon microspheres, thus imparting an exceptionally large, electrochemically accessible surface area for charge accumulation.

Mineralization and optical characterization of copper oxide nanoparticles using a high aspect ratio bio-template

NASA Astrophysics Data System (ADS)

Zaman, Mohammed Shahriar; Haberer, Elaine D.

2014-10-01

Organized chains of copper oxide nanoparticles were synthesized, without palladium (Pd) activation, using the M13 filamentous virus as a biological template. The interaction of Cu precursor ions with the negatively charged viral coat proteins were studied with Fourier transform infrared spectroscopy, transmission electron microscopy, and energy dispersive x-ray spectroscopy. Discrete nanoparticles with an average diameter of 4.5 nm and narrow size distribution were closely spaced along the length of the high aspect ratio templates. The synthesized material was identified as a mixture of cubic Cu2O and monoclinic CuO. UV/Vis absorption measurements were completed and a direct optical band gap of 2.87 eV was determined using Tauc's method. This value was slightly larger than bulk, signaling quantum confinement effects within the templated materials.

Mineralization and optical characterization of copper oxide nanoparticles using a high aspect ratio bio-template

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

Zaman, Mohammed Shahriar; Haberer, Elaine D., E-mail: haberer@ucr.edu; Materials Science and Engineering Program, University of California, Riverside, California 92521

Organized chains of copper oxide nanoparticles were synthesized, without palladium (Pd) activation, using the M13 filamentous virus as a biological template. The interaction of Cu precursor ions with the negatively charged viral coat proteins were studied with Fourier transform infrared spectroscopy, transmission electron microscopy, and energy dispersive x-ray spectroscopy. Discrete nanoparticles with an average diameter of 4.5 nm and narrow size distribution were closely spaced along the length of the high aspect ratio templates. The synthesized material was identified as a mixture of cubic Cu₂O and monoclinic CuO. UV/Vis absorption measurements were completed and a direct optical band gap ofmore » 2.87 eV was determined using Tauc's method. This value was slightly larger than bulk, signaling quantum confinement effects within the templated materials.« less

Aberration of a negative ion beam caused by space charge effect.

PubMed

Miyamoto, K; Wada, S; Hatayama, A

2010-02-01

Aberrations are inevitable when the charged particle beams are extracted, accelerated, transmitted, and focused with electrostatic and magnetic fields. In this study, we investigate the aberration of a negative ion accelerator for a neutral beam injector theoretically, especially the spherical aberration caused by the negative ion beam expansion due to the space charge effect. The negative ion current density profiles with the spherical aberration are compared with those without the spherical aberration. It is found that the negative ion current density profiles in a log scale are tailed due to the spherical aberration.

Space-charge effects in Penning ion traps

NASA Astrophysics Data System (ADS)

Porobić, T.; Beck, M.; Breitenfeldt, M.; Couratin, C.; Finlay, P.; Knecht, A.; Fabian, X.; Friedag, P.; Fléchard, X.; Liénard, E.; Ban, G.; Zákoucký, D.; Soti, G.; Van Gorp, S.; Weinheimer, Ch.; Wursten, E.; Severijns, N.

2015-06-01

The influence of space-charge on ion cyclotron resonances and magnetron eigenfrequency in a gas-filled Penning ion trap has been investigated. Off-line measurements with K39+ using the cooling trap of the WITCH retardation spectrometer-based setup at ISOLDE/CERN were performed. Experimental ion cyclotron resonances were compared with ab initio Coulomb simulations and found to be in agreement. As an important systematic effect of the WITCH experiment, the magnetron eigenfrequency of the ion cloud was studied under increasing space-charge conditions. Finally, the helium buffer gas pressure in the Penning trap was determined by comparing experimental cooling rates with simulations.

Measurement of Doubly Charged Ions in Ion Thruster Plumes

NASA Technical Reports Server (NTRS)

Williams, George J., Jr.; Domonkos, Matthew T.; Chavez, Joy M.

2002-01-01

The ratio of doubly to singly charged ions was measured in the plumes of a 30 cm and of a 40 cm ion thruster. The measured ratio was correlated with observed erosion rates and thruster operating conditions. The measured and calculated erosion rates paralleled variation in the j(sup ++)/j(sup +) ratio and indicated that the erosion was dominated by Xe III. Simple models of cathode potential surfaces which were developed in support of this work were in agreement with this conclusion and provided a predictive capability of the erosion given the ratio of doubly to singly charged ion currents.

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study.

PubMed

He, Yadong; Huang, Jingsong; Sumpter, Bobby G; Kornyshev, Alexei A; Qiao, Rui

2015-01-02

Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores.

Influence of the normalized ion flux on the constitution of alumina films deposited by plasma-assisted chemical vapor deposition

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

Kurapov, Denis; Reiss, Jennifer; Trinh, David H.

2007-07-15

Alumina thin films were deposited onto tempered hot working steel substrates from an AlCl{sub 3}-O{sub 2}-Ar-H{sub 2} gas mixture by plasma-assisted chemical vapor deposition. The normalized ion flux was varied during deposition through changes in precursor content while keeping the cathode voltage and the total pressure constant. As the precursor content in the total gas mixture was increased from 0.8% to 5.8%, the deposition rate increased 12-fold, while the normalized ion flux decreased by approximately 90%. The constitution, morphology, impurity incorporation, and the elastic properties of the alumina thin films were found to depend on the normalized ion flux. Thesemore » changes in structure, composition, and properties induced by normalized ion flux may be understood by considering mechanisms related to surface and bulk diffusion.« less

Hidden Charge States in Soft-X-Ray Laser-Produced Nanoplasmas Revealed by Fluorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Schroedter, L.; Müller, M.; Kickermann, A.; Przystawik, A.; Toleikis, S.; Adolph, M.; Flückiger, L.; Gorkhover, T.; Nösel, L.; Krikunova, M.; Oelze, T.; Ovcharenko, Y.; Rupp, D.; Sauppe, M.; Wolter, D.; Schorb, S.; Bostedt, C.; Möller, T.; Laarmann, T.

2014-05-01

Highly charged ions are formed in the center of composite clusters by strong free-electron laser pulses and they emit fluorescence on a femtosecond time scale before competing recombination leads to neutralization of the nanoplasma core. In contrast to mass spectrometry that detects remnants of the interaction, fluorescence in the extreme ultraviolet spectral range provides fingerprints of transient states of high energy density matter. Spectra from clusters consisting of a xenon core and a surrounding argon shell show that a small fraction of the fluorescence signal comes from multiply charged xenon ions in the cluster core. Initially, these ions are as highly charged as the ions in the outer shells of pure xenon clusters with charge states up to at least 11+.

Measurements of charge state distributions of 0.74 and 1.4 MeV /u heavy ions passing through dilute gases

NASA Astrophysics Data System (ADS)

Scharrer, P.; Düllmann, Ch. E.; Barth, W.; Khuyagbaatar, J.; Yakushev, A.; Bevcic, M.; Gerhard, P.; Groening, L.; Horn, K. P.; Jäger, E.; Krier, J.; Vormann, H.

2017-04-01

In many modern heavy-ion accelerator facilities, gas strippers are used to increase the projectile charge state for improving the acceleration efficiency of ion beams to higher energies. For this application, the knowledge on the behavior of charge state distributions of heavy-ions after passing through dilute gases is of special interest. Charge state distributions of uranium (238U), bismuth (209Bi), titanium (50Ti), and argon (40Ar) ion beams with energies of 0.74 MeV /u and 1.4 MeV /u after passing through hydrogen (H2 ), helium (He), carbon dioxide (CO2 ), nitrogen (N2 ), oxygen (O2 ), neon (Ne), and argon (Ar) gases were measured. Gas stripper target thicknesses up to 100 μ g /cm2 were applied. The observed behavior of the charge state distributions, including their width and mean charge state, are discussed. The measurements show the highest equilibrium charge state at 1.4 MeV /u for 238U on H2 gas of 29.2 ±1.2 . Narrow charge state distributions are observed for 238U and 209Bi on H2 and He gas, which are highly beneficial, e.g., for the production of beams of high intensities in accelerators.

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

DOE PAGES

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; ...

2017-07-26

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. In this paper, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing tomore » the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. Finally, this suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.« less

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

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

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. In this paper, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing tomore » the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. Finally, this suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.« less

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

NASA Astrophysics Data System (ADS)

Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

2017-10-01

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

Numerical simulation of ion charge breeding in electron beam ion source

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

Zhao, L., E-mail: zhao@far-tech.com; Kim, Jin-Soo

2014-02-15

The Electron Beam Ion Source particle-in-cell code (EBIS-PIC) tracks ions in an EBIS electron beam while updating electric potential self-consistently and atomic processes by the Monte Carlo method. Recent improvements to the code are reported in this paper. The ionization module has been improved by using experimental ionization energies and shell effects. The acceptance of injected ions and the emittance of extracted ion beam are calculated by extending EBIS-PIC to the beam line transport region. An EBIS-PIC simulation is performed for a Cs charge-breeding experiment at BNL. The charge state distribution agrees well with experiments, and additional simulation results ofmore » radial profiles and velocity space distributions of the trapped ions are presented.« less

Ion energy distributions in silane-hydrogen plasmas

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

Hamers, E.A.G.; Sark, W.G.J.H.M. van; Bezemer, J.

1996-12-31

For the first time ion energy distributions (IED) of different ions from silane-hydrogen (SiH{sub 4}-H{sub 2}) RF plasmas are presented, i.e., the distributions of SiH{sub 3}{sup +}, SiH{sub 2}{sup +} and Si{sub 2}H{sub 4}{sup +}. The energy distributions of SiH{sub 3}{sup +} and SiH{sub 2}{sup +} ions show peaks, which are caused by a charge exchange process in the sheath. A method is presented by which the net charge density in the sheath is determined from the plasma potential and the energy positions of the charge exchange peaks. Knowing the net charge density in the sheath and the plasma potential,more » the sheath thickness can be determined and an estimation of the absolute ion fluxes can be made. The flux of ions can, at maximum, account for 10% of the observed deposition rate.« less

Secondary ion emission from Ti, V, Cu, Ag and Au surfaces under KeV Cs + irradiation

NASA Astrophysics Data System (ADS)

van der Heide, P. A. W.

2005-02-01

Low energy mono-atomic singly charged secondary ion emissions from Ti, V, Cu, Ag and Au substrates during the initial stages of sputtering with Cs + primary ions have been studied. With the exception of the Ag - secondary ions, all exhibited exponential like correlations with the Cs induced work function changes. This, along with the lack of variations in the valence band structure around the Fermi edge, is consistent with resonance charge transfer to/from states located at the Fermi edge. The insensitivity of Ag - to work function appears to stem from the dominance of a separate ion formation process, namely charge transfer into vacant 4d states in the sputtered population, which themselves appear to be produced through collective oscillations. A similar excitation-mediated process involving different levels also appears to be active in the formation of other negatively charged transition metal ions, albeit to a much lesser degree.

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

EPA Science Inventory

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

Production of High Energy Ions Near an Ion Thruster Discharge Hollow Cathode

NASA Technical Reports Server (NTRS)

Katz, Ira; Mikellides, I. G.; Goebel, D. M.; Jameson, K. K.; Wirz, R.; Polk, James E.

2006-01-01

Several researchers have measured ions leaving ion thruster discharge chambers with energies far greater than measured discharge chamber potentials. Presented in this paper is a new mechanism for the generation of high energy ions and a comparison with measured ion spectra. The source of high energy ions has been a puzzle because they not only have energies in excess of measured steady state potentials, but as reported by Goebel et. al. [1], their flux is independent of the amplitude of time dependent plasma fluctuations. The mechanism relies on the charge exchange neutralization of xenon ions accelerated radially into the potential trough in front of the discharge cathode. Previous researchers [2] have identified the importance of charge exchange in this region as a mechanism for protecting discharge cathode surfaces from ion bombardment. This paper is the first to identify how charge exchange in this region can lead to ion energy enhancement.

Utilization of photoinduced charge-separated state of donor-acceptor-linked molecules for regulation of cell membrane potential and ion transport.

PubMed

Numata, Tomohiro; Murakami, Tatsuya; Kawashima, Fumiaki; Morone, Nobuhiro; Heuser, John E; Takano, Yuta; Ohkubo, Kei; Fukuzumi, Shunichi; Mori, Yasuo; Imahori, Hiroshi

2012-04-11

The control of ion transport across cell membranes by light is an attractive strategy that allows targeted, fast control of precisely defined events in the biological membrane. Here we report a novel general strategy for the control of membrane potential and ion transport by using charge-separation molecules and light. Delivery of charge-separation molecules to the plasma membrane of PC12 cells by a membranous nanocarrier and subsequent light irradiation led to depolarization of the membrane potential as well as inhibition of the potassium ion flow across the membrane. Photoregulation of the cell membrane potential and ion transport by using charge-separation molecules is highly promising for control of cell functions. © 2012 American Chemical Society

A comparison of experimental and computer model results on the charge-exchange plasma flow from a 30 cm mercury ion thruster

NASA Technical Reports Server (NTRS)

Gabriel, S. B.; Kaufman, H. R.

1982-01-01

Ion thrusters can be used in a variety of primary and auxiliary space-propulsion applications. A thruster produces a charge-exchange plasma which can interact with various systems on the spacecraft. The propagation of the charge-exchange plasma is crucial in determining the interaction of that plasma with the spacecraft. This paper compares experimental measurements with computer model predictions of the propagation of the charge-exchange plasma from a 30 cm mercury ion thruster. The plasma potentials, and ion densities, and directed energies are discussed. Good agreement is found in a region upstream of, and close to, the ion thruster optics. Outside of this region the agreement is reasonable in view of the modeling difficulties.

Single-atom detection of isotopes

DOEpatents

Meyer, Fred W.

2002-01-01

A method for performing accelerator mass spectrometry, includes producing a beam of positive ions having different multiple charges from a multicharged ion source; selecting positive ions having a charge state of from +2 to +4 to define a portion of the beam of positive ions; and scattering at least a portion of the portion of the beam of positive ions off a surface of a target to directly convert a portion of the positive ions in the portion of the beam of positive ions to negative ions.

Charge breeding results and future prospects with electron cyclotron resonance ion source and electron beam ion source (invited)

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

Vondrasek, R.; Levand, A.; Pardo, R.

2012-02-15

The Californium Rare Ion Breeder Upgrade (CARIBU) of the Argonne National Laboratory ATLAS facility will provide low-energy and reaccelerated neutron-rich radioactive beams for the nuclear physics program. A 70 mCi {sup 252}Cf source produces fission fragments which are thermalized and collected by a helium gas catcher into a low-energy particle beam with a charge of 1+ or 2+. An electron cyclotron resonance (ECR) ion source functions as a charge breeder in order to raise the ion charge sufficiently for acceleration in the ATLAS linac. The final CARIBU configuration will utilize a 1 Ci {sup 252}Cf source to produce radioactive beamsmore » with intensities up to 10{sup 6} ions/s for use in the ATLAS facility. The ECR charge breeder has been tested with stable beam injection and has achieved charge breeding efficiencies of 3.6% for {sup 23}Na{sup 8+}, 15.6% for {sup 84}Kr{sup 17+}, and 13.7% for {sup 85}Rb{sup 19+} with typical breeding times of 10 ms/charge state. For the first radioactive beams, a charge breeding efficiency of 11.7% has been achieved for {sup 143}Cs{sup 27+} and 14.7% for {sup 143}Ba{sup 27+}. The project has been commissioned with a radioactive beam of {sup 143}Ba{sup 27+} accelerated to 6.1 MeV/u. In order to take advantage of its lower residual contamination, an EBIS charge breeder will replace the ECR charge breeder in the next two years. The advantages and disadvantages of the two techniques are compared taking into account the requirements of the next generation radioactive beam facilities.« less

Compact 2.45 GHz ECR Ion Source for generation of singly-charged ions

NASA Astrophysics Data System (ADS)

Fatkullin, Riyaz; Bogomolov, Sergey; Kuzmenkov, Konstantin; Efremov, Andrey

2018-04-01

2.45 GHz ECR ion sources are widely used for production of protons, single charged heavy ions and secondary radioactive ion beams. This paper describes the development of a compact ECR ion source based on 2.45 GHz coaxial resonator. The first results of extracted current measurements at different resonator configuration as a function of UHF frequency, power and gas flow are presented.

HIAF: New opportunities for atomic physics with highly charged heavy ions

NASA Astrophysics Data System (ADS)

Ma, X.; Wen, W. Q.; Zhang, S. F.; Yu, D. Y.; Cheng, R.; Yang, J.; Huang, Z. K.; Wang, H. B.; Zhu, X. L.; Cai, X.; Zhao, Y. T.; Mao, L. J.; Yang, J. C.; Zhou, X. H.; Xu, H. S.; Yuan, Y. J.; Xia, J. W.; Zhao, H. W.; Xiao, G. Q.; Zhan, W. L.

2017-10-01

A new project, High Intensity heavy ion Accelerator Facility (HIAF), is currently being under design and construction in China. HIAF will provide beams of stable and unstable heavy ions with high energies, high intensities and high quality. An overview of new opportunities for atomic physics using highly charged ions and radioactive heavy ions at HIAF is given.

Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions

DOE PAGES

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet; ...

2016-07-01

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

Electrostatic field and charge distribution in small charged dielectric droplets

NASA Astrophysics Data System (ADS)

Storozhev, V. B.

2004-08-01

The charge distribution in small dielectric droplets is calculated on the basis of continuum medium approximation. There are considered charged liquid spherical droplets of methanol in the range of nanometer sizes. The problem is solved by the following way. We find the free energy of some ion in dielectric droplet, which is a function of distribution of other ions in the droplet. The probability of location of the ion in some element of volume in the droplet is a function of its free energy in this element of volume. The same approach can be applied to other ions in the droplet. The obtained charge distribution differs considerably from the surface distribution. The curve of the charge distribution in the droplet as a function of radius has maximum near the surface. Relative concentration of charges in the vicinity of the center of the droplet does not equal to zero, and it is the higher, the less is the total charge of the droplet. According to the estimates the model is applicable if the droplet radius is larger than 10 nm.

[Probabilistic calculations of biomolecule charge states that generate mass spectra of multiply charged ions].

PubMed

Raznikova, M O; Raznikov, V V

2015-01-01

In this work, information relating to charge states of biomolecule ions in solution obtained using the electrospray ionization mass spectrometry of different biopolymers is analyzed. The data analyses have mainly been carried out by solving an inverse problem of calculating the probabilities of retention of protons and other charge carriers by ionogenic groups of biomolecules with known primary structures. The approach is a new one and has no known to us analogues. A program titled "Decomposition" was developed and used to analyze the charge distribution of ions of native and denatured cytochrome c mass spectra. The possibility of splitting of the charge-state distribution of albumin into normal components, which likely corresponds to various conformational states of the biomolecule, has been demonstrated. The applicability criterion for using previously described method of decomposition of multidimensional charge-state distributions with two charge carriers, e.g., a proton and a sodium ion, to characterize the spatial structure of biopolymers in solution has been formulated. In contrast to known mass-spectrometric approaches, this method does not require the use of enzymatic hydrolysis or collision-induced dissociation of the biopolymers.

Ionization Efficiency of Doubly Charged Ions Formed from Polyprotic Acids in Electrospray Negative Mode

NASA Astrophysics Data System (ADS)

Liigand, Piia; Kaupmees, Karl; Kruve, Anneli

2016-07-01

The ability of polyprotic acids to give doubly charged ions in negative mode electrospray was studied and related to physicochemical properties of the acids via linear discriminant analysis (LDA). It was discovered that the compound has to be strongly acidic (low p K a1 and p K a2) and to have high hydrophobicity (log P ow) to become multiply charged. Ability to give multiply charged ions in ESI/MS cannot be directly predicted from the solution phase acidities. Therefore, for the first time, a quantitative model to predict the charge state of the analyte in ESI/MS is proposed and validated for small anions. Also, a model to predict ionization efficiencies of these analytes was developed. Results indicate that acidity of the analyte, its octanol-water partition coefficient, and charge delocalization are important factors that influence ionization efficiencies as well as charge states of the analytes. The pH of the solvent was also found to be an important factor influencing the ionization efficiency of doubly charged ions.

MOS Circuitry Would Detect Low-Energy Charged Particles

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva; Wadsworth, Mark

2003-01-01

Metal oxide semiconductor (MOS) circuits for measuring spatially varying intensities of beams of low-energy charged particles have been developed. These circuits are intended especially for use in measuring fluxes of ions with spatial resolution along the focal planes of mass spectrometers. Unlike prior mass spectrometer focal-plane detectors, these MOS circuits would not be based on ion-induced generation of electrons, and photons; instead, they would be based on direct detection of the electric charges of the ions. Hence, there would be no need for microchannel plates (for ion-to-electron conversion), phosphors (for electron-to-photon conversion), and photodetectors (for final detection) -- components that degrade spatial resolution and contribute to complexity and size. The developmental circuits are based on linear arrays of charge-coupled devices (CCDs) with associated readout circuitry (see figure). They resemble linear CCD photodetector arrays, except that instead of a photodetector, each pixel contains a capacitive charge sensor. The capacitor in each sensor comprises two electrodes (typically made of aluminum) separated by a layer of insulating material. The exposed electrode captures ions and accumulates their electric charges during signal-integration periods.

The Development Of New Space Charge Compensation Methods For Multi-Components Ion Beam Extracted From ECR Ion Source at IMP

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

Ma, L.; Zhao, H.W.; Cao, Y.

2005-03-15

Two new space charge compensation methods developed in IMP are discussed in this paper. There are negative high voltage electrode method (NHVEM) and electronegative charge gas method (EGM). Some valuable experimental data have been achieved, especially using electronegative gas method in O6+ and O7+ dramatic and stable increasing of ion current was observed.

Synthesis of lithium superionic conductor by growth of a nanoglass within mesoporous silica SBA-15 template

NASA Astrophysics Data System (ADS)

Chatterjee, Soumi; Miah, Milon; Saha, Shyamal Kumar; Chakravorty, Dipankar

2018-04-01

Nanodimensional silica based glasses containing alkali ions have recently been grown using suitable templates. These have shown electrical properties drastically different from those of their bulk counterpart. We have synthesized silicophosphate glasses having lithium ions with concentrations of 15-35 mole% Li2O within mesoporous silica SBA-15 (Santa Barbara amorphous-15) comprising of pores of diameter ~5 nm. The nanoglasses are characterized by electrical conductivities 5-6 orders of magnitude higher than those of the corresponding bulk glasses. These properties are attributed to the presence of a larger free volume in the nanoglasses as compared to their bulk states. The nanocomposites with 35 mole% Li2O exhibit an electrical conductivity of ~3 × 10-4 S · cm-1 at around room temperature. The activation energy for Li+ ion migration has been estimated from the conductivity-temperature variation to be 0.078 eV. These nanocomposites are believed to be ideally suited for the fabrication of solid state lithium ion batteries. We have also explored the efficiency of silicophosphate glass powders as possible electrode materials. Glass of composition 70SiO2/30P2O5 was prepared by using Pluronic P-123 tri-block copolymer along with suitable precursor sols. Cyclic voltammetric and galvanostatic charge/discharge measurements were carried out on the samples prepared in combination with suitable conductive fillers using a two-electrode system. These exhibited a high specific capacitance of 356 F g-1 making them ideally suitable as electrode materials for making a lithium ion solid state battery system.

Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

NASA Technical Reports Server (NTRS)

Wilson, L. B., III

2012-01-01

We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves.

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

NASA Astrophysics Data System (ADS)

Sharma, Pramod; Das, Soumitra; Vatsa, Rajesh K.

2017-07-01

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C2+, Sn2+) at 266 nm, (C4+, Sn4+) at 355 nm, and (C4+, Sn6+) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H2 +) and triatomic molecular hydrogen ion (H3 +). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

The effects of ion adsorption on the potential of zero charge and the differential capacitance of charged aqueous interfaces

NASA Astrophysics Data System (ADS)

Uematsu, Yuki; Netz, Roland R.; Bonthuis, Douwe Jan

2018-02-01

Using a box profile approximation for the non-electrostatic surface adsorption potentials of anions and cations, we calculate the differential capacitance of aqueous electrolyte interfaces from a numerical solution of the Poisson-Boltzmann equation, including steric interactions between the ions and an inhomogeneous dielectric profile. Preferential adsorption of the positive (negative) ion shifts the minimum of the differential capacitance to positive (negative) surface potential values. The trends are similar for the potential of zero charge; however, the potential of zero charge does not correspond to the minimum of the differential capacitance in the case of asymmetric ion adsorption, contrary to the assumption commonly used to determine the potential of zero charge. Our model can be used to obtain more accurate estimates of ion adsorption properties from differential capacitance or electrocapillary measurements. Asymmetric ion adsorption also affects the relative heights of the characteristic maxima in the differential capacitance curves as a function of the surface potential, but even for strong adsorption potentials the effect is small, making it difficult to reliably determine the adsorption properties from the peak heights.

Solar photovoltaic charging of lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gibson, Thomas L.; Kelly, Nelson A.

Solar photovoltaic (PV) charging of batteries was tested by using high efficiency crystalline and amorphous silicon PV modules to recharge lithium-ion battery modules. This testing was performed as a proof of concept for solar PV charging of batteries for electrically powered vehicles. The iron phosphate type lithium-ion batteries were safely charged to their maximum capacity and the thermal hazards associated with overcharging were avoided by the self-regulating design of the solar charging system. The solar energy to battery charge conversion efficiency reached 14.5%, including a PV system efficiency of nearly 15%, and a battery charging efficiency of approximately 100%. This high system efficiency was achieved by directly charging the battery from the PV system with no intervening electronics, and matching the PV maximum power point voltage to the battery charging voltage at the desired maximum state of charge for the battery. It is envisioned that individual homeowners could charge electric and extended-range electric vehicles from residential, roof-mounted solar arrays, and thus power their daily commuting with clean, renewable solar energy.

New Perspectives on the Charging Mechanisms of Supercapacitors

PubMed Central

2016-01-01

Supercapacitors (or electric double-layer capacitors) are high-power energy storage devices that store charge at the interface between porous carbon electrodes and an electrolyte solution. These devices are already employed in heavy electric vehicles and electronic devices, and can complement batteries in a more sustainable future. Their widespread application could be facilitated by the development of devices that can store more energy, without compromising their fast charging and discharging times. In situ characterization methods and computational modeling techniques have recently been developed to study the molecular mechanisms of charge storage, with the hope that better devices can be rationally designed. In this Perspective, we bring together recent findings from a range of experimental and computational studies to give a detailed picture of the charging mechanisms of supercapacitors. Nuclear magnetic resonance experiments and molecular dynamics simulations have revealed that the electrode pores contain a considerable number of ions in the absence of an applied charging potential. Experiments and computer simulations have shown that different charging mechanisms can then operate when a potential is applied, going beyond the traditional view of charging by counter-ion adsorption. It is shown that charging almost always involves ion exchange (swapping of co-ions for counter-ions), and rarely occurs by counter-ion adsorption alone. We introduce a charging mechanism parameter that quantifies the mechanism and allows comparisons between different systems. The mechanism is found to depend strongly on the polarization of the electrode, and the choice of the electrolyte and electrode materials. In light of these advances we identify new directions for supercapacitor research. Further experimental and computational work is needed to explain the factors that control supercapacitor charging mechanisms, and to establish the links between mechanisms and performance. Increased understanding and control of charging mechanisms should lead to new strategies for developing next-generation supercapacitors with improved performances. PMID:27031622

Disordering of ultra thin WO3 films by high-energy ions

NASA Astrophysics Data System (ADS)

Matsunami, N.; Kato, M.; Sataka, M.; Okayasu, S.

2017-10-01

We have studied disordering or atomic structure modification of ultra thin WO3 films under impact of high-energy ions with non-equilibrium and equilibrium charge incidence, by means of X-ray diffraction (XRD). WO3 films were prepared by thermal oxidation of W deposited on MgO substrate. Film thickness obtained by Rutherford backscattering spectrometry (RBS) is as low as 2 nm. Smoothness of film surface was observed by atomic force microscopy. It is found that the ratio of XRD intensity degradation per 90 MeV Ni+10 ion (the incident charge is lower than the equilibrium charge) to that per 90 MeV Ni ion with the equilibrium charge depends on the film thickness. Also, film thickness dependence is observed for 100 MeV Xe+14. By comparison of the experimental result with a simple model calculation based on the assumption that the mean charge of ions along the depth follows a saturation curve with power-law approximation to the charge dependent electronic stopping power, the characteristic length attaining the equilibrium charge is obtained to be ∼7 nm for 90 MeV Ni+10 ion incidence or the electron loss cross section of ∼1016 cm2, demonstrating that disordering of ultra WO3 films has been observed and a fundamental quantity can be derived through material modification.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

DUHOCAMIS: a dual hollow cathode ion source for metal ion beams.

PubMed

Zhao, W J; Müller, M W O; Janik, J; Liu, K X; Ren, X T

2008-02-01

In this paper we describe a novel ion source named DUHOCAMIS for multiply charged metal ion beams. This ion source is derived from the hot cathode Penning ion gauge ion source (JINR, Dubna, 1957). A notable characteristic is the modified Penning geometry in the form of a hollow sputter electrode, coaxially positioned in a compact bottle-magnetic field along the central magnetic line of force. The interaction of the discharge geometry with the inhomogeneous but symmetrical magnetic field enables this device to be operated as hollow cathode discharge and Penning discharge as well. The main features of the ion source are the very high metal ion efficiency (up to 25%), good operational reproducibility, flexible and efficient operations for low charged as well as highly charged ions, compact setup, and easy maintenance. For light ions, e.g., up to titanium, well-collimated beams in the range of several tens of milliamperes of pulsed ion current (1 ms, 10/s) have been reliably performed in long time runs.

Supercharging with Trivalent Metal Ions in Native Mass Spectrometry

PubMed Central

Flick, Tawnya G.; Williams, Evan R.

2012-01-01

Addition of 1.0 mM LaCl3 to aqueous ammonium acetate solutions containing proteins in their folded native forms can result in a significant increase in the molecular ion charging obtained with electrospray ionization as a result of cation adduction. In combination with m-nitrobenzyl alcohol, molecular ion charge states that are greater than the number of basic sites in the protein can be produced from these native solutions, even for lysozyme, which is conformationally constrained by four intramolecular disulfide bonds. Circular dichroism spectroscopy indicates that the conformation of ubiquitin is not measurably affected with up to 1.0 M LaCl3, but ion mobility data indicate that the high charge states that are formed when 1.0 mM LaCl3 is present are more unfolded than the low charge states formed without this reagent. These and other results indicate that the increased charging is a result of La3+ preferentially adducting onto compact or more native-like conformers during ESI and the gas-phase ions subsequently unfolding as a result of increased Coulomb repulsion. Electron capture dissociation of these high charge-state ions formed from these native solutions results in comparable sequence coverage to that obtained for ions formed from denaturing solutions without supercharging reagents, making this method a potentially powerful tool for obtaining structural information in native mass spectrometry. PMID:22948901

Ultra High Resolution Linear Ion Trap Orbitrap Mass Spectrometer (Orbitrap Elite) Facilitates Top Down LC MS/MS and Versatile Peptide Fragmentation Modes*

PubMed Central

Michalski, Annette; Damoc, Eugen; Lange, Oliver; Denisov, Eduard; Nolting, Dirk; Müller, Mathias; Viner, Rosa; Schwartz, Jae; Remes, Philip; Belford, Michael; Dunyach, Jean-Jacques; Cox, Juergen; Horning, Stevan; Mann, Matthias; Makarov, Alexander

2012-01-01

Although only a few years old, the combination of a linear ion trap with an Orbitrap analyzer has become one of the standard mass spectrometers to characterize proteins and proteomes. Here we describe a novel version of this instrument family, the Orbitrap Elite, which is improved in three main areas. The ion transfer optics has an ion path that blocks the line of sight to achieve more robust operation. The tandem MS acquisition speed of the dual cell linear ion trap now exceeds 12 Hz. Most importantly, the resolving power of the Orbitrap analyzer has been increased twofold for the same transient length by employing a compact, high-field Orbitrap analyzer that almost doubles the observed frequencies. An enhanced Fourier Transform algorithm—incorporating phase information—further doubles the resolving power to 240,000 at m/z 400 for a 768 ms transient. For top-down experiments, we combine a survey scan with a selected ion monitoring scan of the charge state of the protein to be fragmented and with several HCD microscans. Despite the 120,000 resolving power for SIM and HCD scans, the total cycle time is within several seconds and therefore suitable for liquid chromatography tandem MS. For bottom-up proteomics, we combined survey scans at 240,000 resolving power with data-dependent collision-induced dissociation of the 20 most abundant precursors in a total cycle time of 2.5 s—increasing protein identifications in complex mixtures by about 30%. The speed of the Orbitrap Elite furthermore allows scan modes in which complementary dissociation mechanisms are routinely obtained of all fragmented peptides. PMID:22159718

Recoil ions from the β decay of 134Sb confined in a Paul trap

NASA Astrophysics Data System (ADS)

Siegl, K.; Scielzo, N. D.; Czeszumska, A.; Clark, J. A.; Savard, G.; Aprahamian, A.; Caldwell, S. A.; Alan, B. S.; Burkey, M. T.; Chiara, C. J.; Greene, J. P.; Harker, J.; Marley, S. T.; Morgan, G. E.; Munson, J. M.; Norman, E. B.; Orford, R.; Padgett, S.; Galván, A. Perez; Sharma, K. S.; Strauss, S. Y.

2018-03-01

The low-energy recoiling ions from the β decay of 134Sb were studied by using the Beta-decay Paul Trap. Using this apparatus, singly charged ions were suspended in vacuum at the center of a detector array used to detect emitted β particles, γ rays, and recoil ions in coincidence. The recoil ions emerge from the trap with negligible scattering, allowing β -decay properties and the charge-state distribution of the daughter ions to be determined from the β -ion coincidences. First-forbidden β -decay theory predicts a β -ν correlation coefficient of nearly unity for the 0- to 0+ transition from the ground state of 134Sb to the ground state of 134Te. Although this transition was expected to have a nearly 100% branching ratio, an additional 17.2(52)% of the β -decay strength must populate high-lying excited states to obtain an angular correlation consistent with unity. The extracted charge-state distribution of the recoiling ions was compared with existing β -decay results and the average charge state was found to be consistent with the results from lighter nuclei.

Effect of Ca2+ ion concentration on adsorption of poly(carboxylate ether)-based (PCE) superplasticizer on mica.

PubMed

Wu, Bo; Chun, Byong-Wa; Gu, Le; Kuhl, Tonya L

2018-05-09

Poly(carboxylate ether)-based (PCE) superplasticizers consist of a carboxylic acid backbone and grafted poly(ethylene glycol) (PEG) side chains. Ca 2+ ion bridging mechanism is commonly purported to control PCE's adsorption on negatively charged cement particle surfaces in cement suspension, thus PCE was expected to adsorb on negatively charged surfaces in synthetic pore solutions via Ca 2+ /COO - interactions. Adsorption behaviors of a commercial PCE on negatively charged mica were studied in aqueous electrolyte solutions by a surface forces apparatus. Direct force measurements indicated that the PCE adsorbed onto mica from 0.1 M K 2 SO 4 due to K + ion chelation by the ether oxygen units CH 2 CH 2 O on the PEG chains, but surprisingly did not adsorb from either 0.1 M K 2 SO 4 with saturated Ca(OH) 2 or 0.1 M Ca(NO 3 ) 2 . The adsorption in K 2 SO 4 was weak, enabling the adsorbed PCE layers to be squeezed out under modest compression. Upon separating the surfaces, the PCE immediately achieved an identical re-adsorption. In high-calcium conditions, the PCE was highly positively charged due to Ca 2+ ion chelation by PEG chains and backbone carboxylic groups COO - , and mica also underwent charge reversal due to electrostatic adsorption/binding of Ca 2+ ions. Consequently, the interaction between mica and PCE was electrostatically repulsive and no PCE adsorption occurred. These findings can be explained by the complex interplay of ion chelation by PEG chains, electrostatic binding and screening interactions with charged surfaces in the presence of monovalent and divalent counterions, and ultimately charge reversal of both the charged surfaces and polyelectrolyte in high divalent ion conditions. Copyright © 2018 Elsevier Inc. All rights reserved.

The charge-energy-mass spectrometer for 0.3-300 keV/e ions on the AMPTE CCE

NASA Technical Reports Server (NTRS)

Gloeckler, G.; Ipavich, F. M.; Hamilton, D. C.; Lundgren, R. A.; Studemann, W.; Wilken, B.; Kremser, G.; Hovestadt, D.; Gliem, F.; Rieck, W.

1985-01-01

The charge-energy-mass (CHEM) spectrometer on the Charge Composition Explorer (CCE) has the function to measure the energy spectra, pitch-angle distributions, and ionization states of ions in the earth's magnetosphere and magnetosheath in the energy range from 0.3 to 300 keV/charge with a time resolution of less than 1 min. The obtained data will provide essential information on outstanding problems related to ion sources and dynamical processes of space plasmas and of suprathermal ions. A description of the CHEM experiment is given, taking into account the principle of operation, the sensor, the electronics, instrument characteristics, specifications, and requirements. Questions of postlaunch performance are also discussed.

Charge reconstruction of the DAMPE Silicon-Tungsten Tracker: A preliminary study with ion beams

NASA Astrophysics Data System (ADS)

Qiao, Rui; Peng, Wen-Xi; Guo, Dong-Ya; Zhao, Hao; Wang, Huan-Yu; Gong, Ke; Zhang, Fei; Wu, Xin; Azzarello, Phillip; Tykhonov, Andrii; Asfandiyarov, Ruslan; Gallo, Valentina; Ambrosi, Giovanni

2018-04-01

The DArk Matter Particle Explorer (DAMPE) is one of the four satellites within Strategic Pioneer Research Program in Space Science of the Chinese Academy of Science (CAS). DAMPE can detect electrons, photons in a wide energy range (5 GeV to 10 TeV) and ions up to iron (100 GeV to 100 TeV). The silicon-Tungsten Tracker (STK) is one of the four subdetectors in DAMPE, providing photon-electron conversion, track reconstruction and charge identification for ions. An ion beam test was carried out in CERN with 60 GeV/u Lead primary beams. Charge reconstruction and charge resolution of the STK detectors were investigated.

Moving Fe2+ from ferritin ion channels to catalytic OH centers depends on conserved protein cage carboxylates

PubMed Central

Behera, Rabindra K.; Theil, Elizabeth C.

2014-01-01

Ferritin biominerals are protein-caged metabolic iron concentrates used for iron–protein cofactors and oxidant protection (Fe2+ and O2 sequestration). Fe2+ passage through ion channels in the protein cages, like membrane ion channels, required for ferritin biomineral synthesis, is followed by Fe2+ substrate movement to ferritin enzyme (Fox) sites. Fe2+ and O2 substrates are coupled via a diferric peroxo (DFP) intermediate, λmax 650 nm, which decays to [Fe3+–O–Fe3+] precursors of caged ferritin biominerals. Structural studies show multiple conformations for conserved, carboxylate residues E136 and E57, which are between ferritin ion channel exits and enzymatic sites, suggesting functional connections. Here we show that E136 and E57 are required for ferritin enzyme activity and thus are functional links between ferritin ion channels and enzymatic sites. DFP formation (Kcat and kcat/Km), DFP decay, and protein-caged hydrated ferric oxide accumulation decreased in ferritin E57A and E136A; saturation required higher Fe2+ concentrations. Divalent cations (both ion channel and intracage binding) selectively inhibit ferritin enzyme activity (block Fe2+ access), Mn2+ << Co2+ < Cu2+ < Zn2+, reflecting metal ion–protein binding stabilities. Fe2+–Cys126 binding in ferritin ion channels, observed as Cu2+–S–Cys126 charge-transfer bands in ferritin E130D UV-vis spectra and resistance to Cu2+ inhibition in ferritin C126S, was unpredicted. Identifying E57 and E136 links in Fe2+ movement from ferritin ion channels to ferritin enzyme sites completes a bucket brigade that moves external Fe2+ into ferritin enzymatic sites. The results clarify Fe2+ transport within ferritin and model molecular links between membrane ion channels and cytoplasmic destinations. PMID:24843174

EBIT spectroscopy of highly charged heavy ions relevant to hot plasmas

NASA Astrophysics Data System (ADS)

Nakamura, Nobuyuki

2013-05-01

An electron beam ion trap (EBIT) is a versatile device for studying highly charged ions. We have been using two types of EBITs for the spectroscopic studies of highly charged ions. One is a high-energy device called the Tokyo-EBIT, and another is a compact low-energy device called CoBIT. Complementary use of them enables us to obtain spectroscopic data for ions over a wide charge-state range interacting with electrons over a wide energy range. In this talk, we present EBIT spectra of highly charged ions for tungsten, iron, bismuth, etc., which are relevant to hot plasmas. Tungsten is considered to be the main impurity in the ITER (the next generation nuclear fusion reactor) plasma, and thus its emission lines are important for diagnosing and controlling the ITER plasma. We have observed many previously unreported lines to supply the lack of spectroscopic data of tungsten ions. Iron is one of the main components of the solar corona, and its spectra are used to diagnose temperature, density, etc. The diagnostics is usually done by comparing observed spectra with model calculations. An EBIT can provide spectra under a well-defined condition; they are thus useful to test the model calculations. Laser-produced bismuth plasma is one of the candidates for a soft x-ray source in the water window region. An EBIT has a narrow charge state distribution; it is thus useful to disentangle the spectra of laser-produced plasma containing ions with a wide charge-state range. Performed with the support and under the auspices of the NIFS Collaboration Research program (NIFS09KOAJ003) and JSPS KAKENHI Number 23246165, and partly supported by the JSPS-NRF-NSFC A3 Foresight Program in the field of Plasma Physics.

Characterization of an atomic hydrogen source for charge exchange experiments

DOE PAGES

Leutenegger, M. A.; Beiersdorfer, P.; Betancourt-Martinez, G. L.; ...

2016-07-02

Here, we characterized the dissociation fraction of a thermal dissociation atomic hydrogen source by injecting the mixed atomic and molecular output of the source into an electron beam ion trap containing highly charged ions and recording the x-ray spectrum generated by charge exchange using a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchange state-selective capture cross sections are very different for atomic and molecular hydrogen incident on the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

Charge breeding of radioactive isotopes at the CARIBU facility with an electron beam ion source

NASA Astrophysics Data System (ADS)

Vondrasek, R. C.; Dickerson, C. A.; Hendricks, M.; Ostroumov, P.; Pardo, R.; Savard, G.; Scott, R.; Zinkann, G.

2018-05-01

An Electron Beam Ion Source Charge Breeder (EBIS-CB) has been developed at Argonne National Laboratory as part of the californium rare ion breeder upgrade. For the past year, the EBIS-CB has been undergoing commissioning as part of the ATLAS accelerator complex. It has delivered both stable and radioactive beams with A/Q < 6, breeding times <30 ms, low background contamination, and charge breeding efficiencies >18% into a single charge state. The operation of this device, challenges during the commissioning phase, and future improvements will be discussed.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

Amplification due to two-stream instability of self-electric and magnetic fields of an ion beam propagating in background plasma

NASA Astrophysics Data System (ADS)

Tokluoglu, Erinc K.; Kaganovich, Igor D.; Carlsson, Johan A.; Hara, Kentaro; Startsev, Edward A.

2018-05-01

Propagation of charged particle beams in background plasma as a method of space charge neutralization has been shown to achieve a high degree of charge and current neutralization and therefore enables nearly ballistic propagation and focusing of charged particle beams. Correspondingly, the use of plasmas for propagation of charged particle beams has important applications for transport and focusing of intense particle beams in inertial fusion and high energy density laboratory plasma physics. However, the streaming of beam ions through a background plasma can lead to the development of two-stream instability between the beam ions and the plasma electrons. The beam electric and magnetic fields enhanced by the two-stream instability can lead to defocusing of the ion beam. Using particle-in-cell simulations, we study the scaling of the instability-driven self-electromagnetic fields and consequent defocusing forces with the background plasma density and beam ion mass. We identify plasma parameters where the defocusing forces can be reduced.

A comparative study on low-energy ion beam and neutralized beam modifications of naked DNA and biological effect on mutation

NASA Astrophysics Data System (ADS)

Sarapirom, S.; Thongkumkoon, P.; Prakrajang, K.; Anuntalabhochai, S.; Yu, L. D.

2012-02-01

DNA conformation change or damage induced by low-energy ion irradiation has been of great interest owing to research developments in ion beam biotechnology and ion beam application in biomedicine. Mechanisms involved in the induction of DNA damage may account for effect from implanting ion charge. In order to check this effect, we used both ion beam and neutralized beam at keV energy to bombard naked DNA. Argon or nitrogen ion beam was generated and extracted from a radiofrequency (RF) ion source and neutralized by microwave-driven plasma in the beam path. Plasmid DNA pGFP samples were irradiated with the ion or neutralized beam in vacuum, followed by gel electrophoresis to observe changes in the DNA conformations. It was revealed that the ion charge played a certain role in inducing DNA conformation change. The subsequent DNA transfer into bacteria Escherichia coli ( E. coli) for mutation analysis indicated that the charged ion beam induced DNA change had high potential in mutation induction while neutralized beam did not. The intrinsic reason was attributed to additional DNA deformation and contortion caused by ion charge exchange effect so that the ion beam induced DNA damage could hardly be completely repaired, whereas the neutralized beam induced DNA change could be more easily recoverable owing to absence of the additional DNA deformation and contortion.

Aggregation and Charge Behavior of Metallic and Nonmetallic Nanoparticles in the Presence of Competing Similarly-Charged Inorganic Ions

EPA Science Inventory

The influence of competing, similarly charged, inorganic ions on the size and charge behavior of suspended titanium-dioxide (nTiO2), silver (nAg) and fullerene (nC60) nanoparticles (NPs) was investigated. Under pH and ionic conditions similar to natural water bodies, Ca2+ induced...

Specific ion effects on membrane potential and the permselectivity of ion exchange membranes.

PubMed

Geise, Geoffrey M; Cassady, Harrison J; Paul, Donald R; Logan, Bruce E; Hickner, Michael A

2014-10-21

Membrane potential and permselectivity are critical parameters for a variety of electrochemically-driven separation and energy technologies. An electric potential is developed when a membrane separates electrolyte solutions of different concentrations, and a permselective membrane allows specific species to be transported while restricting the passage of other species. Ion exchange membranes are commonly used in applications that require advanced ionic electrolytes and span technologies such as alkaline batteries to ammonium bicarbonate reverse electrodialysis, but membranes are often only characterized in sodium chloride solutions. Our goal in this work was to better understand membrane behaviour in aqueous ammonium bicarbonate, which is of interest for closed-loop energy generation processes. Here we characterized the permselectivity of four commercial ion exchange membranes in aqueous solutions of sodium chloride, ammonium chloride, sodium bicarbonate, and ammonium bicarbonate. This stepwise approach, using four different ions in aqueous solution, was used to better understand how these specific ions affect ion transport in ion exchange membranes. Characterization of cation and anion exchange membrane permselectivity, using these ions, is discussed from the perspective of the difference in the physical chemistry of the hydrated ions, along with an accompanying re-derivation and examination of the basic equations that describe membrane potential. In general, permselectivity was highest in sodium chloride and lowest in ammonium bicarbonate solutions, and the nature of both the counter- and co-ions appeared to influence measured permselectivity. The counter-ion type influences the binding affinity between counter-ions and polymer fixed charge groups, and higher binding affinity between fixed charge sites and counter-ions within the membrane decreases the effective membrane charge density. As a result permselectivity decreases. The charge density and polarizability of the co-ions also appeared to influence permselectivity leading to ion-specific effects; co-ions that are charge dense and have low polarizability tended to result in high membrane permselectivity.

Effects of Ion Atomic Number on Single-Event Gate Rupture (SEGR) Susceptibility of Power MOSFETs

NASA Technical Reports Server (NTRS)

Lauenstein, Jean-Marie; Goldsman, Neil; Liu, Sandra; Titus, Jeffrey L.; Ladbury, Raymond L.; Kim, Hak S.; Phan, Anthony M.; LaBel, Kenneth A.; Zafrani, Max; Sherman, Phillip

2012-01-01

The relative importance of heavy-ion interaction with the oxide, charge ionized in the epilayer, and charge ionized in the drain substrate, on the bias for SEGR failure in vertical power MOSFETs is experimentally investigated. The results indicate that both the charge ionized in the epilayer and the ion atomic number are important parameters of SEGR failure. Implications on SEGR hardness assurance are discussed.

Final Technical Report of Project DE-FG02-96ER14647

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

Lundeen, Stephen R.

This is the final technical report of work completed under DOE support over the period Sept. 1, 1996 until May 31, 2015. The title of the project was "Ion/Excited Atom Collision Studies with a Rydberg Target and a CO2 Laser" from 9/1/96 to 10/31/06, and "Properties of Actinide Ions from Measurements of Rydberg Ion Fine Structure" from 11/1/06 until 5/31/15. The primary technical results were a detailed experimental study of resonant charge transfer between Rydberg atoms and highly-charged ions, and unique measurements of many properties of multiply-charged Thorium ions.

Plasma particle simulation of electrostatic ion thrusters

NASA Technical Reports Server (NTRS)

Peng, Xiaohang; Keefer, Dennis; Ruyten, Wilhelmus

1990-01-01

Charge exchange collisons between beam ions and neutral propellant gas can result in erosion of the accelerator grid surfaces of an ion engine. A particle in cell (PIC) is developed along with a Monte Carlo method to simulate the ion dynamics and charge exchange processes in the grid region of an ion thruster. The simulation is two-dimensional axisymmetric and uses three velocity components (2d3v) to investigate the influence of charge exchange collisions on the ion sputtering of the accelerator grid surfaces. An example calculation has been performed for an ion thruster operated on xenon propellant. The simulation shows that the greatest sputtering occurs on the downstream surface of the grid, but some sputtering can also occur on the upstream surface as well as on the interior of the grid aperture.

Aggregation and charging of sulfate and amidine latex particles in the presence of oxyanions.

PubMed

Sugimoto, Takuya; Cao, Tianchi; Szilagyi, Istvan; Borkovec, Michal; Trefalt, Gregor

2018-08-15

Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions. Copyright © 2018 Elsevier Inc. All rights reserved.

Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

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

Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault

2016-01-28

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the timemore » evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.« less

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

Wu, Qin; Zaikowski, Lori; Kaur, Parmeet

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenesmore » or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.« less

The direct injection of intense ion beams from a high field electron cyclotron resonance ion source into a radio frequency quadrupole

NASA Astrophysics Data System (ADS)

Rodrigues, G.; Becker, R.; Hamm, R. W.; Baskaran, R.; Kanjilal, D.; Roy, A.

2014-02-01

The ion current achievable from high intensity ECR sources for highly charged ions is limited by the high space charge. This makes classical extraction systems for the transport and subsequent matching to a radio frequency quadrupole (RFQ) accelerator less efficient. The direct plasma injection (DPI) method developed originally for the laser ion source avoids these problems and uses the combined focusing of the gap between the ion source and the RFQ vanes (or rods) and the focusing of the rf fields from the RFQ penetrating into this gap. For high performance ECR sources that use superconducting solenoids, the stray magnetic field of the source in addition to the DPI scheme provides focusing against the space charge blow-up of the beam. A combined extraction/matching system has been designed for a high performance ECR ion source injecting into an RFQ, allowing a total beam current of 10 mA from the ion source for the production of highly charged 238U40+ (1.33 mA) to be injected at an ion source voltage of 60 kV. In this design, the features of IGUN have been used to take into account the rf-focusing of an RFQ channel (without modulation), the electrostatic field between ion source extraction and the RFQ vanes, the magnetic stray field of the ECR superconducting solenoid, and the defocusing space charge of an ion beam. The stray magnetic field is shown to be critical in the case of a matched beam.

The direct injection of intense ion beams from a high field electron cyclotron resonance ion source into a radio frequency quadrupole.

PubMed

Rodrigues, G; Becker, R; Hamm, R W; Baskaran, R; Kanjilal, D; Roy, A

2014-02-01

The ion current achievable from high intensity ECR sources for highly charged ions is limited by the high space charge. This makes classical extraction systems for the transport and subsequent matching to a radio frequency quadrupole (RFQ) accelerator less efficient. The direct plasma injection (DPI) method developed originally for the laser ion source avoids these problems and uses the combined focusing of the gap between the ion source and the RFQ vanes (or rods) and the focusing of the rf fields from the RFQ penetrating into this gap. For high performance ECR sources that use superconducting solenoids, the stray magnetic field of the source in addition to the DPI scheme provides focusing against the space charge blow-up of the beam. A combined extraction/matching system has been designed for a high performance ECR ion source injecting into an RFQ, allowing a total beam current of 10 mA from the ion source for the production of highly charged (238)U(40+) (1.33 mA) to be injected at an ion source voltage of 60 kV. In this design, the features of IGUN have been used to take into account the rf-focusing of an RFQ channel (without modulation), the electrostatic field between ion source extraction and the RFQ vanes, the magnetic stray field of the ECR superconducting solenoid, and the defocusing space charge of an ion beam. The stray magnetic field is shown to be critical in the case of a matched beam.

Intense highly charged ion beam production and operation with a superconducting electron cyclotron resonance ion source

NASA Astrophysics Data System (ADS)

Zhao, H. W.; Sun, L. T.; Guo, J. W.; Lu, W.; Xie, D. Z.; Hitz, D.; Zhang, X. Z.; Yang, Y.

2017-09-01

The superconducting electron cyclotron resonance ion source with advanced design in Lanzhou (SECRAL) is a superconducting-magnet-based electron cyclotron resonance ion source (ECRIS) for the production of intense highly charged heavy ion beams. It is one of the best performing ECRISs worldwide and the first superconducting ECRIS built with an innovative magnet to generate a high strength minimum-B field for operation with heating microwaves up to 24-28 GHz. Since its commissioning in 2005, SECRAL has so far produced a good number of continuous wave intensity records of highly charged ion beams, in which recently the beam intensities of 40Ar+ and 129Xe26+ have, for the first time, exceeded 1 emA produced by an ion source. Routine operations commenced in 2007 with the Heavy Ion accelerator Research Facility in Lanzhou (HIRFL), China. Up to June 2017, SECRAL has been providing more than 28,000 hours of highly charged heavy ion beams to the accelerator demonstrating its great capability and reliability. The great achievement of SECRAL is accumulation of numerous technical advancements, such as an innovative magnetic system and an efficient double-frequency (24 +18 GHz ) heating with improved plasma stability. This article reviews the development of SECRAL and production of intense highly charged ion beams by SECRAL focusing on its unique magnet design, source commissioning, performance studies and enhancements, beam quality and long-term operation. SECRAL development and its performance studies representatively reflect the achievements and status of the present ECR ion source, as well as the ECRIS impacts on HIRFL.

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

PubMed Central

Xia, Yu; McLuckey, Scott A.

2008-01-01

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

Nanopipette delivery: influence of surface charge.

PubMed

Shi, Wenqing; Sa, Niya; Thakar, Rahul; Baker, Lane A

2015-07-21

In this report, transport through a nanopipette is studied and the interplay between current rectification and ion delivery for small pipettes is examined. First, surface charge dependence of concentration polarization effects in a quartz nanopipette was investigated. Electrical characterization was performed through current-potential (I-V) measurements. In addition, fluorescein (an anionic fluorescent probe) was utilized to optically map ion enrichment and ion depletion in the nanopipette tip. Bare nanopipettes and polyethylenimine (PEI)-modified nanopipettes were examined. Results confirm that concentration polarization is a surface charge dependent phenomenon and delivery can be controlled through modification of surface charge. The relationship between concentration polarization effects and voltage-driven delivery of charged electroactive species was investigated with a carbon ring/nanopore electrode fabricated from pyrolyzed parylene C (PPC). Factors such as surface charge polarity of the nanopipette, electrolyte pH, and electrolyte concentration were investigated. Results indicate that with modification of surface charge, additional control over delivery of charged species can be achieved.

Probing lithium-ion batteries' state-of-charge using ultrasonic transmission - Concept and laboratory testing

NASA Astrophysics Data System (ADS)

Gold, Lukas; Bach, Tobias; Virsik, Wolfgang; Schmitt, Angelika; Müller, Jana; Staab, Torsten E. M.; Sextl, Gerhard

2017-03-01

For electrically powered applications such as consumer electronics and especially for electric vehicles a precise state-of-charge estimation for their lithium-ion batteries is desired to reduce aging, e.g. avoiding detrimental states-of-charge. Today, this estimation is performed by battery management systems that solely rely on charge bookkeeping and cell voltage measurements. In the present work we introduce a new, physical probe for the state-of-charge based on ultrasonic transmission. Within the simple experimental setup raised cosine pulses are applied to lithium-ion battery pouch cells, whose signals are sensitive to changes in porosity of the graphite anode during charging/dis-charging and, therefore, to the state-of-charge. The underlying physical principle can be related to Biot's theory about propagation of waves in fluid saturated porous media and by including scattering by boundary layers inside the cell.

Miniaturized ultrafine particle sizer and monitor

NASA Technical Reports Server (NTRS)

Qi, Chaolong (Inventor); Chen, Da-Ren (Inventor)

2011-01-01

An apparatus for measuring particle size distribution includes a charging device and a precipitator. The charging device includes a corona that generates charged ions in response to a first applied voltage, and a charger body that generates a low energy electrical field in response to a second applied voltage in order to channel the charged ions out of the charging device. The corona tip and the charger body are arranged relative to each other to direct a flow of particles through the low energy electrical field in a direction parallel to a direction in which the charged ions are channeled out of the charging device. The precipitator receives the plurality of particles from the charging device, and includes a disk having a top surface and an opposite bottom surface, wherein a predetermined voltage is applied to the top surface and the bottom surface to precipitate the plurality of particles.

Liquid chromatography-tandem mass spectrometry characterization of five new leucinostatins produced by Paecilomyces lilacinus CG-189.

PubMed

Martinez, Ana Flávia Canovas; Moraes, Luiz Alberto Beraldo

2015-03-01

The fungus Paecilomyces lilacinus produces leucinostatins—peptaibiotics that exert a range of biological activities including antimalarial, antiviral, antitumor and phytotoxicity. In this paper, we developed an analytical method employing LC-MS/MS in the precursor ion and product ion scan modes to elucidate five new leucinostatins. Direct Infusion (DI-MS) helped to identify the most abundant leucinostatins: F, D B2, S, A and K. MS/MS analysis using a triple quadrupole operating at different scan modes is a versatile tool to study natural products, especially peptaibiotics. Although DI-MS full-scan analysis is rapid and sensitive, it cannot distinguish between peptide isomers. On the other hand, LC-MS/MS operated in the precursor ion and product ion modes is time consuming, but allows identifying the structure of isomers or isobar in crude extracts.

Target Plate Material Influence on Fullerene-C60 Laser Desorption/Ionization Efficiency.

PubMed

Zeegers, Guido P; Günthardt, Barbara F; Zenobi, Renato

2016-04-01

Systematic laser desorption/ionization (LDI) experiments of fullerene-C60 on a wide range of target plate materials were conducted to gain insight into the initial ion formation in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The positive and negative ion signal intensities of precursor, fragment, and cluster ions were monitored, varying both the laser fluence (0-3.53 Jcm(-2)) and the ion extraction delay time (0-950 ns). The resulting species-specific ion signal intensities are an indication for the ionization mechanisms that contribute to LDI and the time frames in which they operate, providing insight in the (MA)LDI primary ionization. An increasing electrical resistivity of the target plate material increases the fullerene-C60 precursor and fragment anion signal intensity. Inconel 625 and Ti90/Al6/V4, both highly electrically resistive, provide the highest anion signal intensities, exceeding the cation signal intensity by a factor ~1.4 for the latter. We present a mechanism based on transient electrical field strength reduction to explain this trend. Fullerene-C60 cluster anion formation is negligible, which could be due to the high extraction potential. Cluster cations, however, are readily formed, although for high laser fluences, the preferred channel is formation of precursor and fragment cations. Ion signal intensity depends greatly on the choice of substrate material, and careful substrate selection could, therefore, allow for more sensitive (MA)LDI measurements. Graphical Abstract ᅟ.

Secondary Structures of Ubiquitin Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

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

Hu, Qichi; Laskin, Julia

2016-06-09

The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH 3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known tomore » stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.« less

Fast and efficient charge breeding of the Californium rare isotope breeder upgrade electron beam ion source

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

Ostroumov, P. N.; Barcikowski, A.; Dickerson, C. A.

The Electron Beam Ion Source (EBIS), developed to breed CARIBU radioactive beams at ATLAS, is being tested off-line. A unique property of the EBIS is a combination of short breeding times, high repetition rates and a large acceptance. Overall, we have implemented many innovative features during the design and construction of the CARIBU EBIS as compared to the existing EBIS breeders. The offline charge breeding tests are being performed using a surface ionization source that produces singly-charged cesium ions. The main goal of the off-line commissioning is to demonstrate stable operation of the EBIS at a 10 Hz repetition ratemore » and a breeding efficiency into single charge state higher than 15%. These goals have been successfully achieved and exceeded. We have measured (20±0.7)% breeding efficiency into the single charge state of 28+ cesium ions with the breeding time of 28 ms. In general, the current CARIBU EBIS operational parameters can provide charge breeding of any ions in the full mass range of periodic table with high efficiency, short breeding times and sufficiently low charge-to-mass ratio, 1/6.3 for the heaviest masses, for further acceleration in ATLAS. In this paper we discuss the parameters of the EBIS and the charge breeding results in a pulsed injection mode with repetition rates up to 10 Hz.« less

Dynamic Secondary Ion Mass Spectrometry | Materials Science | NREL

Science.gov Websites

different temperatures. Hydrogen loss is greater for higher temperatures; however, the rate of loss for a ions according to their mass-to-charge ratio. Ions of different mass-to-charge ratios are selected by Identifies all elements or isotopes present in a material, from hydrogen to uranium. Different primary-ion

Electrospray ionization of uranyl-citrate complexes

NASA Astrophysics Data System (ADS)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures and charge state distributions.

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

NASA Astrophysics Data System (ADS)

Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

2016-11-01

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Quantifying the Labeling and the Levels of Plant Cell Wall Precursors Using Ion Chromatography Tandem Mass Spectrometry1[W][OA

PubMed Central

Alonso, Ana P.; Piasecki, Rebecca J.; Wang, Yan; LaClair, Russell W.; Shachar-Hill, Yair

2010-01-01

The biosynthesis of cell wall polymers involves enormous fluxes through central metabolism that are not fully delineated and whose regulation is poorly understood. We have established and validated a liquid chromatography tandem mass spectrometry method using multiple reaction monitoring mode to separate and quantify the levels of plant cell wall precursors. Target analytes were identified by their parent/daughter ions and retention times. The method allows the quantification of precursors at low picomole quantities with linear responses up to the nanomole quantity range. When applying the technique to Arabidopsis (Arabidopsis thaliana) T87 cell cultures, 16 hexose-phosphates (hexose-Ps) and nucleotide-sugars (NDP-sugars) involved in cell wall biosynthesis were separately quantified. Using hexose-P and NDP-sugar standards, we have shown that hot water extraction allows good recovery of the target metabolites (over 86%). This method is applicable to quantifying the levels of hexose-Ps and NDP-sugars in different plant tissues, such as Arabidopsis T87 cells in culture and fenugreek (Trigonella foenum-graecum) endosperm tissue, showing higher levels of galacto-mannan precursors in fenugreek endosperm. In Arabidopsis cells incubated with [U-13CFru]sucrose, the method was used to track the labeling pattern in cell wall precursors. As the fragmentation of hexose-Ps and NDP-sugars results in high yields of [PO3]−/or [H2PO4]− ions, mass isotopomers can be quantified directly from the intensity of selected tandem mass spectrometry transitions. The ability to directly measure 13C labeling in cell wall precursors makes possible metabolic flux analysis of cell wall biosynthesis based on dynamic labeling experiments. PMID:20442274

Image charge effects on electron capture by dust grains in dusty plasmas.

PubMed

Jung, Y D; Tawara, H

2001-07-01

Electron-capture processes by negatively charged dust grains from hydrogenic ions in dusty plasmas are investigated in accordance with the classical Bohr-Lindhard model. The attractive interaction between the electron in a hydrogenic ion and its own image charge inside the dust grain is included to obtain the total interaction energy between the electron and the dust grain. The electron-capture radius is determined by the total interaction energy and the kinetic energy of the released electron in the frame of the projectile dust grain. The classical straight-line trajectory approximation is applied to the motion of the ion in order to visualize the electron-capture cross section as a function of the impact parameter, kinetic energy of the projectile ion, and dust charge. It is found that the image charge inside the dust grain plays a significant role in the electron-capture process near the surface of the dust grain. The electron-capture cross section is found to be quite sensitive to the collision energy and dust charge.

Molecular layer deposition of "vanadicone", a vanadium-based hybrid material, as an electrode for lithium-ion batteries.

PubMed

Van de Kerckhove, Kevin; Mattelaer, Felix; Dendooven, Jolien; Detavernier, Christophe

2017-04-05

Molecular layer deposition (MLD) of hybrid organic-inorganic thin films called "vanadicones" was investigated using tetrakisethylmethylaminovanadium (TEMAV) as the metal precursor and glycerol (GL) or ethylene glycol (EG) as the organic reactant. Linear and continued growth could only be achieved with GL as the organic reactant. The TEMAV/GL process displayed self-limiting reactions for both precursor and reactant pulses in the temperature range from 80 °C to 180 °C, with growth rates of 1.2 to 0.5 Å per cycle, respectively. Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed the hybrid nature of the films. From X-ray reflectivity, the density was estimated at 2.6 g cm -3 . A series of 21 nm vanadicone films were subjected to annealing under oxidizing (air) or inert (He) atmospheres at 500 °C. During annealing in air, the film crystallized to the V 2 O 5 phase and all carbon was removed from the film. The films annealed in helium remained amorphous and retained most of their carbon content. Electrochemical measurements revealed lithium-ion activity during cyclic voltammetry in all treated films, while the as deposited film was inactive. In the 2.9 to 3.5 V vs. Li + /Li potential region, no improvement over the V 2 O 5 reference was observed. However, the helium annealed samples outperformed V 2 O 5 in terms of capacity, rate performance and cyclability when charged and discharged in the 1.0 to 3.5 V vs. Li + /Li region. This result enables the application of V x O y -based hybrid electrodes in a wider potential range without sacrificing the stability and performance.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

PubMed

Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

2018-06-04

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

NASA Astrophysics Data System (ADS)

Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

2018-06-01

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Arbitrary amplitude electrostatic wave propagation in a magnetized dense plasma containing helium ions and degenerate electrons

NASA Astrophysics Data System (ADS)

Mahmood, S.; Sadiq, Safeer; Haque, Q.; Ali, Munazza Z.

2016-06-01

The obliquely propagating arbitrary amplitude electrostatic wave is studied in a dense magnetized plasma having singly and doubly charged helium ions with nonrelativistic and ultrarelativistic degenerate electrons pressures. The Fermi temperature for ultrarelativistic degenerate electrons described by N. M. Vernet [(Cambridge University Press, Cambridge, 2007), p. 57] is used to define ion acoustic speed in ultra-dense plasmas. The pseudo-potential approach is used to solve the fully nonlinear set of dynamic equations for obliquely propagating electrostatic waves in a dense magnetized plasma containing helium ions. The upper and lower Mach number ranges for the existence of electrostatic solitons are found which depends on the obliqueness of the wave propagation with respect to applied magnetic field and charge number of the helium ions. It is found that only compressive (hump) soliton structures are formed in all the cases and only subsonic solitons are formed for a singly charged helium ions plasma case with nonrelativistic degenerate electrons. Both subsonic and supersonic soliton hump structures are formed for doubly charged helium ions with nonrelativistic degenerate electrons and ultrarelativistic degenerate electrons plasma case containing singly as well as doubly charged helium ions. The effect of propagation direction on the soliton amplitude and width of the electrostatic waves is also presented. The numerical plots are also shown for illustration using dense plasma parameters of a compact star (white dwarf) from literature.

Electron parallel closures for various ion charge numbers

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

Ji, Jeong-Young, E-mail: j.ji@usu.edu; Held, Eric D.; Kim, Sang-Kyeun

2016-03-15

Electron parallel closures for the ion charge number Z = 1 [J.-Y. Ji and E. D. Held, Phys. Plasmas 21, 122116 (2014)] are extended for 1 ≤ Z ≤ 10. Parameters are computed for various Z with the same form of the Z = 1 kernels adopted. The parameters are smoothly varying in Z and hence can be used to interpolate parameters and closures for noninteger, effective ion charge numbers.

A Closer Look at Solar Wind Sputtering of Lunar Surface Materials

NASA Technical Reports Server (NTRS)

Barghouty, A. F.; Adams, J. H., Jr.; Meyer, F.; Mansur, L.; Reinhold, C.

2008-01-01

Solar-wind induced potential sputtering of the lunar surface may be a more efficient erosive mechanism than the "standard" kinetic (or physical) sputtering. This is partly based on new but limited laboratory measurements which show marked enhancements in the sputter yields of slow-moving, highly-charged ions impacting oxides. The enhancements seen in the laboratory can be orders of magnitude for some surfaces and highly charged incident ions, but seem to depend very sensitively on the properties of the impacted surface in addition to the fluence, energy and charge of the impacting ion. For oxides, potential sputtering yields are markedly enhanced and sputtered species, especially hydrogen and light ions, show marked dependence on both charge and dose.

A common pathway for charge transport through voltage-sensing domains.

PubMed

Chanda, Baron; Bezanilla, Francisco

2008-02-07

Voltage-gated ion channels derive their voltage sensitivity from the movement of specific charged residues in response to a change in transmembrane potential. Several studies on mechanisms of voltage sensing in ion channels support the idea that these gating charges move through a well-defined permeation pathway. This gating pathway in a voltage-gated ion channel can also be mutated to transport free cations, including protons. The recent discovery of proton channels with sequence homology to the voltage-sensing domains suggests that evolution has perhaps exploited the same gating pathway to generate a bona fide voltage-dependent proton transporter. Here we will discuss implications of these findings on the mechanisms underlying charge (and ion) transport by voltage-sensing domains.

In situ measurement of surface potential developed on MgO thin film surface under ion irradiation using ion scattering spectroscopy

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

Nagatomi, T.; Kuwayama, T.; Takai, Y.

2009-11-15

The application of ion scattering spectroscopy (ISS) to the in situ measurement of the surface potential developed on an insulator surface under positive ion irradiation was investigated. The ISS spectra measured for a MgO film of 600 nm thickness on a Si substrate by the irradiation of 950 eV He{sup +} ions revealed that the surface is positively charged by approximately 180 V. For accurate measurement of the surface potential, a correction to take into account the angular deflection of primary ions induced by the high surface potential is required. The dependence of the surface potential on the sample temperaturemore » revealed that no charging is induced above 700 deg. C, indicating that accumulated charges can be removed by heating to 700 deg. C. From the measurement of the ion-induced secondary electron yield using a collector electrode located in front of the sample surface, the surface potential and ion-induced secondary electron yield were found to be strongly affected by the experimental setup. Secondary electrons produced by the impact of slow positive secondary ions, the maximum energy of which corresponds to the surface potential, play an important role when the bias voltage applied to the collector electrode is positively high for the present experimental setup. The surface potential developed on the surface of MgO films of 600 and 200 nm thickness was measured in situ, revealing that the amount of accumulated charges and the time required to attain the steady state of charging are slightly dependent on the beam current of primary ions and strongly dependent on the thickness of the MgO film. The present results confirmed that the application of ISS has high potential for investigating charging phenomena and the secondary electron emission from insulator surfaces under positive ion irradiation.« less

Design and simulation of ion optics for ion sources for production of singly charged ions

NASA Astrophysics Data System (ADS)

Zelenak, A.; Bogomolov, S. L.

2004-05-01

During the last 2 years different types of the singly charged ion sources were developed for FLNR (JINR) new projects such as Dubna radioactive ion beams, (Phase I and Phase II), the production of the tritium ion beam and the MASHA mass separator. The ion optics simulations for 2.45 GHz electron cyclotron resonance source, rf source, and the plasma ion source were performed. In this article the design and simulation results of the optics of new ion sources are presented. The results of simulation are compared with measurements obtained during the experiments.

Ion guiding in macro-size insulating capillaries: straight, tapered, and curved shapes

NASA Astrophysics Data System (ADS)

Kojima, Takao M.

2018-02-01

When keV energy ions are injected into a tilted insulating capillary, a certain fraction of the injected ions are transported through the tilt angle of the capillary. This ion guiding phenomenon is considered to be caused by a self-organizing charge distribution, where the inner wall of the capillary becomes charged by initial incoming ions. The charge distribution, which is formed, can guide following ions toward the exit of the capillary. Since the initial discovery of this effect, studies of ion guiding by insulating capillaries have been extended to various materials, and different sizes and shapes of capillaries. In recent years, some investigations of the guiding effect of macro-size curved capillaries have also been reported. In this review, relevant studies in a history of ion guiding in curved capillaries are discussed and future directions in this field are considered.

Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson-Nernst-Planck equations involving ionization in a weak electrolyte

NASA Astrophysics Data System (ADS)

Suzuki, Yohichi; Seki, Kazuhiko

2018-03-01

We studied ion concentration profiles and the charge density gradient caused by electrode reactions in weak electrolytes by using the Poisson-Nernst-Planck equations without assuming charge neutrality. In weak electrolytes, only a small fraction of molecules is ionized in bulk. Ion concentration profiles depend on not only ion transport but also the ionization of molecules. We considered the ionization of molecules and ion association in weak electrolytes and obtained analytical expressions for ion densities, electrostatic potential profiles, and ion currents. We found the case that the total ion density gradient was given by the Kuramoto length which characterized the distance over which an ion diffuses before association. The charge density gradient is characterized by the Debye length for 1:1 weak electrolytes. We discuss the role of these length scales for efficient water splitting reactions using photo-electrocatalytic electrodes.

Synchrotron radiation-based 61Ni Mössbauer spectroscopic study of Li(Ni1/3Mn1/3Co1/3)O2 cathode materials of lithium ion rechargeable battery

NASA Astrophysics Data System (ADS)

Segi, Takashi; Masuda, Ryo; Kobayashi, Yasuhiro; Tsubota, Takayuki; Yoda, Yoshitaka; Seto, Makoto

2016-12-01

Layered rocksalt type oxides, such as Li(Ni1/3Mn1/3Co1/3)O2, are widely used as the cathode active materials of lithium-ion rechargeable batteries. Because the nickel ions are associated with the role of the charge compensation at discharge and charge, the 61Ni Mössbauer measurements at 6 K using synchrotron radiation were performed to reveal the role of Ni. The Ni ions of the active materials play two roles for the redox process between the charge and discharge states of lithium-ion batteries. Half of the total Ni ions change to the low-spin Ni3+ with Jahn-Teller distortion from the Ni2+ ions of the discharge state. The remainder exhibit low-spin state divalent Ni ions.

Ponderomotive ion acceleration in dense magnetized laser-irradiated thick target plasmas

NASA Astrophysics Data System (ADS)

Sinha, Ujjwal; Kaw, Predhiman

2012-03-01

When a circularly polarized laser pulse falls on an overdense plasma, it displaces the electrons via ponderomotive force creating a double layer. The double layer constitutes of an ion and electron sheath with in which the electrostatic field present is responsible for ion acceleration. In this paper, we have analyzed the effect a static longitudinal magnetic field has over the ion acceleration mechanism. The longitudinal magnetic field changes the plasma dielectric constant due to cyclotron effects which in turn enhances or reduces the ponderomotive force exerted by the laser depending on whether the laser is left or right circularly polarized. Also, the analysis of the ion space charge region present behind the ion sheath of the laser piston that undergoes coulomb explosion has been explored for the first time. We have studied the interaction of an incoming ion beam with the laser piston and the ion space charge. It has been found that the exploding ion space charge has the ability to act as an energy amplifier for incoming ion beams.

A -100 kV Power Supply for Ion Acceleration in Space-based Mass Spectrometers

NASA Astrophysics Data System (ADS)

Gilbert, J. A.; Zurbuchen, T.; Battel, S.

2017-12-01

High voltage power supplies are used in many space-based time-of-flight (TOF) mass spectrometer designs to accelerate incoming ions and increase the probability of their measurement and proper identification. Ions are accelerated in proportion to their charge state, so singly charged ions such as pickup ions are accelerated less than their multiple-charge state solar wind counterparts. This lack of acceleration results in pickup ion measurements with lower resolution and without determinations of absolute energy. Acceleration reduces the effects of angular scattering and energy straggling when ions pass through thin membranes such as carbon foils, and it brings ion energies above the detection threshold of traditional solid state detectors. We have developed a power supply capable of operating at -100 kV for ion acceleration while also delivering up to 10 W of power for the operation of a floating TOF system. We also show results of benchtop calibration and ion beam tests to demonstrate the functionality and success of this approach.

One-dimension modeling on the parallel-plate ion extraction process based on a non-electron-equilibrium fluid model

NASA Astrophysics Data System (ADS)

Li, He-Ping; Chen, Jian; Guo, Heng; Jiang, Dong-Jun; Zhou, Ming-Sheng; Department of Engineering Physics Team

2017-10-01

Ion extraction from a plasma under an externally applied electric field involve multi-particle and multi-field interactions, and has wide applications in the fields of materials processing, etching, chemical analysis, etc. In order to develop the high-efficiency ion extraction methods, it is indispensable to establish a feasible model to understand the non-equilibrium transportation processes of the charged particles and the evolutions of the space charge sheath during the extraction process. Most of the previous studies on the ion extraction process are mainly based on the electron-equilibrium fluid model, which assumed that the electrons are in the thermodynamic equilibrium state. However, it may lead to some confusions with neglecting the electron movement during the sheath formation process. In this study, a non-electron-equilibrium model is established to describe the transportation of the charged particles in a parallel-plate ion extraction process. The numerical results show that the formation of the Child-Langmuir sheath is mainly caused by the charge separation. And thus, the sheath shielding effect will be significantly weakened if the charge separation is suppressed during the extraction process of the charged particles.

Oriented epitaxial TiO2 nanowires for water splitting

NASA Astrophysics Data System (ADS)

Hou, Wenting; Cortez, Pablo; Wuhrer, Richard; Macartney, Sam; Bozhilov, Krassimir N.; Liu, Rong; Sheppard, Leigh R.; Kisailus, David

2017-06-01

Highly oriented epitaxial rutile titanium dioxide (TiO2) nanowire arrays have been hydrothermally grown on polycrystalline TiO2 templates with their orientation dependent on the underlying TiO2 grain. Both the diameter and areal density of the nanowires were tuned by controlling the precursor concentration, and the template surface energy and roughness. Nanowire tip sharpness was influenced by precursor solubility and diffusivity. A new secondary ion mass spectrometer technique has been developed to install additional nucleation sites in single crystal TiO2 templates and the effect on nanowire growth was probed. Using the acquired TiO2 nanowire synthesis knowhow, an assortment of nanowire arrays were installed upon the surface of undoped TiO2 photo-electrodes and assessed for their photo-electrochemical water splitting performance. The key result obtained was that the presence of short and dispersed nanowire arrays significantly improved the photocurrent when the illumination intensity was increased from 100 to 200 mW cm-2. This is attributed to the alignment of the homoepitaxially grown nanowires to the [001] direction, which provides the fastest charge transport in TiO2 and an improved pathway for photo-holes to find water molecules and undertake oxidation. This result lays a foundation for achieving efficient water splitting under conditions of concentrated solar illumination.

Intercalation of Li Ions into a Graphite Anode Material: Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Abou Hamad, Ibrahim; Novotny, Mark

2008-03-01

Large-scale molecular dynamics simulations of the anode half-cell of a lithium-ion battery are presented. The model system is composed of an anode represented by a stack of graphite sheets, an electrolyte of ethylene carbonate and propylene carbonate molecules, and lithium and hexafluorophosphate ions. The simulations are done in the NVT ensemble and at room temperature. One charging scheme explored is normal charging in which intercalation is enhanced by electric charges on the graphitic sheets. The second charging mechanism has an external applied oscillatory electric field of amplitude A and frequency f. The simulations were performed on 2.6 GHz Opteron processors, using 160 processors at a time. Our simulation results show an improvement in the intercalation time of the lithium ions for the second charging mechanism. The dependence of the intercalation time on A and f will be discussed.

A Charge-Exchange Neutral Particle Analyzer for an Inertial Electrostatic Confinement Fusion Device

NASA Astrophysics Data System (ADS)

Becerra, Gabriel; Kulcinski, Gerald; Santarius, John; Emmert, Gilbert

2013-10-01

An electrostatic energy analyzer for outgoing charge-exchange neutral particles has been designed and constructed for application on HELIOS, an inertial electrostatic confinement (IEC) fusion device designed for advanced fuel studies. Ions are extracted from an external helicon plasma source and subsequently accelerated radially into an electrostatic potential well set up by a semi-transparent cathode grid inside the HELIOS spherical chamber. Analysis of fast neutrals produced by charge exchange between energetic ions and background gas yields information on primary ion energy spectra, as well as a quantitative measure of charge exchange as an energy loss mechanism in IEC devices. Preliminary data with helium is used to benchmark the two-charge-state helium formalism of VICTER, a numerical code on spherically convergent ion flow, as it relates to IEC operation with helium-3 fuel. Research supported by the Greatbatch Foundation.

Photodissociation spectroscopy of (benzene-toluene) +. Charge delocalization in the hetero-dimer ion

NASA Astrophysics Data System (ADS)

Ohashi, Kazuhiko; Nakane, Youko; Inokuchi, Yoshiya; Nakai, Yasuhiro; Nishi, Nobuyuki

1998-12-01

The electronic spectrum of the benzene-toluene hetero-dimer ion is measured in the 380-1400 nm region. The spectrum shows intense bands around 1175 and 670 nm and a weaker band around 920 nm, which correspond to charge resonance (CR) bands of homo-dimer ions. The observation indicates that the positive charge stays on the benzene part in some probability, although the ionization potential of benzene is 0.4162 eV higher than that of toluene. A local excitation (LE) band is observed around 420 nm, where a π←π transition is locally excited in the charged benzene or toluene molecule. On the basis of the positions of the CR-like bands, as well as the intensity of the LE band relative to that of homo-dimer ions, the probability of finding the charge on the benzene molecule is analyzed to be approximately 36%.

Tuning the Fabrication of Nanostructures by Low-Energy Highly Charged Ions.

PubMed

El-Said, Ayman S; Wilhelm, Richard A; Heller, Rene; Sorokin, Michael; Facsko, Stefan; Aumayr, Friedrich

2016-09-16

Slow highly charged ions have been utilized recently for the creation of monotype surface nanostructures (craters, calderas, or hillocks) in different materials. In the present study, we report on the ability of slow highly charged xenon ions (^{129}Xe^{Q+}) to form three different types of nanostructures on the LiF(100) surface. By increasing the charge state from Q=15 to Q=36, the shape of the impact induced nanostructures changes from craters to hillocks crossing an intermediate stage of caldera structures. A dimensional analysis of the nanostructures reveals an increase of the height up to 1.5 nm as a function of the potential energy of the incident ions. Based on the evolution of both the geometry and size of the created nanostructures, defect-mediated desorption and the development of a thermal spike are utilized as creation mechanisms of the nanostructures at low and high charge states, respectively.

Pyramidal pits created by single highly charged ions in BaF{sub 2} single crystals

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

El-Said, A. S.; Physics Department, Faculty of Science, Mansoura University, 35516 Mansoura; Heller, R.

2010-07-15

In various insulators, the impact of individual slow highly charged ions (eV-keV) creates surface nanostructures, whose size depends on the deposited potential energy. Here we report on the damage created on a cleaved BaF{sub 2} (111) surface by irradiation with 4.5xq keV highly charged xenon ions from a room-temperature electron-beam ion trap. Up to charge states q=36, no surface topographic changes on the BaF{sub 2} surface are observed by scanning force microscopy. The hidden stored damage, however, can be made visible using the technique of selective chemical etching. Each individual ion impact develops into a pyramidal etch pits, as canmore » be concluded from a comparison of the areal density of observed etch pits with the applied ion fluence (typically 10{sup 8} ions/cm{sup 2}). The dimensional analysis of the measured pits reveals the significance of the deposited potential energy in the creation of lattice distortions/defects in BaF{sub 2}.« less

Electron Transfer Ion/Ion Reactions in a Three-Dimensional Quadrupole Ion Trap: Reactions of Doubly and Triply Protonated Peptides with SO2·−

PubMed Central

Pitteri, Sharon J.; Chrisman, Paul A.; Hogan, Jason M.; McLuckey, Scott A.

2005-01-01

Ion–ion reactions between a variety of peptide cations (doubly and triply charged) and SO2 anions have been studied in a 3-D quadrupole ion trap, resulting in proton and electron transfer. Electron transfer dissociation (ETD) gives many c- and z-type fragments, resulting in extensive sequence coverage in the case of triply protonated peptides with SO2·−. For triply charged neurotensin, in which a direct comparison can be made between 3-D and linear ion trap results, abundances of ETD fragments relative to one another appear to be similar. Reactions of doubly protonated peptides with SO2·− give much less structural information from ETD than triply protonated peptides. Collision-induced dissociation (CID) of singly charged ions formed in reactions with SO2·− shows a combination of proton and electron transfer products. CID of the singly charged species gives more structural information than ETD of the doubly protonated peptide, but not as much information as ETD of the triply protonated peptide. PMID:15762593

SINGLE AND DOUBLE PHOTOIONIZATION AND PHOTODISSOCIATION OF TOLUENE BY SOFT X-RAYS IN A CIRCUMSTELLAR ENVIRONMENT

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

Monfredini, T.; Boechat-Roberty, H. M.; Fantuzzi, F.

The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C–H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large numbermore » of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.« less

Ionization and Corona Discharges from Stressed Rocks

NASA Astrophysics Data System (ADS)

Winnick, M. J.; Kulahci, I.; Cyr, G.; Tregloan-Reed, J.; Freund, F. T.

2008-12-01

Pre-earthquake signals have long been observed and documented, though they have not been adequately explained scientifically. These signals include air ionization, occasional flashes of light from the ground, radio frequency emissions, and effects on the ionosphere that occur hours or even days before large earthquakes. The theory that rocks function as p-type semiconductors when deviatoric stresses are applied offers a mechanism for this group of earthquake precursors. When an igneous or high-grade metamorphic rock is subjected to deviatoric stresses, peroxy bonds that exist in the rock's minerals as point defects dissociate, releasing positive hole charge carriers. The positive holes travel by phonon-assisted electron hopping from the stressed into and through the unstressed rock volume and build up a positive surface charge. At sufficiently large electric fields, especially along edges and sharp points of the rock, air molecules become field-ionized, loosing an electron to the rock surface and turning into airborne positive ions. This in turn can lead to corona discharges, which manifest themselves by flashes of light and radio frequency emissions. We applied concentrated stresses to one end of a block of gabbro, 30 x 15 x 10 cm3, inside a shielded Faraday cage and observed positive ion currents through an air gap about 25 cm from the place where the stresses were applied, punctuated by short bursts, accompanied by flashes of light and radio frequency emissions characteristic of a corona discharge. These observations may serve to explain a range of pre-earthquake signals, in particular changes in air conductivity, luminous phenomena, radio frequency noise, and ionospheric perturbations.

Single and Double Photoionization and Photodissociation of Toluene by Soft X-Rays in a Circumstellar Environment

NASA Astrophysics Data System (ADS)

Monfredini, T.; Fantuzzi, F.; Nascimento, M. A. C.; Wolff, W.; Boechat-Roberty, H. M.

2016-04-01

The formation of polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives mainly occurs in the dust shells of asymptotic giant branch (AGB) stars. The bands at 3.3 and 3.4 μm, observed in infrared emission spectra of several objects, are attributed C-H vibrational modes in aromatic and aliphatic structures, respectively. In general, the feature at 3.3 μm is more intense than that at 3.4 μm. Photoionization and photodissociation processes of toluene, the precursor of methylated PAHs, were studied using synchrotron radiation at soft X-ray energies around the carbon K edge using time-of-flight mass spectrometry. Partial ion yields of a large number of ionic fragments were extracted from single and 2D-spectra, where electron-ion coincidences have revealed the doubly charged parent molecule and several doubly charged fragments containing seven carbon atoms with considerable abundance. Ab initio calculations based on density functional theory were performed in order to elucidate the chemical structure of these stable dicationic species. The survival of the dications subjected to hard inner shell ionization suggests that they could be observed in the interstellar medium, especially in regions where PAHs are detected. The ionization and destruction of toluene induced by X-rays were examined in the T Dra conditions, a carbon-rich AGB star. In this context, a minimum photodissociation radius and the half-life of toluene subjected to the incidence of the soft X-ray flux emitted from a companion white dwarf star were determined.

Numerical simulations of gas mixing effect in electron cyclotron resonance ion sources

NASA Astrophysics Data System (ADS)

Mironov, V.; Bogomolov, S.; Bondarchenko, A.; Efremov, A.; Loginov, V.

2017-01-01

The particle-in-cell Monte Carlo collisions code nam-ecris is used to simulate the electron cyclotron resonance ion source (ECRIS) plasma sustained in a mixture of Kr with O2 , N2 , Ar, Ne, and He. The model assumes that ions are electrostatically confined in the ECR zone by a dip in the plasma potential. A gain in the extracted krypton ion currents is seen for the highest charge states; the gain is maximized when oxygen is used as a mixing gas. The special feature of oxygen is that most of the singly charged oxygen ions are produced after the dissociative ionization of oxygen molecules with a large kinetic energy release of around 5 eV per ion. The increased loss rate of energetic lowly charged ions of the mixing element requires a building up of the retarding potential barrier close to the ECR surface to equilibrate electron and ion losses out of the plasma. In the mixed plasmas, the barrier value is large (˜1 V ) compared to pure Kr plasma (˜0.01 V ), with longer confinement times of krypton ions and with much higher ion temperatures. The temperature of the krypton ions is increased because of extra heating by the energetic oxygen ions and a longer time of ion confinement. In calculations, a drop of the highly charged ion currents of lighter elements is observed when adding small fluxes of krypton into the source. This drop is caused by the accumulation of the krypton ions inside plasma, which decreases the electron and ion confinement times.

Fe(+) chemical ionization of peptides.

PubMed

Speir, J P; Gorman, G S; Amster, I J

1993-02-01

Laser-desorbed peptide neutral molecules were allowed to react with Fe(+) in a Fourier transform mass spectrometer, using the technique of laser desorption/chemical ionization. The Fe(+) ions are formed by laser ablation of a steel target, as well as by dissociative charge-exchange ionization of ferrocene with Ne(+). Prior to reaction with laser-desorbed peptide molecules, Fe(+) ions undergo 20-100 thermalizin collisions with xenon to reduce the population of excited-state metal ion species. The Fe(+) ions that have not experienced thermalizing collisions undergo charge exchange with peptide molecules. Iron ions that undergo thermalizing collisions before they are allowed to react with peptides are found to undergo charge exchange and to form adduct species [M + Fe(+)] and fragment ions that result from the loss of small, stable molecules, such as H2O, CO, and CO2, from the metal ion-peptide complex.

Charging dynamics of supercapacitors with narrow cylindrical nanopores.

PubMed

Lee, Alpha A; Kondrat, Svyatoslav; Oshanin, Gleb; Kornyshev, Alexei A

2014-08-08

We present a coarse-grained, continuum kinetic theory for charging supercapacitors with narrow cylindrical nanopores. The theory reveals that the occupancy of a nonpolarized pore and the energy barrier for ion-ion interdiffusion are the key issues controlling the different regimes of dynamic response. For 'ionophobic' pores, where the pore is empty at no applied voltage, charge density advances into the pore via diffusion-like dynamics. The mechanism of charging an 'ionophilic' pore is starkly different: for moderate ionophilicities, co-ions are expelled from the pore in a front-like manner, with significant 'congestion' at the pore entrance predicted for strong ionophilicity. We thus show that pore ionophilicity is detrimental to the speed of charging/discharging cycles, whereas making pores more ionophobic can substantially accelerate charging and cyclic recharging.

Charging dynamics of supercapacitors with narrow cylindrical nanopores

NASA Astrophysics Data System (ADS)

Lee, Alpha A.; Kondrat, Svyatoslav; Oshanin, Gleb; Kornyshev, Alexei A.

2014-08-01

We present a coarse-grained, continuum kinetic theory for charging supercapacitors with narrow cylindrical nanopores. The theory reveals that the occupancy of a nonpolarized pore and the energy barrier for ion-ion interdiffusion are the key issues controlling the different regimes of dynamic response. For ‘ionophobic’ pores, where the pore is empty at no applied voltage, charge density advances into the pore via diffusion-like dynamics. The mechanism of charging an ‘ionophilic’ pore is starkly different: for moderate ionophilicities, co-ions are expelled from the pore in a front-like manner, with significant ‘congestion’ at the pore entrance predicted for strong ionophilicity. We thus show that pore ionophilicity is detrimental to the speed of charging/discharging cycles, whereas making pores more ionophobic can substantially accelerate charging and cyclic recharging.

Semiconductor hierarchically structured flower-like clusters for dye-sensitized solar cells with nearly 100% charge collection efficiency.

PubMed

Xin, Xukai; Liu, Hsiang-Yu; Ye, Meidan; Lin, Zhiqun

2013-11-21

By combining the ease of producing ZnO nanoflowers with the advantageous chemical stability of TiO2, hierarchically structured hollow TiO2 flower-like clusters were yielded via chemical bath deposition (CBD) of ZnO nanoflowers, followed by their conversion into TiO2 flower-like clusters in the presence of TiO2 precursors. The effects of ZnO precursor concentration, precursor amount, and reaction time on the formation of ZnO nanoflowers were systematically explored. Dye-sensitized solar cells fabricated by utilizing these hierarchically structured ZnO and TiO2 flower clusters exhibited a power conversion efficiency of 1.16% and 2.73%, respectively, under 100 mW cm(-2) illumination. The intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) studies suggested that flower-like structures had a fast electron transit time and their charge collection efficiency was nearly 100%.

Performance and operation of advanced superconducting electron cyclotron resonance ion source SECRAL at 24 GHza)

NASA Astrophysics Data System (ADS)

Zhao, H. W.; Lu, W.; Zhang, X. Z.; Feng, Y. C.; Guo, J. W.; Cao, Y.; Li, J. Y.; Guo, X. H.; Sha, S.; Sun, L. T.; Xie, D. Z.

2012-02-01

SECRAL (superconducting ECR ion source with advanced design in Lanzhou) ion source has been in routine operation for Heavy Ion Research Facility in Lanzhou (HIRFL) accelerator complex since May 2007. To further enhance the SECRAL performance in order to satisfy the increasing demand for intensive highly charged ion beams, 3-5 kW high power 24 GHz single frequency and 24 GHz +18 GHz double frequency with an aluminum plasma chamber were tested, and some exciting results were produced with quite a few new record highly charged ion beam intensities, such as 129Xe35+ of 64 eμA, 129Xe42+ of 3 eμA, 209Bi41+ of 50 eμA, 209Bi50+ of 4.3 eμA and 209Bi54+ of 0.2 eμA. In most cases SECRAL is operated at 18 GHz to deliver highly charged heavy ion beams for the HIRFL accelerator, only for those very high charge states and very heavy ion beams such as 209Bi36+ and 209Bi41+, SECRAL has been operated at 24 GHz. The total operation beam time provided by SECRAL up to July 2011 has exceeded 7720 hours. In this paper, the latest performance, development, and operation status of SECRAL ion source are presented. The latest results and reliable long-term operation for the HIRFL accelerator have demonstrated that SECRAL performance for production of highly charged heavy ion beams remains improving at higher RF power with optimized tuning.

Simulation of perturbation produced by an absorbing spherical body in collisionless plasma

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

Krasovsky, V. L., E-mail: vkrasov@iki.rssi.ru; Kiselyov, A. A., E-mail: alexander.kiselyov@stonehenge-3.net.ru; Dolgonosov, M. S.

2017-01-15

A steady plasma state reached in the course of charging of an absorbing spherical body is found using computational methods. Numerical simulations provide complete information on this process, thereby allowing one to find the spatiotemporal dependences of the physical quantities and observe the kinetic phenomena accompanying the formation of stable electron and ion distributions in phase space. The distribution function of trapped ions is obtained, and their contribution to the screening of the charged sphere is determined. The sphere charge and the charge of the trapped-ion cloud are determined as functions of the unperturbed plasma parameters.

Carbon Dioxide Removal by Salty Aerosols

NASA Astrophysics Data System (ADS)

Gokturk, H.

2016-12-01

Aerosols consisting of salt ions dissolved in water are observed in nature as sea spray particles generated by breaking waves. Such aerosols can be also generated artificially by spraying seawater to the atmosphere to create clouds, which was suggested as a method of solar radiation management (SRM). Salty aerosols can be utilized not only for SRM, but also for carbon dioxide removal from the atmosphere, if salt ions carrying charges -2 or more negative are added to the seawater. CO2 is a very stable molecule where carbon to oxygen double bond has a bond strength of 8.3 eV (190 kcal/mol). Therefore the approach chosen here to modify CO2 is to further oxidize it to CO3. Quantum mechanical calculations indicate that CO2 reacts readily with hydroxyl minus ion (OH-) or oxygen double minus ion (O-) to form HCO3- or CO3-, respectively. What is studied in this paper is the utilization of hydrated negative salt ions to create OH- and possibly even O-. The negative ions chosen are chlorine minus ion (Cl-), sulfate double minus ion (SO4-), phosphate triple minus ion (PO4--) and silicate quadruple minus ion (SiO4--). The former two ions exist in seawater, but the latter two ions do not, though they are available as part of water soluble salts such as potassium phosphate. Using quantum mechanical calculations, following reactions were investigated: R1: (Cl-) + H2O => HCl + (OH-), R2: (SO4-) + H2O => (HSO4-) + (OH-), R3: (PO4--) + H2O => (HPO4-) + (OH-), R4: (SiO4--) + H2O => (HSiO4--) + (OH-), R5: (HPO4-) + H2O => (H2PO4-) + (OH-), R6: (HSiO4--) + H2O => (H2SiO4-) + (OH-), R7: (H2SiO4-) + H2O => (H3SiO4-) + (OH-), R8: (SiO4--) + H2O => (H2SiO4-) + (O-). Results indicate that singly charged negative salt ions, such as Cl- in R1, cannot create OH-. Doubly charged negative salt ions, such as SO4- in R2, can create OH-, though the amount of SO4- in seawater is relatively small. Triply or quadruply charged negative ions are even more favorable than doubly charged ions in creating OH- (R3, R4, R6). Quadruply charged negative ions can also create O- (R8), however in practice O- is likely to react with other water molecules to create more OH-. In conclusion, seawater fortified with highly charged negative salt ions and sprayed into the atmosphere has the potential to create aerosols containing OH- which can react with the CO2 and modify it to a carbonate.

Proceeding of the 18th Intl. Workshop on Inelastic Ion-Surface Collisions (IISC-18)

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

Reinhold, Carlos O; Krstic, Predrag S; Meyer, Fred W

2011-01-01

The main topics of this proceedings were: (1) Energy loss of particles at surfaces; (2) Scattering of atoms, ions, molecules and clusters; (3) Charge exchange between particles and surfaces; (4) Ion induced desorption, electronic and kinetic sputtering; (5) Defect formation, surface modification and nanostructuring; (6) Electron, photon and secondary ion emission due to particle impact on surfaces; (7) Sputtering, fragmentation, cluster and ion formation in SIMS and SNMS; (8) Cluster/molecular and highly charged ion beams; and (9) Laser induced desorption.

Semi-empirical calculations for the ranges of fast ions in silicon

NASA Astrophysics Data System (ADS)

Belkova, Yu. A.; Teplova, Ya. A.

2018-04-01

A semi-empirical method is proposed to calculate the ion ranges in energy region E = 0.025-10 MeV/nucleon. The dependence of ion ranges on the projectile nuclear charge, mass and velocity is analysed. The calculations presented for ranges of ions with nuclear charges Z = 2-10 in silicon are compared with SRIM results and experimental data.

Facile synthesis of surface-functionalized magnetic nanocomposites for effectively selective adsorption of cationic dyes

NASA Astrophysics Data System (ADS)

Hua, Yani; Xiao, Juan; Zhang, Qinqin; Cui, Chang; Wang, Chuan

2018-04-01

A new magnetic nano-adsorbent, polycatechol modified Fe3O4 magnetic nanoparticles (Fe3O4/PCC MNPs) were prepared by a facile chemical coprecipitation method using iron salts and catechol solution as precursors. Fe3O4/PCC MNPs owned negatively charged surface with oxygen-containing groups and showed a strong adsorption capacity and fast adsorption rates for the removal of cationic dyes in water. The adsorption capacity of methylene blue (MB), cationic turquoise blue GB (GB), malachite green (MG), crystal violet (CV) and cationic pink FG (FG) were 60.06 mg g- 1, 70.97 mg g- 1, 66.84 mg g- 1, 66.01 mg g- 1 and 50.27 mg g- 1, respectively. The adsorption mechanism was proposed by the analyses of the adsorption isotherms and adsorption kinetics of cationic dyes on Fe3O4/PCC MNPs. Moreover, the cationic dyes adsorbed on the MNPs as a function of contact time, pH value, temperature, coexisting cationic ions and ion strength were also investigated. These results suggested that the Fe3O4/PCC MNPs is promising to be used as a magnetic adsorbent for selective adsorption of cationic dyes in wastewater treatment.

Aggregation Pathways of Native-Like Ubiquitin Promoted by Single-Point Mutation, Metal Ion Concentration, and Dielectric Constant of the Medium.

PubMed

Fermani, Simona; Calvaresi, Matteo; Mangini, Vincenzo; Falini, Giuseppe; Bottoni, Andrea; Natile, Giovanni; Arnesano, Fabio

2018-03-15

Ubiquitin-positive protein aggregates are biomarkers of neurodegeneration, but the molecular mechanism responsible for their formation and accumulation is still unclear. Possible aggregation pathways of human ubiquitin (hUb) promoted by both intrinsic and extrinsic factors, are here investigated. By a computational analysis, two different hUb dimers are indicated as possible precursors of amyloid-like structures, but their formation is disfavored by an electrostatic repulsion involving Glu16 and other carboxylate residues present at the dimer interface. Experimental data on the E16V mutant of hUb shows that this single-point mutation, although not affecting the overall protein conformation, promotes protein aggregation. It is sufficient to shift the same mutation by only two residues (E18V) to regain the behavior of wild-type hUb. The neutralization of Glu16 negative charge by a metal ion and a decrease of the dielectric constant of the medium by addition of trifluoroethanol (TFE), also promote hUb aggregation. The outcomes of this research have important implications for the prediction of physiological parameters that favor aggregate formation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous silicon-carbon nanospheres synthesized by chemical vapor deposition using cheap methyltrichlorosilane as improved anode materials for Li-ion batteries.

PubMed

Zhang, Zailei; Zhang, Meiju; Wang, Yanhong; Tan, Qiangqiang; Lv, Xiao; Zhong, Ziyi; Li, Hong; Su, Fabing

2013-06-21

We report the preparation and characterization of amorphous silicon-carbon (Si-C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si-C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400-600 nm and a surface area of 43.8 m(2) g(-1). Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g(-1) at 50, 200, 500, 1000, and 50 mA g(-1) after 50 cycles, higher than that of the commercial graphite anode. The Si-C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si-C anode materials for Li-ion batteries.

Electrospray ionization tandem mass spectrometry of ammonium cationized polyethers.

PubMed

Nasioudis, Andreas; Heeren, Ron M A; van Doormalen, Irene; de Wijs-Rot, Nicolette; van den Brink, Oscar F

2011-05-01

Quaternary ammonium salts (Quats) and amines are known to facilitate the MS analysis of high molar mass polyethers by forming low charge state adduct ions. The formation, stability, and behavior upon collision-induced dissociation (CID) of adduct ions of polyethers with a variety of Quats and amines were studied by electrospray ionization quadrupole time-of-flight, quadrupole ion trap, and linear ion trap tandem mass spectrometry (MS/MS). The linear ion trap instrument was part of an Orbitrap hybrid mass spectrometer that allowed accurate mass MS/MS measurements. The Quats and amines studied were of different degree of substitution, structure, and size. The stability of the adduct ions was related to the structure of the cation, especially the amine's degree of substitution. CID of singly/doubly charged primary and tertiary ammonium cationized polymers resulted in the neutral loss of the amine followed by fragmentation of the protonated product ions. The latter reveals information about the monomer unit, polymer sequence, and endgroup structure. In addition, the detection of product ions retaining the ammonium ion was observed. The predominant process in the CID of singly charged quaternary ammonium cationized polymers was cation detachment, whereas their doubly charged adduct ions provided the same information as the primary and tertiary ammonium cationized adduct ions. This study shows the potential of specific amines as tools for the structural elucidation of high molar mass polyethers. © American Society for Mass Spectrometry, 2011

Laser ion source for high brightness heavy ion beam

DOE PAGES

Okamura, M.

2016-09-01

A laser ion source is known as a high current high charge state heavy ion source. But, we place great emphasis on the capability to realize a high brightness ion source. A laser ion source has a pinpoint small volume where materials are ionized and can achieve quite uniform low temperature ion beam. Those features may enable us to realize very small emittance beams. Furthermore, a low charge state high brightness laser ion source was successfully commissioned in Brookhaven National Laboratory in 2014. Now most of all the solid based heavy ions are being provided from the laser ion sourcemore » for regular operation.« less

Porous solid ion exchange wafer for immobilizing biomolecules

DOEpatents

Arora, Michelle B.; Hestekin, Jamie A.; Lin, YuPo J.; St. Martin, Edward J.; Snyder, Seth W.

2007-12-11

A porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer. Also disclosed is a porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer containing a biomolecule with a tag. A separate bioreactor is also disclosed incorporating the wafer described above.

Charge compensation mechanisms in favor of the incorporation of the Eu3+ ion into the ZnO host lattice

NASA Astrophysics Data System (ADS)

Baira, M.; Bekhti-Siad, A.; Hebali, K.; Bouhani-Benziane, H.; Sahnoun, M.

2018-05-01

Eu3+ doped phosphors with charge compensation are potential candidates of red emitting phosphors for lamp applications. Charge compensation improves the luminescence performance of the material. The charge compensation can most probably be achieved by three possible mechanisms: (a) two Zn2+ ions are replaced by one Eu3+ ions and one monovalent cation, 2Zn2+ →Eu3++ Li+, where Li+ is acting as a charge compensator; (b) the charge compensation is provided by a zinc vacancy (VZn) defects, 3Zn2+ → 2Eu3++ VZn, the subscript Zn denotes an ion in a normal zinc site in the lattice; (c) two Zn2+ ions are replaced by one Eu3+ ions with the presence of interstitial oxygen (Oi), 2Zn2+ → 2Eu3++ Oi. Electronic structures of the crystals corresponding to the three models are evaluated by the first-principles quantum mechanical calculations based on the density functional theory. It is found that the charge compensator defects make Eu3+ doping in ZnO energetically more favorable. They break the local symmetry around the Eu3+ ion and lead to deep states below the empty upper band, the conduction band that could facilitate intra-4f shell transitions, which can obviously improve the emission intensity of Eu3+-doped ZnO. Therefore, the effect of these defects on the host crystals electronic band states relative to the Eu3+ states is reported, since both electron transfer and electronically energy transfer processes enhance the performance of optoelectronic devices based on this material. These theoretical insights are helpful for designing rare-earth doped oxide materials with high photoluminescence (PL) performance.

The effect of dust charge variation, due to ion flow and electron depletion, on dust levitation

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

Land, Victor; Douglass, Angela; Qiao Ke

2011-11-29

Using a fluid model, the plasma densities, electron temperature and ion Mach number in front of a powered electrode in different plasma discharges is computed. The dust charge is computed using OML theory for Maxwellian electrons and ions distributed according to a shifted-Maxwellian. By assuming force balance between gravity and the electrostatic force, the dust levitation height is obtained. The importance of the dust charge variation is investigated.

Method and apparatus for detection of charge on ions and particles

DOEpatents

Fuerstenau, Stephen Douglas; Soli, George Arthur

2002-01-01

The present invention provides a tessellated array detector with charge collecting plate (or cup) electrode pixels and amplifying circuitry integrated into each pixel making it sensitive to external electrostatic charge; a micro collector/amplifier pixel design possessing a small capacitance to ensure a high charge to voltage signal conversion for low noise/high sensitivity operation; a micro-fabricated array of such pixels to create a useful macroscopic target area for ion and charged particle collection.

AC and DC conductivity due to hopping mechanism in double ion doped ceramics

NASA Astrophysics Data System (ADS)

Rizwana, Mahboob, Syed; Sarah, P.

2018-04-01

Sr1-2xNaxNdxBi4Ti4O15 (x = 0.1, 0.2 and 0.4) system is prepared by sol gel method involving Pechini process of modified polymeric precursor method. Phase identification is done using X-ray diffraction. Conduction in prepared materials involves different mechanisms and is explained through detailed AC and DC conductivity studies. AC conductivity studies carried out on the samples at different frequencies and different temperatures gives more information about electrical transport. Exponents used in two term power relation helps us to understand the different hopping mechanism involved at low as well as high frequencies. Activation energies calculated from the Arrhenius plots are used to calculate activation energies at different temperatures and frequencies. Hopping frequency calculated from the measured data explains hopping of charge carriers at different temperatures. DC conductivity studies help us to know the role of oxygen vacancies in conduction.

Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

PubMed

Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

2015-04-21

Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.