Electron ionization and dissociation of aliphatic amino acids

NASA Astrophysics Data System (ADS)

Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

2012-09-01

We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

Gas-phase study on uridine: Conformation and X-ray photofragmentation

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

Itälä, Eero, E-mail: ersita@utu.fi; Kooser, Kuno; Levola, Helena

2015-05-21

Fragmentation of RNA nucleoside uridine, induced by carbon 1s core ionization, has been studied. The measurements by combined electron and ion spectroscopy have been performed in gas phase utilizing synchrotron radiation. As uridine is a combination of d-ribose and uracil, which have been studied earlier with the same method, this study also considers the effect of chemical environment and the relevant functional groups. Furthermore, since in core ionization the initial core hole is always highly localized, charge migration prior to fragmentation has been studied here. This study also demonstrates the destructive nature of core ionization as in most cases themore » C 1s ionization of uridine leads to concerted explosions producing only small fragments with masses ≤43 amu. In addition to fragmentation patterns, we found out that upon evaporation the sugar part of the uridine molecule attains hexagonal form.« less

Ionization, evaporation and fragmentation of C60 in collisions with highly charged C, O and F ions—effect of projectile charge state.

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Misra, D.; Tribedi, L. C.

2007-09-01

We study the various inelastic processes such ionization, fragmentation and evaporation of C60 molecule in collisions with fast heavy ions. We have used 2.33 MeV/u C, O and F projectile ion beams. Various ionization and fragmentation products were detected using time-of-flight mass spectrometer. The multiply charged C60r+ ions were detected for maximum r = 4. The projectile charge state (qp) dependence of the single and double ionization cross sections is well reproduced by a model based on the giant dipole plasmon resonance (GDPR). The qp-dependence of the fragmentation yields, was found to be linear. Variation of relative yields of the evaporation products of C602+ (i.e. C582+, C562+ etc) and C603+ (i.e. C583+, C563+ etc) with qp has also been investigated for various projectiles.

Characteristics study of projectile's lightest fragment for 84Kr36-emulsion interaction at around 1 A GeV

NASA Astrophysics Data System (ADS)

Marimuthu, N.; Singh, V.; Inbanathan, S. S. R.

2017-04-01

In this article, we present the results of our investigations on the projectile's lightest fragment (proton) multiplicity and probability distributions with 84Kr36 emulsion collision at around 1 A GeV. The multiplicity and normalized multiplicity of projectile's lightest fragment (proton) are correlated with the compound particles, shower particles, black particles, grey particles; alpha (helium nucleus) fragments and heavily ionizing charged particles. It is found that projectile's lightest fragment (proton) is strongly correlated with compound particles and shower particles rather than other particles and the average multiplicity of projectile's lightest fragment (proton) increases with increasing compound, shower and heavily ionizing charge particles. Normalized projectile's lightest fragment (proton) is strongly correlated with compound particles, shower particles and heavily ionizing charge particles. The multiplicity distribution of the projectile's lightest fragment (proton) emitted in the 84Kr36 + emulsion interaction at around 1 A GeV with different target has been well explained by KNO scaling. The mean multiplicity of projectile's lightest fragments (proton) depends on the mass number of the projectile and does not significantly dependent of the projectile energy. The mean multiplicity of projectile's lightest fragment (proton) increases with increasing the target mass number.

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

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

Schwartz, Andrew J.; Shelley, Jacob T.; Walton, Courtney L.

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-likemore » spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.« less

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

DOE PAGES

Schwartz, Andrew J.; Shelley, Jacob T.; Walton, Courtney L.; ...

2016-06-27

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-likemore » spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.« less

Dissociative-ionization cross sections for 12-keV-electron impact on CO{sub 2}

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

Bhatt, Pragya; Singh, Raj; Yadav, Namita

The dissociative ionization of a CO{sub 2} molecule is studied at an electron energy of 12 keV using the multiple ion coincidence imaging technique. The absolute partial ionization cross sections and the precursor-specific absolute partial ionization cross sections of resulting fragment ions are obtained and reported. It is found that {approx}75% of single ionization, 22% of double ionization, and {approx}2% of triple ionization of the parent molecule contribute to the total fragment ion yield; quadruple ionization of CO{sub 2} is found to make a negligibly small contribution. Furthermore, the absolute partial ionization cross sections for ion-pair and ion-triple formation aremore » measured for nine dissociative ionization channels of up to a quadruply ionized CO{sub 2} molecule. In addition, the branching ratios for single-ion, ion-pair, and ion-triple formation are also determined.« less

Vacuum ultraviolet photoionization of carbohydrates and nucleotides

NASA Astrophysics Data System (ADS)

Shin, Joong-Won; Bernstein, Elliot R.

2014-01-01

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5'-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02032a Click here for additional data file.

PubMed Central

Schwartz, Andrew J.; Walton, Courtney L.; Williams, Kelsey L.; Hieftje, Gary M.

2016-01-01

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-like spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma. PMID:28451101

Vacuum ultraviolet photoionization of carbohydrates and nucleotides.

PubMed

Shin, Joong-Won; Bernstein, Elliot R

2014-01-28

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5(')-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C-C and C-O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

VUV and soft x-ray ionization of a plant volatile: Vanillin (C{sub 8}H{sub 8}O{sub 3})

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

Betancourt, A. Moreno; Moura, C. E. V. de; Rocha, A. B.

2016-03-21

Plant volatiles are emitted by plants in response to several forms of stress, including interaction with energetic photons. In the present work, we discuss the interaction of extreme UV and soft X-ray photons with a plant volatile, vanillin. The single and double (multiple) ionization of the vanillin molecule have been studied for the first time using time-of-flight mass spectrometry and VUV and soft X-ray photons (synchrotron radiation, at 12.0 eV, 21.2 eV, 130 eV, 310 eV, 531 eV, and 550 eV). At 12.0 and 21.2 eV, only singly charged species are observed and the parent ion, C{sub 8}H{sub 8}O{sub 3}{supmore » +}, is the dominant species. Energy differences for some selected fragments were calculated theoretically in this energy region. At 130 eV, direct double and triple ionization of the valence electrons may occur. The fragmentation increases and CHO{sup +} becomes one of the main cations in the mass spectrum. The molecular ion is still the dominant species, but other fragments, such as C{sub 6}H{sub 5}O{sup +}, begin to present similar intensities. At 310 eV, C 1s electrons may be ionized and Auger processes give rise to dissociative doubly ionized cations. Ionization around the O 1s edge has been studied both at the 531 eV resonance and above the ionization edge. Resonant and normal Auger processes play a significant role in each case and a large fragmentation of the molecule is observed at both photon energies, with intense fragments such as CHO{sup +} and CH{sub 3}{sup +} being clearly observed. A near edge X-ray absorption fine structure spectrum of the vanillin molecule was obtained around the O 1s ionization threshold. In addition, the fragmentation of vanillin has also been studied using a fast beam of electrons (800 eV), for the sake of comparison.« less

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

Inhester, Ludger; Oostenrijk, Bart; Patanen, Minna

In many cases fragmentation of molecules upon inner-shell ionization is very unspecific with respect to the initially localized ionization site. Often this finding is interpreted in terms of an equilibration of internal energy into vibrational degrees of freedom after Auger decay. In this paper, we investigate the X-ray photofragmentation of ethyl trifluoroacetate upon core electron ionization at environmentally distinct carbon sites using photoelectron–photoion–photoion coincidence measurements and ab initio electronic structure calculations. For all four carbon ionization sites, the Auger decay weakens the same bonds and transfers the two charges to opposite ends of the molecule, which leads to a rapidmore » dissociation into three fragments, followed by further fragmentation steps. Finally, the lack of site specificity is attributed to the character of the dicationic electronic states after Auger decay instead of a fast equilibration of internal energy.« less

Simultaneous ESI-APCI+ ionization and fragmentation pathways for nine benzodiazepines and zolpidem using single quadrupole LC-MS.

PubMed

Galaon, Toma; Vacaresteanu, Catalina; Anghel, Dan-Florin; David, Victor

2014-05-01

Nine important 1,4-benzodiazepines and zolpidem were characterized by liquid chromatography-mass spectrometry using a multimode ionization source able to generate ions using both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), and a single quadrupole mass analyzer. An optimum chromatographic separation was applied for all target compounds in less than 8 minutes using a Zorbax Eclipse Plus column (100 × 4.6 mm, 3.5 µm) kept at 35°C and a 0.3% HCOOH/ACN/IPA (61:34:5) mobile phase pumped at 1 ml/min. Optimization of LC-MS method generated low limit of quantitation (LOQ) values situated in the range 0.3-20.5 ng/ml. Comparison between differences in method sensitivity, under specified chromatographic conditions, when using ESI-only, APCI-only, and simultaneous ESI-APCI ionization with such a multimode source was discussed. Mixed ESI-APCI(+) mode proved to be the most sensitive ionization generating an average 35% detector response increase compared to ESI-only ionization and 350% detector response increase with respect to APCI-only ionization. Characterization of the nine benzodiazepines and zolpidem concerning their MS fragmentation pathway following 'in-source' collision-induced dissociation is discussed in detail and some general trends regarding these fragmentations are set. Copyright © 2013 John Wiley & Sons, Ltd.

Electron-impact total ionization cross sections of DNA sugar-phosphate backbone and an additivity principle

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Dateo, Christopher E.

2005-01-01

The improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64, 042719-1 (2001)l is used to study the total ionization cross sections of the DNA sugar-phosphate backbone by electron impact. Calculations using neutral fragments found that the total ionization cross sections of C3' - and C5', -deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3' - and C5" -deoxyribose-phospate cross sections, differing by less than 10%. The result implies that certain properties of the-DNA, like the total singly ionization cross section, are localized properties and a building-up or additivity principle may apply. This allows us to obtain accurate properties of larger molecular systems built up from the results of smaller subsystem fragments. Calculations are underway using a negatively charged sugar-phosphate backbone with a metal counter-ion.

Solubility, ionization, and partitioning behavior of unsymmetrical disulfide compounds: alkyl 2-imidazolyl disulfides.

PubMed

Hashash, Ahmad; Kirkpatrick, D Lynn; Lazo, John S; Block, Lawrence H

2002-07-01

Alkyl 2-imidazolyl disulfide compounds are novel antitumor agents, one of which is currently being evaluated in Phase I clinical trials. These molecules contain an unsymmetrical disulfide fragment, the lipophilic and electronic contributions of which are still not defined in the literature. Lipophilicity, ionization, and solubility of a number of alkyl 2-imidazolyl disulfides were studied. Based on the additivity of lipophilicity and ionization properties, the contribution of the unsymmetrical disulfide fragment to lipophilicity and ionization was elucidated. The unsymmetrical disulfide fragment contributed a Rekker's hydrophobic constant of 0.761 to the lipophilicity of these compounds and an approximated Hammett constant (sigma) of 0.30 to their ionization. The applicability of the general solubility equation (GSE) proposed by Jain and Yalkowsky in predicting the aqueous solubility of these analogs was evaluated. The GSE correctly ranked the aqueous solubilities of these compounds and estimated their log molar solubilities with an average absolute error of 0.35. Copyright 2002 Wiley-Liss Inc.

Measuring Fission Fragment Mass Distributions as a Function of Incident Neutron Energy Using the fissionTPC

NASA Astrophysics Data System (ADS)

Gearhart, Joshua; Niffte Collaboration

2017-09-01

Fission fragment mass distributions are important observables for developing next generation dynamical models of fission. Many previous measurements have utilized ionization chambers to measure fission fragment energies and emission angles which are then used for mass calculations. The Neutron Induced Fission Fragment Tracking Experiment (NIFFTE) collaboration has built a time projection chamber (fissionTPC) that is capable of measuring additional quantities such as the ionization profiles of detected particles, allowing for the association of an individual fragment's ionization profile with its mass. The fragment masses are measured using the previously established 2E method. The fissionTPC takes its data using a continuous incident neutron energy spectrum provided by the Los Alamos Neutron Science CEnter (LANSCE). Mass distribution measurements across a continuous range of neutron energies put stronger constraints on fission models than similar measurements conducted at a handful of discrete neutron energies. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Numbers DE-NA0003180 and DE-NA0002921.

Vacuum ultraviolet photoionization of carbohydrates and nucleotides

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

Shin, Joong-Won, E-mail: jshin@govst.edu; Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872; Bernstein, Elliot R., E-mail: erb@lamar.colostate.edu

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5{sup ′}-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate,more » rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C–C and C–O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.« less

Extreme ultraviolet photoionization of aldoses and ketoses

NASA Astrophysics Data System (ADS)

Shin, Joong-Won; Dong, Feng; Grisham, Michael E.; Rocca, Jorge J.; Bernstein, Elliot R.

2011-04-01

Gas phase monosaccharides (2-deoxyribose, ribose, arabinose, xylose, lyxose, glucose galactose, fructose, and tagatose), generated by laser desorption of solid sample pellets, are ionized with extreme ultraviolet photons (EUV, 46.9 nm, 26.44 eV). The resulting fragment ions are analyzed using a time of flight mass spectrometer. All aldoses yield identical fragment ions regardless of size, and ketoses, while also generating same ions as aldoses, yields additional features. Extensive fragmentation of the monosaccharides is the result the EUV photons ionizing various inner valence orbitals. The observed fragmentation patterns are not dependent upon hydrogen bonding structure or OH group orientation.

Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation

DOE PAGES

Inhester, Ludger; Oostenrijk, Bart; Patanen, Minna; ...

2018-02-14

In many cases fragmentation of molecules upon inner-shell ionization is very unspecific with respect to the initially localized ionization site. Often this finding is interpreted in terms of an equilibration of internal energy into vibrational degrees of freedom after Auger decay. In this paper, we investigate the X-ray photofragmentation of ethyl trifluoroacetate upon core electron ionization at environmentally distinct carbon sites using photoelectron–photoion–photoion coincidence measurements and ab initio electronic structure calculations. For all four carbon ionization sites, the Auger decay weakens the same bonds and transfers the two charges to opposite ends of the molecule, which leads to a rapidmore » dissociation into three fragments, followed by further fragmentation steps. Finally, the lack of site specificity is attributed to the character of the dicationic electronic states after Auger decay instead of a fast equilibration of internal energy.« less

Investigation on the absolute and relative photoionization cross sections of 3 potential propargylic fuels.

PubMed

Winfough, Matthew; Meloni, Giovanni

2017-12-01

Absolute photoionization cross sections for 2 potential propargylic fuels (propargylamine and dipropargyl ether) along with the partial ionization cross sections for their dissociative fragments are measured and presented for the first time via synchrotron photoionization mass spectrometry. The experimental setup consists of a multiplexed orthogonal time-of-flight mass spectrometer and is located at the Advanced Light Source facility of the Lawrence Berkeley National Laboratory in Berkeley, California. Data for a third propargylic compound (propargyl alcohol) were taken; however, because of its low signal, due to its weakly bound cation, only the dissociative ionization fragment from the H-loss channel is observed and presented. Suggested pathways leading to formation of dissociative photoionization fragments along with CBS-QB3 calculated adiabatic ionization energies and appearance energies for the dissociative fragments are also presented. Copyright © 2017 John Wiley & Sons, Ltd.

Motion of the Debris from a High-Altitude Nuclear Explosion: Simulations Including Collisionless Shock and Charge Exchange

DTIC Science & Technology

2014-06-01

14   Figure 3.   Distribution of mass of fission fragments from the fission of uranium-235 by a thermal neutron (after Krane, 1988...1962 to the present underscores how critical this effect can be to the Department of Defense (DOD) and to the Nation. In addition to the...overhead of Johnston Island.”3 Fission of an actinide generally produces two ionized fission fragments. These fission fragments are highly ionized

Conversion of fullerenes to diamond

DOEpatents

Gruen, Dieter M.

1994-01-01

A method of forming synthetic hydrogen defect free diamond or diamond like films on a substrate. The method involves providing vapor containing fullerene molecules with or without an inert gas, providing a device to impart energy to the fullerene molecules, fragmenting at least in part some of the fullerene molecules in the vapor or energizing the molecules to incipient fragmentation, ionizing the fullerene molecules, impinging ionized fullerene molecules on the substrate to assist in causing fullerene fragmentation to obtain a thickness of diamond on the substrate.

Systematic trends in photonic reagent induced reactions in a homologous chemical family.

PubMed

Tibbetts, Katharine Moore; Xing, Xi; Rabitz, Herschel

2013-08-29

The growing use of ultrafast laser pulses to induce chemical reactions prompts consideration of these pulses as "photonic reagents" in analogy to chemical reagents. This work explores the prospect that photonic reagents may affect systematic trends in dissociative ionization reactions of a homologous family of halomethanes, much as systematic outcomes are often observed for reactions between homologous families of chemical reagents and chemical substrates. The experiments in this work with photonic reagents of varying pulse energy and linear spectral chirp reveal systematic correlations between observable ion yields and the following set of natural variables describing the substrate molecules: the ionization energy of the parent molecule, the appearance energy of each fragment ion, and the relative strength of carbon-halogen bonds in molecules containing two different halogens. The results suggest that reactions induced by photonic reagents exhibit systematic behavior analogous to that observed in reactions driven by chemical reagents, which provides a basis to consider empirical "rules" for predicting the outcomes of photonic reagent induced reactions.

Laser desorption/ionization from nanostructured surfaces: nanowires, nanoparticle films and silicon microcolumn arrays

NASA Astrophysics Data System (ADS)

Chen, Yong; Luo, Guanghong; Diao, Jiajie; Chornoguz, Olesya; Reeves, Mark; Vertes, Akos

2007-04-01

Due to their optical properties and morphology, thin films formed of nanoparticles are potentially new platforms for soft laser desorption/ionization (SLDI) mass spectrometry. Thin films of gold nanoparticles (with 12±1 nm particle size) were prepared by evaporation-driven vertical colloidal deposition and used to analyze a series of directly deposited polypeptide samples. In this new SLDI method, the required laser fluence for ion detection was equal or less than what was needed for matrix-assisted laser desorption/ionization (MALDI) but the resulting spectra were free of matrix interferences. A silicon microcolumn array-based substrate (a.k.a. black silicon) was developed as a new matrix-free laser desorption ionization surface. When low-resistivity silicon wafers were processed with a 22 ps pulse length 3×ω Nd:YAG laser in air, SF6 or water environment, regularly arranged conical spikes emerged. The radii of the spike tips varied with the processing environment, ranging from approximately 500 nm in water, to ~2 µm in SF6 gas and to ~5 µm in air. Peptide mass spectra directly induced by a nitrogen laser showed the formation of protonated ions of angiotensin I and II, substance P, bradykinin fragment 1-7, synthetic peptide, pro14-arg, and insulin from the processed silicon surfaces but not from the unprocessed areas. Threshold fluences for desorption/ionization were similar to those used in MALDI. Although compared to silicon nanowires the threshold laser pulse energy for ionization is significantly (~10×) higher, the ease of production and robustness of microcolumn arrays offer complementary benefits.

Peptide Fragmentation by Corona Discharge Induced Electrochemical Ionization

PubMed Central

Lloyd, John R.; Hess, Sonja

2010-01-01

Fundamental studies have greatly improved our understanding of electrospray, including the underlying electrochemical reactions. Generally regarded as disadvantageous, we have recently shown that corona discharge (CD) can be used as an effective method to create a radical cation species [M]+•, thus optimizing the electrochemical reactions that occur on the surface of the stainless steel (SS) electrospray capillary tip. This technique is known as CD initiated electrochemical ionization (CD-ECI). Here, we report on the fundamental studies using CD-ECI to induce analytically useful in-source fragmentation of a range of molecules that complex transition metals. Compounds that have been selectively fragmented using CD-ECI include enolate forming phenylglycine containing peptides, glycopeptides, nucleosides and phosphopeptides. Collision induced dissociation (CID) or other activation techniques were not necessary for CD-ECI fragmentation. A four step mechanism was proposed: 1. Complexation using either Fe in the SS capillary tip material or Cu(II) as an offline complexation reagent; 2. Electrochemical oxidation of the complexed metal and thus formation of a radical cation (e.g.; Fe - e− → Fe +•); 3. Radical fragmentation of the complexed compound. 4. Electrospray ionization of the fragmented neutrals. Fragmentation patterns resembling b- and y-type ions were observed and allowed the localization of the phosphorylation sites. PMID:20869880

Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

PubMed Central

Li, Zheng; Vendrell, Oriol

2016-01-01

The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects. PMID:26798842

The investigation of substituent effects on the fragmentation pathways of pentacoordinated phenoxyspirophosphoranes by ESI-MSn.

PubMed

Cui, Xiaoyan; Sun, Can; Zhao, Pei; Wang, Yanyan; Guo, Yanchun; Zhao, Yufen; Cao, Shuxia

2018-04-01

The fragmentation pathways of pentacoordinated phenoxyspirophosphoranes were investigated in the positive mode by electrospray ionization multistage mass spectrometry. The results demonstrate that the sodium adducts of the title compounds undergo two competitive fragmentation pathways, and the fragmentation patterns are heavily dependent on the various substituent patterns at the phenolic group. An electron-withdrawing substituent at the ortho-position always results in the removal of a corresponding phenol analogue, while cleavage by spiroring opening becomes the predominant fragmentation pathway if an electron-donating substituent is at the phenolic group. The substituent effects on the competitive fragmentation pathways were further elucidated by theoretical calculations, single crystal structure analysis, and high-resolution mass spectrometry. The results contribute to the understanding of the gas-phase fragmentation reactions and the structure identification of spirophosphorane analogues by electrospray ionization multistage mass spectrometry. Copyright © 2018 John Wiley & Sons, Ltd.

Tandem mass spectrometry characteristics of polyester anions and cations formed by electrospray ionization.

PubMed

Arnould, Mark A; Buehner, Rita W; Wesdemiotis, Chrys; Vargas, Rafael

2005-01-01

Electrospray ionization of polyesters composed of isophthalic acid and neopentyl glycol produces carboxylate anions in negative mode and mainly sodium ion adducts in positive mode. A tandem mass spectrometry (MS/MS) study of these ions in a quadrupole ion trap shows that the collisionally activated dissociation pathways of the anions are simpler than those of the corresponding cations. Charge-remote fragmentations predominate in both cases, but the spectra obtained in negative mode are devoid of the complicating cation exchange observed in positive mode. MS/MS of the Na(+) adducts gives rise to a greater number of fragments but not necessarily more structural information. In either positive or negative mode, polyester oligomers with different end groups fragment by similar mechanisms. The observed fragments are consistent with rearrangements initiated by the end groups. Single-stage ESI mass spectra also are more complex in positive mode because of extensive H/Na substitutions; this is also true for matrix-assisted laser desorption ionization (MALDI) mass spectra. Hence, formation and analysis of anions might be the method of choice for determining block length, end group structure and copolymer sequence, provided the polyester contains at least one carboxylic acid end group that is ionizable to anions.

Effect of internal and external conditions on ionization processes in the FAPA ambient desorption/ionization source.

PubMed

Orejas, Jaime; Pfeuffer, Kevin P; Ray, Steven J; Pisonero, Jorge; Sanz-Medel, Alfredo; Hieftje, Gary M

2014-11-01

Ambient desorption/ionization (ADI) sources coupled to mass spectrometry (MS) offer outstanding analytical features: direct analysis of real samples without sample pretreatment, combined with the selectivity and sensitivity of MS. Since ADI sources typically work in the open atmosphere, ambient conditions can affect the desorption and ionization processes. Here, the effects of internal source parameters and ambient humidity on the ionization processes of the flowing atmospheric pressure afterglow (FAPA) source are investigated. The interaction of reagent ions with a range of analytes is studied in terms of sensitivity and based upon the processes that occur in the ionization reactions. The results show that internal parameters which lead to higher gas temperatures afforded higher sensitivities, although fragmentation is also affected. In the case of humidity, only extremely dry conditions led to higher sensitivities, while fragmentation remained unaffected.

Attosecond-recollision-controlled selective fragmentation of polyatomic molecules.

PubMed

Xie, Xinhua; Doblhoff-Dier, Katharina; Roither, Stefan; Schöffler, Markus S; Kartashov, Daniil; Xu, Huailiang; Rathje, Tim; Paulus, Gerhard G; Baltuška, Andrius; Gräfe, Stefanie; Kitzler, Markus

2012-12-14

Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

Influence of field ionization effect on the divergence of laser-driven fast electrons

NASA Astrophysics Data System (ADS)

Lang, Y.; Yang, X. H.; Xu, H.; Jin, Z.; Zhuo, H. B.

2018-07-01

The effect of field ionization on the divergence of fast electrons (E k ≥ 50 keV), driven by ultrashort-ultraintense laser pulse interaction with plasma, is studied by using 2D3V particle-in-cell simulations. It is found that, due to temperature anisotropy of the fast electrons in the ionizing target, strong fluctuant magnetic fields in the preplasma region is generated through Weibel instability. In turn, the field induces an enhancement of the hot electron divergence for the target with ionization process. Meanwhile, compared with the target without an ionization process, larger divergence of hot electrons can also be seen in the ionizing target with laser intensity varying from 5 × 1019 W/cm2 to 5 × 1020 W/cm2 and the divergence is weakly dependent on target materials for a fixed profile of preplasma. The results here are useful for the application of laser-driven fast electron beams.

The effect of pi-stacking, h-bonding, and electrostatic interactions on the ionization energies of nucleic acid bases: adenine-adenine, thymine-thymine and adenine-thymine dimers

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

Bravaya, Ksenia B.; Kostko, Oleg; Ahmed, Musahid

A combined theoretical and experimental study of the ionized dimers of thymine and adenine, TT, AA, and AT, is presented. Adiabatic and vertical ionization energies(IEs) for monomers and dimers as well as thresholds for the appearance of the protonated species are reported and analyzed. Non-covalent interactions stronglyaffect the observed IEs. The magnitude and the nature of the effect is different for different isomers of the dimers. The computations reveal that for TT, the largestchanges in vertical IEs (0.4 eV) occur in asymmetric h-bonded and symmetric pi- stacked isomers, whereas in the lowest-energy symmetric h-bonded dimer the shiftin IEs is muchmore » smaller (0.1 eV). The origin of the shift and the character of the ionized states is different in asymmetric h-bonded and symmetric stacked isomers. Inthe former, the initial hole is localized on one of the fragments, and the shift is due to the electrostatic stabilization of the positive charge of the ionized fragment by thedipole moment of the neutral fragment. In the latter, the hole is delocalized, and the change in IE is proportional to the overlap of the fragments' MOs. The shifts in AAare much smaller due to a less effcient overlap and a smaller dipole moment. The ionization of the h-bonded dimers results in barrierless (or nearly barrierless) protontransfer, whereas the pi-stacked dimers relax to structures with the hole stabilized by the delocalization or electrostatic interactions.« less

Gas chromatography/chemical ionization triple quadrupole mass spectrometry analysis of anabolic steroids: ionization and collision-induced dissociation behavior.

PubMed

Polet, Michael; Van Gansbeke, Wim; Van Eenoo, Peter; Deventer, Koen

2016-02-28

The detection of new anabolic steroid metabolites and new designer steroids is a challenging task in doping analysis. Switching from electron ionization gas chromatography triple quadrupole mass spectrometry (GC/EI-MS/MS) to chemical ionization (CI) has proven to be an efficient way to increase the sensitivity of GC/MS/MS analyses and facilitate the detection of anabolic steroids. CI also extends the possibilities of GC/MS/MS analyses as the molecular ion is retained in its protonated form due to the softer ionization. In EI it can be difficult to find previously unknown but expected metabolites due to the low abundance or absence of the molecular ion and the extensive (and to a large extent unpredictable) fragmentation. The main aim of this work was to study the CI and collision-induced dissociation (CID) behavior of a large number of anabolic androgenic steroids (AAS) as their trimethylsilyl derivatives in order to determine correlations between structures and CID fragmentation. Clarification of these correlations is needed for the elucidation of structures of unknown steroids and new metabolites. The ionization and CID behavior of 65 AAS have been studied using GC/CI-MS/MS with ammonia as the reagent gas. Glucuronidated AAS reference standards were first hydrolyzed to obtain their free forms. Afterwards, all the standards were derivatized to their trimethylsilyl forms. Full scan and product ion scan analyses were used to examine the ionization and CID behavior. Full scan and product ion scan analyses revealed clear correlations between AAS structure and the obtained mass spectra. These correlations were confirmed by analysis of multiple hydroxylated, methylated, chlorinated and deuterated analogs. AAS have been divided into three groups according to their ionization behavior and into seven groups according to their CID behavior. Correlations between fragmentation and structure were revealed and fragmentation pathways were postulated. Copyright © 2016 John Wiley & Sons, Ltd.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

PubMed

Neustetter, M; Jabbour Al Maalouf, E; Limão-Vieira, P; Denifl, S

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

CF3+ fragmentation by electron impact ionization of perfluoro-propyl-vinyl-ethers, C5F10O, in gas phase

NASA Astrophysics Data System (ADS)

Kondo, Yusuke; Ishikawa, Kenji; Hayashi, Toshio; Miyawaki, Yudai; Takeda, Keigo; Kondo, Hiroki; Sekine, Makoto; Hori, Masaru

2015-04-01

The gas phase fragmentations of perfluoro-propyl-vinyl ether (PPVE, C5F10O) are studied experimentally. Dominant fragmentations of PPVE are found to be the result of a dissociative ionization reaction, i.e., CF3+ via direct bond cleavage, and C2F3O- and C3F7O- via electron attachment. Regardless of the appearance energy of around 14.5 eV for the dissociative ionization of CF3+, the observed ion efficiency for the CF3+ ion was extremely large the order of 10-20 cm-2, compared with only 10-21 cm-2 for the other channels. PPVE characteristically generated CF3+ as the largest abundant ion are advantageous for use of feedstock gases in plasma etching processes.

Enhanced sensitivity of the RET proto-oncogene to ionizing radiation in vitro.

PubMed

Volpato, Claudia Béu; Martínez-Alfaro, Minerva; Corvi, Raffaella; Gabus, Coralie; Sauvaigo, Sylvie; Ferrari, Pietro; Bonora, Elena; De Grandi, Alessandro; Romeo, Giovanni

2008-11-01

Exposure to ionizing radiation is a well-known risk factor for a number of human cancers, including leukemia and thyroid cancer. It has been known for a long time that exposure of cells to radiation results in extensive DNA damage; however, a small number of studies have tried to explain the mechanisms of radiation-induced carcinogenesis. The high prevalence of RET/PTC rearrangements in patients who have received external radiation, and the evidence of in vitro induction of RET rearrangements in human cells, suggest an enhanced sensitivity of the RET genomic region to damage by ionizing radiation. To assess whether RET is indeed more sensitive to radiations than other genomic regions, we used a COMET assay coupled with fluorescence in situ hybridization, which allows the measurement of DNA fragmentation in defined genomic regions of single cells. We compared the initial DNA damage of the genomic regions of RET, CXCL12/SDF1, ABL, MYC, PLA2G2A, p53, and JAK2 induced by ionizing radiation in both a lymphoblastoid and a fetal thyroid cell line. In both cell lines, RET fragmentation was significantly higher than in other genomic regions. Moreover, a differential distribution of signals within the COMET was associated with a higher percentage of RET fragments in the tail. RET was more susceptible to fragmentation in the thyroid-derived cells than in lymphoblasts. This enhanced susceptibility of RET to ionizing radiation suggests the possibility of using it as a radiation exposure marker.

Some Dynamical Features of Molecular Fragmentation by Electrons and Swift Ions

NASA Astrophysics Data System (ADS)

Montenegro, E. C.; Sigaud, L.; Wolff, W.; Luna, H.; Natalia, Ferreira

To date, the large majority of studies on molecular fragmentation by swift charged particles have been carried out using simple molecules, for which reliable Potential Energy Curves are available to interpret the measured fragmentation yields. For complex molecules the scenario is quite different and such guidance is not available, obscuring even a simple organization of the data which are currently obtained for a large variety of molecules of biological or technological interest. In this work we show that a general and relatively simple methodology can be used to obtain a broader picture of the fragmentation pattern of an arbitrary molecule. The electronic ionization or excitation cross section of a given molecular orbital, which is the first part of the fragmentation process, can be well scaled by a simple and general procedure at high projectile velocities. The fragmentation fractions arising from each molecular orbital can then be achieved by matching the calculated ionization with the measured fragmentation cross sections. Examples for Oxygen, Chlorodifluoromethane and Pyrimidine molecules are presented.

Water cluster fragmentation probed by pickup experiments

NASA Astrophysics Data System (ADS)

Huang, Chuanfu; Kresin, Vitaly V.; Pysanenko, Andriy; Fárník, Michal

2016-09-01

Electron ionization is a common tool for the mass spectrometry of atomic and molecular clusters. Any cluster can be ionized efficiently by sufficiently energetic electrons, but concomitant fragmentation can seriously obstruct the goal of size-resolved detection. We present a new general method to assess the original neutral population of the cluster beam. Clusters undergo a sticking collision with a molecule from a crossed beam, and the velocities of neat and doped cluster ion peaks are measured and compared. By making use of longitudinal momentum conservation, one can reconstruct the sizes of the neutral precursors. Here this method is applied to H2O and D2O clusters in the detected ion size range of 3-10. It is found that water clusters do fragment significantly upon electron impact: the deduced neutral precursor size is ˜3-5 times larger than the observed cluster ions. This conclusion agrees with beam size characterization by another experimental technique: photoionization after Na-doping. Abundant post-ionization fragmentation of water clusters must therefore be an important factor in the interpretation of experimental data; interestingly, there is at present no detailed microscopic understanding of the underlying fragmentation dynamics.

Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

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

Li, Zheng; Vendrell, Oriol

2016-01-13

The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. As a result, for situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20more » to 40 fs driven by strong non-adiabatic effects.« less

Radical Anions of Oxidized vs. Reduced Oxytocin: Influence of Disulfide Bridges on CID and Vacuum UV Photo-Fragmentation

NASA Astrophysics Data System (ADS)

MacAleese, Luke; Girod, Marion; Nahon, Laurent; Giuliani, Alexandre; Antoine, Rodolphe; Dugourd, Philippe

2018-06-01

The nonapeptide oxytocin (OT) is used as a model sulfur-containing peptide to study the damage induced by vacuum UV (VUV) radiations. In particular, the effect of the presence (or absence in reduced OT) of oxytocin's internal disulfide bridge is evaluated in terms of photo-fragmentation yield and nature of the photo-fragments. Intact, as well as reduced, OT is studied as dianions and radical anions. Radical anions are prepared and photo-fragmented in two-color experiments (UV + VUV) in a linear ion trap. VUV photo-fragmentation patterns are analyzed and compared, and radical-induced mechanisms are proposed. The effect of VUV is principally to ionize but secondary fragmentation is also observed. This secondary fragmentation seems to be considerably enabled by the initial position of the radical on the molecule. In particular, the possibility to form a radical on free cysteines seems to increase the susceptibility to VUV fragmentation. Interestingly, disulfide bridges, which are fundamental for protein structure, could also be responsible for an increased resistance to ionizing radiations. [Figure not available: see fulltext.

Gas-Phase Stability of Negatively Charged Organophosphate Metabolites Produced by Electrospray Ionization and Matrix-Assisted Laser Desorption/Ionization

NASA Astrophysics Data System (ADS)

Asakawa, Daiki; Mizuno, Hajime; Toyo'oka, Toshimasa

2017-12-01

The formation mechanisms of singly and multiply charged organophosphate metabolites by electrospray ionization (ESI) and their gas phase stabilities were investigated. Metabolites containing multiple phosphate groups, such as adenosine 5'-diphosphate (ADP), adenosine 5'-triphosphate (ATP), and D- myo-inositol-1,4,5-triphosphate (IP3) were observed as doubly deprotonated ions by negative-ion ESI mass spectrometry. Organophosphates with multiple negative charges were found to be unstable and often underwent loss of PO3 -, although singly deprotonated analytes were stable. The presence of fragments due to the loss of PO3 - in the negative-ion ESI mass spectra could result in the misinterpretation of analytical results. In contrast to ESI, matrix-assisted laser desorption ionization (MALDI) produced singly charged organophosphate metabolites with no associated fragmentation, since the singly charged anions are stable. The stability of an organophosphate metabolite in the gas phase strongly depends on its charge state. The fragmentations of multiply charged organophosphates were also investigated in detail through density functional theory calculations. [Figure not available: see fulltext.

Ultrasound ionization of biomolecules.

PubMed

Wu, Chen-I; Wang, Yi-Sheng; Chen, Nelson G; Wu, Chung-Yi; Chen, Chung-Hsuan

2010-09-15

To date, mass spectrometric analysis of biomolecules has been primarily performed with either matrix-assisted laser desorption/ionization (MALDI) or electrospray ionization (ESI). In this work, ultrasound produced by a simple piezoelectric device is shown as an alternative method for soft ionization of biomolecules. Precursor ions of proteins, saccharides and fatty acids showed little fragmentation. Cavitation is considered as a primary mechanism for the ionization of biomolecules. Copyright 2010 John Wiley & Sons, Ltd.

Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

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

Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.

2011-01-01

Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS n ) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at differentmore » collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.« less

Fragmentation of neutral amino acids and small peptides by intense, femtosecond laser pulses.

PubMed

Duffy, Martin J; Kelly, Orla; Calvert, Christopher R; King, Raymond B; Belshaw, Louise; Kelly, Thomas J; Costello, John T; Timson, David J; Bryan, William A; Kierspel, Thomas; Turcu, I C Edmond; Cacho, Cephise M; Springate, Emma; Williams, Ian D; Greenwood, Jason B

2013-09-01

High power femtosecond laser pulses have unique properties that could lead to their application as ionization or activation sources in mass spectrometry. By concentrating many photons into pulse lengths approaching the timescales associated with atomic motion, very strong electric field strengths are generated, which can efficiently ionize and fragment molecules without the need for resonant absorption. However, the complex interaction between these pulses and biomolecular species is not well understood. To address this issue, we have studied the interaction of intense, femtosecond pulses with a number of amino acids and small peptides. Unlike previous studies, we have used neutral forms of these molecular targets, which allowed us to investigate dissociation of radical cations without the spectra being complicated by the action of mobile protons. We found fragmentation was dominated by fast, radical-initiated dissociation close to the charge site generated by the initial ionization or from subsequent ultrafast migration of this charge. Fragments with lower yields, which are useful for structural determinations, were also observed and attributed to radical migration caused by hydrogen atom transfer within the molecule.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

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

Neustetter, M.; Jabbour Al Maalouf, E.; Denifl, S., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt

2016-08-07

Electron ionization of neat tungsten hexacarbonyl (W(CO){sub 6}) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO){sub 6} clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO){sub n}{sup +} (0 ≤ n ≤ 6) and W{sub 2}(CO){sub n}{sup +} (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO){sub n}{sup +} (0 ≤more » n ≤ 3) and W{sub 2}C(CO){sub n}{sup +} (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.« less

Method for the elucidation of the elemental composition of low molecular mass chemicals using exact masses of product ions and neutral losses: application to environmental chemicals measured by liquid chromatography with hybrid quadrupole/time-of-flight mass spectrometry.

PubMed

Suzuki, Shigeru; Ishii, Tetsuko; Yasuhara, Akio; Sakai, Shinichi

2005-01-01

A method for elucidating the elemental compositions of low molecular weight chemicals, based primarily on mass measurements made using liquid chromatography (LC) with time-of-flight mass spectrometry (TOFMS) and quadrupole/time-of-flight mass spectrometry (LC/QTOFMS), was developed and tested for 113 chemicals of environmental interest with molecular masses up to approximately 400 Da. As the algorithm incorporating the method is not affected by differences in the instrument used, or by the ionization method and other ionization conditions, the method is useful not only for LC/TOFMS, but also for all kinds of mass spectra measured with higher accuracy and precision (uncertainties of a few mDa) employing all ionization methods and on-line separation techniques. The method involves calculating candidate compositions for intact ionized molecules (ionized forms of the sample molecule that have lost or gained no more than a proton, i.e., [M+H](+) or [M-H](-)) as well as for fragment ions and corresponding neutral losses, and eliminating those atomic compositions for the molecules that are inconsistent with the corresponding candidate compositions of fragment ions and neutral losses. Candidate compositions were calculated for the measured masses of the intact ionized molecules and of the fragment ions and corresponding neutral losses, using mass uncertainties of 2 and 5 mDa, respectively. Compositions proposed for the ionized molecule that did not correspond to the sum of the compositions of a candidate fragment ion and its corresponding neutral loss were discarded. One, 2-5, 6-10, 11-20, and >20 candidate compositions were found for 65%, 39%, 1%, 1%, and 0%, respectively, for the 124 ionized molecules formed from the 113 chemicals tested (both positive and negative ions were obtained from 11 of the chemicals). However, no candidate composition was found for 2% of the test cases (i.e., 3 chemicals), for each of which the measured mass of one of the product ions was in error by 5-6.7 mDa.

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

PubMed

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

NASA Astrophysics Data System (ADS)

Newsome, G. Asher; Ackerman, Luke K.; Johnson, Kevin J.

2016-01-01

Post-plasma ambient desorption/ionization (ADI) sources are fundamentally dependent on surrounding water vapor to produce protonated analyte ions. There are two reports of humidity effects on ADI spectra. However, it is unclear whether humidity will affect all ADI sources and analytes, and by what mechanism humidity affects spectra. Flowing atmospheric pressure afterglow (FAPA) ionization and direct analysis in real time (DART) mass spectra of various surface-deposited and gas-phase analytes were acquired at ambient temperature and pressure across a range of observed humidity values. A controlled humidity enclosure around the ion source and mass spectrometer inlet was used to create programmed humidity and temperatures. The relative abundance and fragmentation of molecular adduct ions for several compounds consistently varied with changing ambient humidity and also were controlled with the humidity enclosure. For several compounds, increasing humidity decreased protonated molecule and other molecular adduct ion fragmentation in both FAPA and DART spectra. For others, humidity increased fragment ion ratios. The effects of humidity on molecular adduct ion fragmentation were caused by changes in the relative abundances of different reagent protonated water clusters and, thus, a change in the average difference in proton affinity between an analyte and the population of water clusters. Control of humidity in ambient post-plasma ion sources is needed to create spectral stability and reproducibility.

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources.

PubMed

Newsome, G Asher; Ackerman, Luke K; Johnson, Kevin J

2016-01-01

Post-plasma ambient desorption/ionization (ADI) sources are fundamentally dependent on surrounding water vapor to produce protonated analyte ions. There are two reports of humidity effects on ADI spectra. However, it is unclear whether humidity will affect all ADI sources and analytes, and by what mechanism humidity affects spectra. Flowing atmospheric pressure afterglow (FAPA) ionization and direct analysis in real time (DART) mass spectra of various surface-deposited and gas-phase analytes were acquired at ambient temperature and pressure across a range of observed humidity values. A controlled humidity enclosure around the ion source and mass spectrometer inlet was used to create programmed humidity and temperatures. The relative abundance and fragmentation of molecular adduct ions for several compounds consistently varied with changing ambient humidity and also were controlled with the humidity enclosure. For several compounds, increasing humidity decreased protonated molecule and other molecular adduct ion fragmentation in both FAPA and DART spectra. For others, humidity increased fragment ion ratios. The effects of humidity on molecular adduct ion fragmentation were caused by changes in the relative abundances of different reagent protonated water clusters and, thus, a change in the average difference in proton affinity between an analyte and the population of water clusters. Control of humidity in ambient post-plasma ion sources is needed to create spectral stability and reproducibility.

Clusters of DNA induced by ionizing radiation: formation of short DNA fragments. I. Theoretical modeling

NASA Technical Reports Server (NTRS)

Holley, W. R.; Chatterjee, A.

1996-01-01

We have developed a general theoretical model for the interaction of ionizing radiation with chromatin. Chromatin is modeled as a 30-nm-diameter solenoidal fiber comprised of 20 turns of nucleosomes, 6 nucleosomes per turn. Charged-particle tracks are modeled by partitioning the energy deposition between primary track core, resulting from glancing collisions with 100 eV or less per event, and delta rays due to knock-on collisions involving energy transfers >100 eV. A Monte Carlo simulation incorporates damages due to the following molecular mechanisms: (1) ionization of water molecules leading to the formation of OH, H, eaq, etc.; (2) OH attack on sugar molecules leading to strand breaks: (3) OH attack on bases; (4) direct ionization of the sugar molecules leading to strand breaks; (5) direct ionization of the bases. Our calculations predict significant clustering of damage both locally, over regions up to 40 bp and over regions extending to several kilobase pairs. A characteristic feature of the regional damage predicted by our model is the production of short fragments of DNA associated with multiple nearby strand breaks. The shapes of the spectra of DNA fragment lengths depend on the symmetries or approximate symmetries of the chromatin structure. Such fragments have subsequently been detected experimentally and are reported in an accompanying paper (B. Rydberg, Radiat, Res. 145, 200-209, 1996) after exposure to both high- and low-LET radiation. The overall measured yields agree well quantitatively with the theoretical predictions. Our theoretical results predict the existence of a strong peak at about 85 bp, which represents the revolution period about the nucleosome. Other peaks at multiples of about 1,000 bp correspond to the periodicity of the particular solenoid model of chromatin used in these calculations. Theoretical results in combination with experimental data on fragmentation spectra may help determine the consensus or average structure of the chromatin fibers in mammalian DNA.

Absolute photoionization cross sections of two cyclic ketones: cyclopentanone and cyclohexanone.

PubMed

Price, Chelsea; Fathi, Yasmin; Meloni, Giovanni

2017-05-01

Absolute photoionization cross sections for cyclopentanone and cyclohexanone, as well as partial ionization cross sections for the dissociative ionized fragments, are presented in this investigation. Experiments are performed via a multiplexed photoionization mass spectrometer utilizing vacuum ultraviolet (VUV) synchrotron radiation supplied by the Advanced Light Source of Lawrence Berkeley National Laboratory. These results allow the quantification of these species that is relevant to investigate the kinetics and combustion reactions of potential biofuels. The CBS-QB3 calculated values for the adiabatic ionization energies agree well with the experimental values, and the identification of possible dissociative fragments is discussed for both systems. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Fragmentation pathways of 2-substituted pyrrole derivatives using electrospray ionization ion trap and electrospray ionization quadrupole time-of-flight mass spectrometry.

PubMed

Liang, Xianrui; Guo, Zili; Yu, Chuanming

2013-10-30

Pyrrole derivatives are of considerable importance and are present in a wide range of natural products and used extensively in drug discovery. Fragmentation pathway studies play an important role in the structural identification of pyrrole derivatives. As a part of our ongoing work on heterocycles, fragmentation pathways of 2-substituted pyrrole derivatives were investigated by mass spectrometry (MS). Twelve pyrrole derivatives were synthesized and analyzed. Low-resolution fragmentation ions of all the compounds were generated by ion trap mass spectrometry (ITMS(n) ) with an electrospray ionization (ESI) source in positive mode. Hybrid quadrupole time-of-flight mass spectrometry (QTOFMS) was used to determine the elemental compositions of the resultant product ions. The side-chain substituents at the 2-position influence the fragmentation pathways. Typical losses of H2 O, aldehydes and pyrrole moieties from the [M + H](+) ion are observed for the compounds with side chains bearing aromatic groups at the 2-position of the pyrrole. However, losses of H2 O, alcohols and C3 H6 are the main cleavage pathways for compounds 6 and 12 with nonphenyl-substituted side chains at the 2-position. Typical fragmentation mechanisms of 2-substituted pyrrole derivatives are proposed and elucidated based on the observations of ITMS(n) and QTOFMS spectra. The results showed that the fragmentation pathways were remarkably influenced by the side-chain substituents at the 2-position of pyrrole. This investigation should have value in the structural identification of this series of molecules or compounds with similar structures. Copyright © 2013 John Wiley & Sons, Ltd.

Comparison of Atmospheric Pressure Chemical Ionization and Field Ionization Mass Spectrometry for the Analysis of Large Saturated Hydrocarbons.

PubMed

Jin, Chunfen; Viidanoja, Jyrki; Li, Mingzhe; Zhang, Yuyang; Ikonen, Elias; Root, Andrew; Romanczyk, Mark; Manheim, Jeremy; Dziekonski, Eric; Kenttämaa, Hilkka I

2016-11-01

Direct infusion atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was compared to field ionization mass spectrometry (FI-MS) for the determination of hydrocarbon class distributions in lubricant base oils. When positive ion mode APCI with oxygen as the ion source gas was employed to ionize saturated hydrocarbon model compounds (M) in hexane, only stable [M - H] + ions were produced. Ion-molecule reaction studies performed in a linear quadrupole ion trap suggested that fragment ions of ionized hexane can ionize saturated hydrocarbons via hydride abstraction with minimal fragmentation. Hence, APCI-MS shows potential as an alternative of FI-MS in lubricant base oil analysis. Indeed, the APCI-MS method gave similar average molecular weights and hydrocarbon class distributions as FI-MS for three lubricant base oils. However, the reproducibility of APCI-MS method was found to be substantially better than for FI-MS. The paraffinic content determined using the APCI-MS and FI-MS methods for the base oils was similar. The average number of carbons in paraffinic chains followed the same increasing trend from low viscosity to high viscosity base oils for the two methods.

Electron-impact-ionization dynamics of S F6

NASA Astrophysics Data System (ADS)

Bull, James N.; Lee, Jason W. L.; Vallance, Claire

2017-10-01

A detailed understanding of the dissociative electron ionization dynamics of S F6 is important in the modeling and tuning of dry-etching plasmas used in the semiconductor manufacture industry. This paper reports a crossed-beam electron ionization velocity-map imaging study on the dissociative ionization of cold S F6 molecules, providing complete, unbiased kinetic energy distributions for all significant product ions. Analysis of these distributions suggests that fragmentation following single ionization proceeds via formation of S F5 + or S F3 + ions that then dissociate in a statistical manner through loss of F atoms or F2, until most internal energy has been liberated. Similarly, formation of stable dications is consistent with initial formation of S F4 2 + ions, which then dissociate on a longer time scale. These data allow a comparison between electron ionization and photoionization dynamics, revealing similar dynamical behavior. In parallel with the ion kinetic energy distributions, the velocity-map imaging approach provides a set of partial ionization cross sections for all detected ionic fragments over an electron energy range of 50-100 eV, providing partial cross sections for S2 +, and enables the cross sections for S F4 2 + from S F+ to be resolved.

Electron-Impact Ionization and Dissociative Ionization of Biomolecules

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Chaban, Galina M.; Dateo, Christopher E.

2006-01-01

It is well recognized that secondary electrons play an important role in radiation damage to humans. Particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. Our study of electron-impact ionization of DNA fragments uses the improved binary-encounter dipole model and covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3(sup prime)- and C5 (sup prime)-deoxyribose-phospate cross sections, differing by less than 5%. Investigation of tandem double lesion initiated by electron-impact dissociative ionization of guanine, followed by proton reaction with the cytosine in the Watson-Crick pair, is currently being studied to see if tandem double lesion can be initiated by electron impact. Up to now only OH-induced tandem double lesion has been studied.

Comparison of Three Plasma Sources for Ambient Desorption/Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

McKay, Kirsty; Salter, Tara L.; Bowfield, Andrew; Walsh, James L.; Gilmore, Ian S.; Bradley, James W.

2014-09-01

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources.

Comparison of three plasma sources for ambient desorption/ionization mass spectrometry.

PubMed

McKay, Kirsty; Salter, Tara L; Bowfield, Andrew; Walsh, James L; Gilmore, Ian S; Bradley, James W

2014-09-01

Plasma-based desorption/ionization sources are an important ionization technique for ambient surface analysis mass spectrometry. In this paper, we compare and contrast three competing plasma based desorption/ionization sources: a radio-frequency (rf) plasma needle, a dielectric barrier plasma jet, and a low-temperature plasma probe. The ambient composition of the three sources and their effectiveness at analyzing a range of pharmaceuticals and polymers were assessed. Results show that the background mass spectrum of each source was dominated by air species, with the rf needle producing a richer ion spectrum consisting mainly of ionized water clusters. It was also seen that each source produced different ion fragments of the analytes under investigation: this is thought to be due to different substrate heating, different ion transport mechanisms, and different electric field orientations. The rf needle was found to fragment the analytes least and as a result it was able to detect larger polymer ions than the other sources.

Electron scattering measurements from molecules of technological relevance

NASA Astrophysics Data System (ADS)

Jones, Darryl

2014-10-01

Biomass represents a significant opportunity to provide renewable and sustainable biofuels. Non-thermal atmospheric pressure plasmas provide an opportunity to efficiently breakdown the naturally-resilient biomass into its useful subunits. Free electrons produced in the plasma may assist in this process by inducing fragmentation though dissociative excitation, ionization or attachment processes. To assist in understanding and refining this process, we have performed electron energy loss experiments from phenol (C6H5OH), a key structural building block of biomass. This enables a quantitative assessment of the excited electronic states of phenol. Differential cross sections for the electron-driven excitation of phenol have also been obtained for incident electron energies in the 20--250 eV range and over 3--90° scattering angles. DBJ acknowledges financial support provided by an Australian Research Council DECRA.

Microsynthesis and electron ionization mass spectral studies of O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates for Chemical Weapons Convention verification.

PubMed

Saeidian, Hamdollah; Babri, Mehran; Abdoli, Morteza; Sarabadani, Mansour; Ashrafi, Davood; Naseri, Mohammad Taghi

2012-12-15

The availability of mass spectra and interpretation skills are essential for unambiguous identification of the Chemical Weapons Convention (CWC)-related chemicals. The O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates are included in the list of scheduled CWC-related compounds, but there are very few spectra from these compounds in the literature. This paper examines these spectra and their mass spectral fragmentation routes. The title chemicals were prepared through microsynthetic protocols and were analyzed using electron ionization mass spectrometry with gas chromatography as a MS-inlet system. Structures of fragments were confirmed using analysis of fragment ions of deuterated analogs, tandem mass spectrometry and density functional theory (DFT) calculations. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as alkene and amine elimination and McLafferty-type rearrangements. The most important fragmentation route of the chemicals is the thiono-thiolo rearrangement. DFT calculations are used to support MS results and to reveal relative preference formation of fragment ions. The retention indices (RIs) of all the studied compounds are also reported. Mass spectra of the synthesized compounds were investigated with the aim to enrich the Organization for the Prohibition of Chemical Weapons (OPCW) Central Analytical Database (OCAD) which may be used for detection and identification of CWC-related chemicals during on-site inspection and/or off-site analysis such as OPCW proficiency tests. Copyright © 2012 John Wiley & Sons, Ltd.

Fragmentation study of iridoid glucosides through positive and negative electrospray ionization, collision-induced dissociation and tandem mass spectrometry.

PubMed

Es-Safi, Nour-Eddine; Kerhoas, Lucien; Ducrot, Paul-Henri

2007-01-01

Mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) has been applied to the mass spectral study of a series of six naturally occurring iridoids through in-source fragmentation of the protonated [M+H]+, deprotonated [M--H]- and sodiated [M+Na]+ ions. This led to the unambiguous determination of the molecular masses of the studied compounds and allowed CID spectra of the molecular ions to be obtained. Valuable structural information regarding the nature of both the glycoside and the aglycone moiety was thus obtained. Glycosidic cleavage and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during CID, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. The formation of the ionized aglycones, sugars and their product ions was thus obtained giving information on their basic skeleton. The protonated, i.e. [M+H]+ and deprotonated [M--H]-, ions were found to fragment mainly by glycosidic cleavages. MS/MS spectra of the [M+Na]+ ions gave complementary information for the structural characterization of the studied compounds. Unlike the dissociation of protonated molecular ions, that of sodiated molecules also provided sodiated sugar fragments where the C0+ fragment corresponding to the glucose ion was obtained as base peak for all the studied compounds. Copyright (c) 2007 John Wiley & Sons, Ltd.

The laser desorption/laser ionization mass spectra of some anti-inflammatory drugs

NASA Astrophysics Data System (ADS)

Milnes, John; Rogers, Kevin; Jones, Sian; Gormally, John

1994-03-01

The IR laser desorption/ultraviolet laser ionization time-of-flight mass spectra are reported for the anti-inflammatory drugs indomethacin, acemetacin, ibuprofen, flurbiprofen, diflunisal and mefenamic acid. It is found that the six compounds can be readily ionized by two photon absorption at a fixed wavelength of 266 nm. Mass spectra have been obtained under conditions of high ionizing irradiance and the observed fragmentation behaviour is discussed.

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

USGS Publications Warehouse

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

2001-01-01

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

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.

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

NASA Technical Reports Server (NTRS)

Getty, Stephanie; Brickerhoff, William; Cornish, Timothy; Ecelberger, Scott; Floyd, Melissa

2012-01-01

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Electrospray ionization mass spectrometry: a technique to access the information beyond the molecular weight of the analyte.

PubMed

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research.

Fragmentation of ionized doped helium nanodroplets: theoretical evidence for a dopant ejection mechanism.

PubMed

Bonhommeau, D; Lewerenz, M; Halberstadt, N

2008-02-07

We report a theoretical study of the effect induced by a helium nanodroplet environment on the fragmentation dynamics of a dopant. The dopant is an ionized neon cluster Ne(n) (+) (n=4-6) surrounded by a helium nanodroplet composed of 100 atoms. A newly designed mixed quantum/classical approach is used to take into account both the large helium cluster zero-point energy due to the light mass of the helium atoms and all the nonadiabatic couplings between the Ne(n) (+) potential-energy surfaces. The results reveal that the intermediate ionic dopant can be ejected from the droplet, possibly with some helium atoms still attached, thereby reducing the cooling power of the droplet. Energy relaxation by helium atom evaporation and dissociation, the other mechanism which has been used in most interpretations of doped helium cluster dynamics, also exhibits new features. The kinetic energy distribution of the neutral monomer fragments can be fitted to the sum of two Boltzmann distributions, one with a low kinetic energy and the other with a higher kinetic energy. This indicates that cooling by helium atom evaporation is more efficient than was believed so far, as suggested by recent experiments. The results also reveal the predominance of Ne(2) (+) and He(q)Ne(2) (+) fragments and the absence of bare Ne(+) fragments, in agreement with available experimental data (obtained for larger helium nanodroplets). Moreover, the abundance in fragments with a trimeric neon core is found to increase with the increase in dopant size. Most of the fragmentation is achieved within 10 ps and the only subsequent dynamical process is the relaxation of hot intermediate He(q)Ne(2) (+) species to Ne(2) (+) by helium atom evaporation. The dependence of the ionic fragment distribution on the parent ion electronic state reached by ionization is also investigated. It reveals that He(q)Ne(+) fragments are produced only from the highest electronic state, whereas He(q)Ne(2) (+) fragments originate from all the electronic states. Surprisingly, the highest electronic states also lead to fragments that still contain the original ionic dopant species. A mechanism is conjectured to explain this fragmentation inhibition.

Glycomics expression analysis of sulfated glycosaminoglycans of human colorectal cancer tissues and non-neoplastic mucosa by electrospray ionization mass spectrometry.

PubMed

Marolla, Ana Paula Cleto; Waisberg, Jaques; Saba, Gabriela Tognini; Waisberg, Daniel Reis; Margeotto, Fernando Beani; Pinhal, Maria Aparecida da Silva

2015-01-01

To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student'st test. The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues.

Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hollstein, Maximilian; Santra, Robin; Pfannkuche, Daniela

2017-05-01

We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999), 10.1016/S0009-2614(99)00508-4], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

PubMed

Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

2018-05-09

Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

Unexpected methyl migrations of ethanol dimer under synchrotron VUV radiation

NASA Astrophysics Data System (ADS)

Xiao, Weizhan; Hu, Yongjun; Li, Weixing; Guan, Jiwen; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

2015-01-01

While methyl transfer is well known to occur in the enzyme- and metal-catalyzed reactions, the methyl transfer in the metal-free organic molecules induced by the photon ionization has been less concerned. Herein, vacuum ultraviolet single photon ionization and dissociation of ethanol dimer are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical methods. Besides the protonated clusters cation (C2H5OH) ṡ H+ (m/z = 47) and the β-carbon-carbon bond cleavage fragment CH2O ṡ (C2H5OH)H+ (m/z = 77), the measured mass spectra revealed that a new fragment (C2H5OH) ṡ (CH3)+ (m/z = 61) appeared at the photon energy of 12.1 and 15.0 eV, where the neutral dimer could be vertically ionized to higher ionic state. Thereafter, the generated carbonium ions are followed by a Wagner-Meerwein rearrangement and then dissociate to produce this new fragment, which is considered to generate after surmounting a few barriers including intra- and inter-molecular methyl migrations by the aid of theoretical calculations. The appearance energy of this new fragment is measured as 11.55 ± 0.05 eV by scanning photoionization efficiency curve. While the signal intensity of fragment m/z = 61 starts to increase, the fragments m/z = 47 and 77 tend to slowly incline around 11.55 eV photon energy. This suggests that the additional fragment channels other than (C2H5OH) ṡ H+ and CH2O ṡ (C2H5OH)H+ have also been opened, which consume some dimer cations. The present report provides a clear description of the photoionization and dissociation processes of the ethanol dimer in the range of the photon energy 12-15 eV.

Waveform control of orientation-dependent ionization of DCl in few-cycle laser fields.

PubMed

Znakovskaya, I; von den Hoff, P; Schirmel, N; Urbasch, G; Zherebtsov, S; Bergues, B; de Vivie-Riedle, R; Weitzel, K-M; Kling, M F

2011-05-21

Strong few-cycle light fields with stable electric field waveforms allow controlling electrons on time scales down to the attosecond domain. We have studied the dissociative ionization of randomly oriented DCl in 5 fs light fields at 720 nm in the tunneling regime. Momentum distributions of D(+) and Cl(+) fragments were recorded via velocity-map imaging. A waveform-dependent anti-correlated directional emission of D(+) and Cl(+) fragments is observed. Comparison of our results with calculations indicates that tailoring of the light field via the carrier envelope phase permits the control over the orientation of DCl(+) and in turn the directional emission of charged fragments upon the breakup of the molecular ion. © The Owner Societies 2011

High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

PubMed

Hourani, Nadim; Kuhnert, Nikolai

2012-10-15

High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

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.

Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry.

PubMed

Setner, Bartosz; Rudowska, Magdalena; Klem, Ewelina; Cebrat, Marek; Szewczuk, Zbigniew

2014-10-01

Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1-azabicyclo[2.2.2]octane (ABCO) or 1,4-diazabicyclo[2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI-MS) and longer retention times on the reverse-phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision-induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a- and b-type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision-induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI-MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.

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.

Glycomics expression analysis of sulfated glycosaminoglycans of human colorectal cancer tissues and non-neoplastic mucosa by electrospray ionization mass spectrometry

PubMed Central

Marolla, Ana Paula Cleto; Waisberg, Jaques; Saba, Gabriela Tognini; Waisberg, Daniel Reis; Margeotto, Fernando Beani; Pinhal, Maria Aparecida da Silva

2015-01-01

ABSTRACT Objective To determine the presence of glycosaminoglycans in the extracellular matrix of connective tissue from neoplastic and non-neoplastic colorectal tissues, since it has a central role in tumor development and progression. Methods Tissue samples from neoplastic and non-neoplastic colorectal tissues were obtained from 64 operated patients who had colorectal carcinoma with no distant metastases. Expressions of heparan sulphate, chondroitin sulphate, dermatan sulphate and their fragments were analyzed by electrospray ionization mass spectrometry, with the technique for extraction and quantification of glycosaminoglycans after proteolysis and electrophoresis. The statistical analysis included mean, standard deviation, and Student’s t test. Results The glycosaminoglycans extracted from colorectal tissue showed three electrophoretic bands in agarose gel. Electrospray ionization mass spectrometry showed characteristic disaccharide fragments from glycosaminoglycans, indicating their structural characterization in the tissues analyzed. Some peaks in the electrospray ionization mass spectrometry were not characterized as fragments of sugars, indicating the presence of fragments of the protein structure of proteoglycans generated during the glycosaminoglycan purification. The average amount of chondroitin and dermatan increased in the neoplastic tissue compared to normal tissue (p=0.01). On the other hand, the average amount of heparan decreased in the neoplastic tissue compared to normal tissue (p= 0.03). Conclusion The method allowed the determination of the glycosaminoglycans structural profile in colorectal tissue from neoplastic and non-neoplastic colorectal tissue. Neoplastic tissues showed greater amounts of chondroitin sulphate and dermatan sulphate compared to non-neoplastic tissues, while heparan sulphate was decreased in neoplastic tissues. PMID:26761548

Intertwined electron-nuclear motion in frustrated double ionization in driven heteronuclear molecules

NASA Astrophysics Data System (ADS)

Vilà, A.; Zhu, J.; Scrinzi, A.; Emmanouilidou, A.

2018-03-01

We study frustrated double ionization (FDI) in a strongly-driven heteronuclear molecule HeH+ and compare with H2. We compute the probability distribution of the sum of the final kinetic energies of the nuclei for strongly-driven HeH+. We find that this distribution has more than one peak for strongly-driven HeH+, a feature we do not find to be present for strongly-driven H2. Moreover, we compute the probability distribution of the principal quantum number n of FDI. We find that this distribution has several peaks for strongly-driven HeH+, while the respective distribution has one main peak and a ‘shoulder’ at lower principal quantum numbers n for strongly-driven H2. Surprisingly, we find this feature to be a clear signature of the intertwined electron-nuclear motion.

MS/MS studies on the selective on-line detection of sesquiterpenes using a Flowing Afterglow-Tandem Mass Spectrometer (FA-TMS)

NASA Astrophysics Data System (ADS)

Rimetz-Planchon, J.; Dhooghe, F.; Schoon, N.; Vanhaecke, F.; Amelynck, C.

2011-04-01

A Flowing Afterglow-Tandem Mass Spectrometer (FA-TMS) was used to investigate the feasibility of selective on-line detection of a series of seven sesquiterpenes (SQTs). These SQTs were chemically ionized by either H3O+ or NO+ reagent ions in the FA, resulting among others in protonated SQT and SQT molecular ions, respectively. These and other Chemical Ionization (CI) product ions were subsequently subjected to dissociation by collisions with Ar atoms in the collision cell of the tandem mass spectrometer. The fragmentation spectra show similarities with mass spectra obtained for these compounds with other instruments such as a Proton Transfer Reaction-Linear Ion Trap (PTR-LIT), a Proton Transfer Reaction-Mass Spectrometer (PTR-MS), a Triple Quadrupole-Mass Spectrometer (QqQ-MS) and a Selected Ion Flow Tube-Mass Spectrometer (SIFT-MS). Fragmentation of protonated SQT is characterized by fragment ions at the same masses but with different intensities for the individual SQT. Distinction of SQTs is based on well-chosen intensity ratios and collision energies. The fragmentation patterns of SQT molecular ions show specific fragment ion tracers at m/z 119, m/z162, m/z 137 and m/z 131 for α-cedrene, δ-neoclovene, isolongifolene and α-humulene, respectively. Consequently, chemical ionization of SQT by NO+, followed by MS/MS of SQT+ seems to open a way for selective quantification of SQTs in mixtures.

A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation.

PubMed

Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

2017-11-01

Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi 3 + beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm 2 . The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

A new instrument of VUV laser desorption/ionization mass spectrometry imaging with micrometer spatial resolution and low level of molecular fragmentation

NASA Astrophysics Data System (ADS)

Wang, Jia; Liu, Feng; Mo, Yuxiang; Wang, Zhaoying; Zhang, Sichun; Zhang, Xinrong

2017-11-01

Mass spectrometry imaging (MSI) has important applications in material research, biology, and medicine. The MSI method based on UV laser desorption/ionization (UVLDI) can obtain images of intact samples, but has a high level of molecular fragmentation. In this work, we report a new MSI instrument that uses a VUV laser (125.3 nm) as a desorption/ionization source to exploit its advantages of high single photon energy and small focus size. The new instrument was tested by the mass spectra of Nile red and FGB (Fibrinogen beta chain) samples and mass spectrometric images of a fly brain section. For the tested samples, the VUVDI method offers lower levels of molecular fragmentations and higher sensitivities than those of the UVLDI method and second ion mass spectrometry imaging method using a Bi3+ beam. The ablation crater produced by the focused VUV laser on a quartz plate has an area of 10 μm2. The VUV laser is prepared based on the four-wave mixing method using three collimated laser beams and a heated Hg cell.

Sperm quality and DNA damage in men from Jilin Province, China, who are occupationally exposed to ionizing radiation.

PubMed

Zhou, D D; Hao, J L; Guo, K M; Lu, C W; Liu, X D

2016-03-22

Long-term radiation exposure affects human health. Ionizing radiation has long been known to raise the risk of cancer. In addition to high doses of radiation, low-dose ionizing radiation might increase the risk of cardiovascular disease, lens opacity, and some other non-cancerous diseases. Low- and high-dose exposures to ionizing radiation elicit different signaling events at the molecular level, and may involve different response mechanisms. The health risks arising from exposure to low doses of ionizing radiation should be re-evaluated. Health workers exposed to ionizing radiation experience low-dose radiation and have an increased risk of hematological malignancies. Reproductive function is sensitive to changes in the physical environment, including ionizing radiation. However, data is scarce regarding the association between occupational radiation exposure and risk to human fertility. Sperm DNA integrity is a functional parameter of male fertility evaluation. Hence, we aimed to report sperm quality and DNA damage in men from Jilin Province, China, who were occupationally exposed to ionizing radiation. Sperm motility and normal morphology were significantly lower in the exposed compared with the non-exposed men. There was no statistically significant difference in sperm concentration between exposed and non-exposed men. The sperm DNA fragmentation index was significantly higher in the exposed than the non-exposed men. Chronic long-term exposure to low doses of ionizing radiation could affect sperm motility, normal morphology, and the sperm DNA fragmentation index in the Chinese population. Sperm quality and DNA integrity are functional parameters that could be used to evaluate occupational exposure to ionizing radiation.

Identification of process related trace level impurities in the actinide decorporation agent 3,4,3-LI(1,2-HOPO): Nozzle–skimmer fragmentation via ESI LC–QTOFMS

DOE PAGES

Panyala, Nagender R.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2014-08-12

We report that 3,4,3-LI(1,2-HOPO) is a chelating ligand and decorporation agent that can remove radioactive lanthanides and actinides from the body. Identification of trace impurities in drug samples is gaining much interest due to their significant influence on drug activity. In this study, trace impurities were detected in manufactured lots of 3,4,3-LI(1,2-HOPO) by a developed method of Liquid Chromatography coupled with photo-diode array UV detection and Electrospray Ionization-Quadrupole Time of Flight Mass spectrometry (LC-QTOFMS), via induced-in-source or collision-induced mass fragmentation (Nozzle-Skimmer Fragmentation). Molecular ions were fragmented within the nozzle-skimmer region of electrospray ionization (ESI) mass spectrometer equipped with a Timemore » of Flight detector. Eight major (detected at levels higher than a 0.1% threshold) and seven minor trace impurities were identified. The respective structures of these impurities were elucidated via analysis of the generated fragment ions using mass fragmentation and elemental composition software. Proposed structures of impurities were further confirmed via isotopic modeling.« less

Electron impact fragmentation of adenine: partial ionization cross sections for positive fragments

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Finnegan, Sinead; Eden, Samuel

2015-07-01

Using computer-controlled data acquisition we have measured mass spectra of positive ions for electron impact on adenine, with electron energies up to 100 eV. Ion yield curves for 50 ions have been obtained and normalized by comparing their sum to the average of calculated total ionization cross sections. Appearance energies have been determined for 37 ions; for 20 ions for the first time. All appearance energies are consistent with the fragmentation pathways identified in the literature. Second onset energies have been determined for 12 fragment ions (for 11 ions for the first time), indicating the occurrence of more than one fragmentation process e.g. for 39 u (C2HN+) and 70 u (C2H4N3+). Matching ion yield shapes (118-120 u, 107-108 u, 91-92 u, and 54-56 u) provide new evidence supporting closely related fragmentation pathways and are attributed to hydrogen rearrangement immediately preceding the fragmentation. We present the first measurement of the ion yield curve of the doubly charged parent ion (67.5 u), with an appearance energy of 23.5 ± 1.0 eV. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Tailored nanopost arrays (NAPA) for laser desorption ionization in mass spectrometry

DOEpatents

Vertes, Akos; Walker, Bennett N.; Stolee, Jessica A.; Retterer, Scott T.

2016-11-08

The production and use of semiconducting nanopost arrays made by nanofabrication is described herein. These nanopost arrays (NAPA) provide improved laser ionization yields and controllable fragmentation with switching or modulation capabilities for mass spectrometric detection and identification of samples deposited on them.

Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte

PubMed Central

Banerjee, Shibdas; Mazumdar, Shyamalava

2012-01-01

The Electrospray Ionization (ESI) is a soft ionization technique extensively used for production of gas phase ions (without fragmentation) of thermally labile large supramolecules. In the present review we have described the development of Electrospray Ionization mass spectrometry (ESI-MS) during the last 25 years in the study of various properties of different types of biological molecules. There have been extensive studies on the mechanism of formation of charged gaseous species by the ESI. Several groups have investigated the origin and implications of the multiple charge states of proteins observed in the ESI-mass spectra of the proteins. The charged analytes produced by ESI can be fragmented by activating them in the gas-phase, and thus tandem mass spectrometry has been developed, which provides very important insights on the structural properties of the molecule. The review will highlight recent developments and emerging directions in this fascinating area of research. PMID:22611397

All-solid-state deep ultraviolet laser for single-photon ionization mass spectrometry.

PubMed

Yuan, Chengqian; Liu, Xianhu; Zeng, Chenghui; Zhang, Hanyu; Jia, Meiye; Wu, Yishi; Luo, Zhixun; Fu, Hongbing; Yao, Jiannian

2016-02-01

We report here the development of a reflectron time-of-flight mass spectrometer utilizing single-photon ionization based on an all-solid-state deep ultraviolet (DUV) laser system. The DUV laser was achieved from the second harmonic generation using a novel nonlinear optical crystal KBe2BO3F2 under the condition of high-purity N2 purging. The unique property of this laser system (177.3-nm wavelength, 15.5-ps pulse duration, and small pulse energy at ∼15 μJ) bears a transient low power density but a high single-photon energy up to 7 eV, allowing for ionization of chemicals, especially organic compounds free of fragmentation. Taking this advantage, we have designed both pulsed nanospray and thermal evaporation sources to form supersonic expansion molecular beams for DUV single-photon ionization mass spectrometry (DUV-SPI-MS). Several aromatic amine compounds have been tested revealing the fragmentation-free performance of the DUV-SPI-MS instrument, enabling applications to identify chemicals from an unknown mixture.

Fragmentation of mercury compounds under ultraviolet light irradiation

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

Kokkonen, E.; Hautala, L.; Jänkälä, K.

2015-08-21

Ultraviolet light induced photofragmentation of mercury compounds is studied experimentally with electron energy resolved photoelectron-photoion coincidence techniques and theoretically with computational quantum chemical methods. A high resolution photoelectron spectrum using synchrotron radiation is presented. Fragmentation of the molecule is studied subsequent to ionization to the atomic-mercury-like d orbitals. State dependent fragmentation behaviour is presented and specific reactions for dissociation pathways are given. The fragmentation is found to differ distinctly in similar orbitals of different mercury compounds.

ACE-SWICS In Situ Plasma Composition of Fragmented Comet 73P/Schwassmann-Wachmann 3

NASA Astrophysics Data System (ADS)

Gilbert, J. A.; Lepri, S. T.; Rubin, M.; Zurbuchen, T.

2013-12-01

The interiors of comets contain some of the most pristine material in the solar system. Comet 73P/Schwassmann-Wachmann 3, discovered in 1930 with a double nucleus, is a Jupiter-family comet with a 5.34-year period. This comet split into 5 fragments in 1995 and disintegrated into nearly 70 pieces in 2006. In May and June of 2006, recently ionized cometary particles originating from some of these fragments were collected with the ACE-SWICS sensor. Due to a combination of the close proximity of the fragments passing between ACE-SWICS and the Sun, and the instrument characteristics, unique measurements regarding the charge state composition and the elemental abundances of both cometary and heliospheric plasma were made during this time. The cometary material released from some of these fragments can be identified by the concentrations of water-group pick-up ions having a mass-per-charge of 16-18 amu/e. With a focus on Helium, Carbon, and water-group ions, we present an analysis of the cometary plasma. Charge state ratios of C+/O+ fall below 0.1 during detection of comet fragment plasma, and there is a clear increase in He+ during fragment crossings. The C/O ratio and He charge states are used to provide constraints on the activity of the cometary fragments and also the spatial distribution of the extended and ionized cometary tail.

Electron impact ionization of size selected hydrogen clusters (H2)N: ion fragment and neutral size distributions.

PubMed

Kornilov, Oleg; Toennies, J Peter

2008-05-21

Clusters consisting of normal H2 molecules, produced in a free jet expansion, are size selected by diffraction from a transmission nanograting prior to electron impact ionization. For each neutral cluster (H2)(N) (N=2-40), the relative intensities of the ion fragments Hn+ are measured with a mass spectrometer. H3+ is found to be the most abundant fragment up to N=17. With a further increase in N, the abundances of H3+, H5+, H7+, and H9+ first increase and, after passing through a maximum, approach each other. At N=40, they are about the same and more than a factor of 2 and 3 larger than for H11+ and H13+, respectively. For a given neutral cluster size, the intensities of the ion fragments follow a Poisson distribution. The fragmentation probabilities are used to determine the neutral cluster size distribution produced in the expansion at a source temperature of 30.1 K and a source pressure of 1.50 bar. The distribution shows no clear evidence of a magic number N=13 as predicted by theory and found in experiments with pure para-H2 clusters. The ion fragment distributions are also used to extract information on the internal energy distribution of the H3+ ions produced in the reaction H2+ + H2-->H3+ +H, which is initiated upon ionization of the cluster. The internal energy is assumed to be rapidly equilibrated and to determine the number of molecules subsequently evaporated. The internal energy distribution found in this way is in good agreement with data obtained in an earlier independent merged beam scattering experiment.

Characterization of nonpolar lipids and selected steroids by using laser-induced acoustic desorption/chemical ionization, atmospheric pressure chemical ionization, and electrospray ionization mass spectrometry

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

Jin, Zhicheng; Daiya, Shivani; Kenttämaa, Hilkka I.

2011-03-01

Laser-induced acoustic desorption (LIAD) combined with ClMn(H2O)+ chemical ionization (CI) was tested for the analysis of nonpolar lipids and selected steroids in a Fourier-transform ion cyclotron resonance mass spectrometer (FT-ICR). The nonpolar lipids studied, cholesterol, 5α-cholestane, cholesta-3,5-diene, squalene, and β-carotene, were found to solely form the desired water replacement product (adduct-H2O) upon reaction with the ClMn(H2O)+ ions. The steroids, androsterone, dehydroepiandrosterone (DHEA), estrone, estradiol, and estriol, also form abundant adduct-H2O ions, but less abundant adduct-2H2O ions were also observed. Neither (+)APCI nor (+)ESI can ionize the saturated hydrocarbon lipid, cholestane. APCI successfully ionizes the unsaturated hydrocarbon lipids to form exclusivelymore » the intact protonated analytes. However, it causes extensive fragmentation for cholesterol and the steroids. The worst case is cholesterol that does not produce any stable protonated molecules. On the other hand, ESI cannot ionize any of the hydrocarbon analytes, saturated or unsaturated. However, ESI can be used to protonate the oxygen-containing analytes with substantially less fragmentation than for APCI in all cases except for cholesterol and estrone. In conclusion, LIAD/ClMn(H2O)+ chemical ionization is superior over APCI and ESI for the mass spectrometric characterization of underivatized nonpolar lipids and steroids.« less

Size dependent fragmentation of argon clusters in the soft x-ray ionization regime

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

Gisselbrecht, Mathieu; Lindgren, Andreas; Burmeister, Florian

Photofragmentation of argon clusters of average size ranging from 10 up to 1000 atoms is studied using soft x-ray radiation below the 2p threshold and multicoincidence mass spectroscopy technique. For small clusters (=10), ionization induces fast fragmentation with neutral emission imparting a large amount of energy. While the primary dissociation takes place on a picosecond time scale, the fragments undergo slow degradation in the spectrometer on a microsecond time scale. For larger clusters ({>=}100) we believe that we observe the fragmentation pattern of multiply charged species on a time-scale which lasts a few hundred nanoseconds. The reason for these slowermore » processes is the large number of neutral atoms which act as an efficient cooling bath where the excess energy ('heat') dissipates among all degrees of freedom. Further degradation of the photoionic cluster in spectrometer then takes place on the microsecond time scale, similar to small clusters.« less

Driven fragmentation of granular gases.

PubMed

Cruz Hidalgo, Raúl; Pagonabarraga, Ignacio

2008-06-01

The dynamics of homogeneously heated granular gases which fragment due to particle collisions is analyzed. We introduce a kinetic model which accounts for correlations induced at the grain collisions and analyze both the kinetics and relevant distribution functions these systems develop. The work combines analytical and numerical studies based on direct simulation Monte Carlo calculations. A broad family of fragmentation probabilities is considered, and its implications for the system kinetics are discussed. We show that generically these driven materials evolve asymptotically into a dynamical scaling regime. If the fragmentation probability tends to a constant, the grain number diverges at a finite time, leading to a shattering singularity. If the fragmentation probability vanishes, then the number of grains grows monotonously as a power law. We consider different homogeneous thermostats and show that the kinetics of these systems depends weakly on both the grain inelasticity and driving. We observe that fragmentation plays a relevant role in the shape of the velocity distribution of the particles. When the fragmentation is driven by local stochastic events, the long velocity tail is essentially exponential independently of the heating frequency and the breaking rule. However, for a Lowe-Andersen thermostat, numerical evidence strongly supports the conjecture that the scaled velocity distribution follows a generalized exponential behavior f(c) approximately exp(-cn) , with n approximately 1.2 , regarding less the fragmentation mechanisms.

An investigation of electronic states of some molecules and molecular cations using mass analyzed threshold ionization and photoinduced Rydberg ionization spectroscopy

NASA Astrophysics Data System (ADS)

Hofstein, Jason David

1999-11-01

Mass analyzed threshold ionization (MATI) experiments have enabled mapping of the n-dependent Rydberg state survival probability for a series of molecules. Utilizing vacuum and extreme ultraviolet (VUV/XUV) photons, one photon Rydberg manifold spectra of argon, hydrogen chloride, nitrogen, benzene, and oxygen were produced, and the prospects of photoinduced Rydberg ionization (PIRI) experiments examined. It was found that the widths of Rydberg manifolds for the molecules studied are quite different. Hydrogen chloride and nitrogen have the narrowest manifold width, followed by benzene, and then oxygen. These varying widths are most strongly correlated with the angular momentum (i.e., quantum defect) of the initially prepared Rydberg orbital. PIRI experiments required the use of a static cell, rather than a molecular jet assembly, for the more efficient production of higher amounts of VUV/XUV radiation, and hence more Rydberg signal needed to observe PIRI. Armed with the ability to produce tunable VUV/XUV radiation, and to determine the feasibility of a PIRI experiment, the MATI and fragment PIRI spectra of trans-1,3-butadiene (BD) were recorded. The MATI spectrum is vibrationally resolved and was analyzed with the help of ab initio calculations and other published results. The fragment PIRI spectrum of the A<==X transition of BD+ is not vibrationally resolved, but information regarding the wavelength dependence of fragmentation pathways has been gathered and interpreted. It was found that at low photodissociation photon energies, production of C3H3+ dominates, but at higher photon energies, C2H4 + is also produced. The production of each fragment showed a definite PIRI wavelength dependence.

Characterization of Hydrophobic Peptides in the Presence of Detergent by Photoionization Mass Spectrometry

PubMed Central

Bagag, Aïcha; Jault, Jean-Michel; Sidahmed-Adrar, Nazha; Réfrégiers, Matthieu; Giuliani, Alexandre; Le Naour, François

2013-01-01

The characterization of membrane proteins is still challenging. The major issue is the high hydrophobicity of membrane proteins that necessitates the use of detergents for their extraction and solubilization. The very poor compatibility of mass spectrometry with detergents remains a tremendous obstacle in studies of membrane proteins. Here, we investigated the potential of atmospheric pressure photoionization (APPI) for mass spectrometry study of membrane proteins. This work was focused on the tetraspanin CD9 and the multidrug transporter BmrA. A set of peptides from CD9, exhibiting a broad range of hydropathicity, was investigated using APPI as compared to electrospray ionization (ESI). Mass spectrometry experiments revealed that the most hydrophobic peptides were hardly ionized by ESI whereas all peptides, including the highly hydrophobic one that corresponds to the full sequence of the first transmembrane domain of CD9, were easily ionized by APPI. The native protein BmrA purified in the presence of the non-ionic detergent beta-D-dodecyl maltoside (DDM) was digested in-solution using trypsin. The resulting peptides were investigated by flow injection analysis of the mixture followed by mass spectrometry. Upon ESI, only detergent ions were detected and the ionic signals from the peptides were totally suppressed. In contrast, APPI allowed many peptides distributed along the sequence of the protein to be detected. Furthermore, the parent ion corresponding to the first transmembrane domain of the protein BmrA was detected under APPI conditions. Careful examination of the APPI mass spectrum revealed a-, b-, c- and y- fragment ions generated by in-source fragmentation. Those fragment ions allowed unambiguous structural characterization of the transmembrane domain. In conclusion, APPI–MS appears as a versatile method allowing the ionization and fragmentation of hydrophobic peptides in the presence of detergent. PMID:24236085

Non-random distribution of DNA double-strand breaks induced by particle irradiation

NASA Technical Reports Server (NTRS)

Lobrich, M.; Cooper, P. K.; Rydberg, B.; Chatterjee, A. (Principal Investigator)

1996-01-01

Induction of DNA double-strand breaks (dsbs) in mammalian cells is dependent on the spatial distribution of energy deposition from the ionizing radiation. For high LET particle radiations the primary ionization sites occur in a correlated manner along the track of the particles, while for X-rays these sites are much more randomly distributed throughout the volume of the cell. It can therefore be expected that the distribution of dsbs linearly along the DNA molecule also varies with the type of radiation and the ionization density. Using pulsed-field gel and conventional gel techniques, we measured the size distribution of DNA molecules from irradiated human fibroblasts in the total range of 0.1 kbp-10 Mbp for X-rays and high LET particles (N ions, 97 keV/microns and Fe ions, 150 keV/microns). On a mega base pair scale we applied conventional pulsed-field gel electrophoresis techniques such as measurement of the fraction of DNA released from the well (FAR) and measurement of breakage within a specific NotI restriction fragment (hybridization assay). The induction rate for widely spaced breaks was found to decrease with LET. However, when the entire distribution of radiation-induced fragments was analysed, we detected an excess of fragments with sizes below about 200 kbp for the particles compared with X-irradiation. X-rays are thus more effective than high LET radiations in producing large DNA fragments but less effective in the production of smaller fragments. We determined the total induction rate of dsbs for the three radiations based on a quantitative analysis of all the measured radiation-induced fragments and found that the high LET particles were more efficient than X-rays at inducing dsbs, indicating an increasing total efficiency with LET. Conventional assays that are based only on the measurement of large fragments are therefore misleading when determining total dsb induction rates of high LET particles. The possible biological significance of this non-randomness for dsb induction is discussed.

Onset of space charge effects in liquid argon ionization chambers

NASA Astrophysics Data System (ADS)

Toggerson, B.; Newcomer, A.; Rutherfoord, J.; Walker, R. B.

2009-09-01

Using a thin-gap liquid argon ionization chamber and Strontium-90 beta sources we have measured ionization currents over a wide range of gap potentials. These precision "HV plateau curves" advance the understanding of liquid argon sampling calorimeter signals, particularly at high ionization rates. The order of magnitude differences in the activities of the beta sources allow us to estimate where the ionization chamber is driven into the space-charge dominated regime.

Characterization of limonin glucoside metabolites from human prostate cell culture medium using high-performance liquid chromatography/electrospray ionization mass spectrometry and tandem mass spectrometry.

PubMed

Tian, Qingguo; Kent, Kyle D; Bomser, Joshua A; Schwartz, Steven J

2004-01-01

The metabolism of limonin 17-beta-D-glucopyranoside (LG) by non-cancerous (RWPE-1) and cancerous (PC-3) human prostate epithelial cells was investigated using high-performance liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) with in-source fragmentation and tandem mass spectrometry (MS/MS). During positive ion LC/ESI-MS, LG formed an abundant sodiated species ([M+Na]+) while the protonated molecule was barely observable. [M+Na]+ further fragmented into the less abundant [LARL+H]+ and a predominantly protonated aglycone molecule (limonin) due to in-source fragmentation. The major metabolite, limonin A-ring lactone (LARL), formed an abundant protonated molecule that was fragmented into a protonated molecule of limonin by loss of one molecule of water. In MS/MS by collisionally activated dissociation (CAD), LG produced the sodiated aglycone, [aglycone+Na]+, while LARL fragmented into [M+H]+ of limonin and fragment ions resulted by further loss of water, carbon monoxide and carbon dioxide, indicating the presence of oxygenated-ring structures. The limits of detection of LG were 0.4 and 20 fmol in selected-ion monitoring (SIM) and selected-reaction monitoring (SRM) detection, respectively. Copyright 2004 John Wiley & Sons, Ltd.

Dose equivalent near the bone-soft tissue interface from nuclear fragments produced by high-energy protons

NASA Technical Reports Server (NTRS)

Shavers, M. R.; Poston, J. W.; Cucinotta, F. A.; Wilson, J. W.

1996-01-01

During manned space missions, high-energy nucleons of cosmic and solar origin collide with atomic nuclei of the human body and produce a broad linear energy transfer spectrum of secondary particles, called target fragments. These nuclear fragments are often more biologically harmful than the direct ionization of the incident nucleon. That these secondary particles increase tissue absorbed dose in regions adjacent to the bone-soft tissue interface was demonstrated in a previous publication. To assess radiological risks to tissue near the bone-soft tissue interface, a computer transport model for nuclear fragments produced by high energy nucleons was used in this study to calculate integral linear energy transfer spectra and dose equivalents resulting from nuclear collisions of 1-GeV protons transversing bone and red bone marrow. In terms of dose equivalent averaged over trabecular bone marrow, target fragments emitted from interactions in both tissues are predicted to be at least as important as the direct ionization of the primary protons-twice as important, if recently recommended radiation weighting factors and "worst-case" geometry are used. The use of conventional dosimetry (absorbed dose weighted by aa linear energy transfer-dependent quality factor) as an appropriate framework for predicting risk from low fluences of high-linear energy transfer target fragments is discussed.

Measurements of charge distributions of the fragments in the low energy fission reaction

NASA Astrophysics Data System (ADS)

Wang, Taofeng; Han, Hongyin; Meng, Qinghua; Wang, Liming; Zhu, Liping; Xia, Haihong

2013-01-01

The measurement for charge distributions of fragments in spontaneous fission 252Cf has been performed by using a unique style of detector setup consisting of a typical grid ionization chamber and a ΔΕ-Ε particle telescope, in which a thin grid ionization chamber served as the ΔΕ-section and the E-section was an Au-Si surface barrier detector. The typical physical quantities of fragments, such as mass number and kinetic energies as well as the deposition in the gas ΔΕ detector and E detector were derived from the coincident measurement data. The charge distributions of the light fragments for the fixed mass number A2* and total kinetic energy (TKE) were obtained by the least-squares fits for the response functions of the ΔΕ detector with multi-Gaussian functions representing the different elements. The results of the charge distributions for some typical fragments are shown in this article which indicates that this detection setup has the charge distribution capability of Ζ:ΔΖ>40:1. The experimental method developed in this work for determining the charge distributions of fragments is expected to be employed in the neutron induced fissions of 232Th and 238U or other low energy fission reactions.

Insights into the Impact of Linker Flexibility and Fragment Ionization on the Design of CK2 Allosteric Inhibitors: Comparative Molecular Dynamics Simulation Studies.

PubMed

Zhou, Yue; Zhang, Na; Qi, Xiaoqian; Tang, Shan; Sun, Guohui; Zhao, Lijiao; Zhong, Rugang; Peng, Yongzhen

2018-01-01

Protein kinase is a novel therapeutic target for human diseases. The off-target and side effects of ATP-competitive inhibitors preclude them from the clinically relevant drugs. The compounds targeting the druggable allosteric sites outside the highly conversed ATP binding pocket have been identified as promising alternatives to overcome current barriers of ATP-competitive inhibitors. By simultaneously interacting with the αD region (new allosteric site) and sub-ATP binding pocket, the attractive compound CAM4066 was named as allosteric inhibitor of CK2α. It has been demonstrated that the rigid linker and non-ionizable substituted fragment resulted in significant decreased inhibitory activities of compounds. The molecular dynamics simulations and energy analysis revealed that the appropriate coupling between the linker and pharmacophore fragments were essential for binding of CAM4066 with CK2α. The lower flexible linker of compound 21 lost the capability of coupling fragments A and B to αD region and positive area, respectively, whereas the methyl benzoate of fragment B induced the re-orientated Pre-CAM4066 with the inappropriate polar interactions. Most importantly, the match between the optimized linker and pharmacophore fragments is the challenging work of fragment-linking based drug design. These results provide rational clues to further structural modification and development of highly potent allosteric inhibitors of CK2.

Insights into the Impact of Linker Flexibility and Fragment Ionization on the Design of CK2 Allosteric Inhibitors: Comparative Molecular Dynamics Simulation Studies

PubMed Central

Zhou, Yue; Zhang, Na; Qi, Xiaoqian; Tang, Shan; Zhao, Lijiao; Zhong, Rugang; Peng, Yongzhen

2018-01-01

Protein kinase is a novel therapeutic target for human diseases. The off-target and side effects of ATP-competitive inhibitors preclude them from the clinically relevant drugs. The compounds targeting the druggable allosteric sites outside the highly conversed ATP binding pocket have been identified as promising alternatives to overcome current barriers of ATP-competitive inhibitors. By simultaneously interacting with the αD region (new allosteric site) and sub-ATP binding pocket, the attractive compound CAM4066 was named as allosteric inhibitor of CK2α. It has been demonstrated that the rigid linker and non-ionizable substituted fragment resulted in significant decreased inhibitory activities of compounds. The molecular dynamics simulations and energy analysis revealed that the appropriate coupling between the linker and pharmacophore fragments were essential for binding of CAM4066 with CK2α. The lower flexible linker of compound 21 lost the capability of coupling fragments A and B to αD region and positive area, respectively, whereas the methyl benzoate of fragment B induced the re-orientated Pre-CAM4066 with the inappropriate polar interactions. Most importantly, the match between the optimized linker and pharmacophore fragments is the challenging work of fragment-linking based drug design. These results provide rational clues to further structural modification and development of highly potent allosteric inhibitors of CK2. PMID:29301250

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.

Differentiating chondroitin sulfate glycosaminoglycans using collision-induced dissociation; uronic acid cross-ring diagnostic fragments in a single stage of tandem mass spectrometry.

PubMed

Kailemia, Muchena J; Patel, Anish B; Johnson, Dane T; Li, Lingyun; Linhardt, Robert J; Amster, I Jonathan

2015-01-01

The stereochemistry of the hexuronic acid residues of the structure of glycosaminoglycans (GAGs) is a key feature that affects their interactions with proteins and other biological functions. Electron based tandem mass spectrometry methods, in particular electron detachment dissociation (EDD), have been able to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA) residues in some heparan sulfate tetrasaccharides by producing epimer-specific fragments. Similarly, the relative abundance of glycosidic fragment ions produced by collision-induced dissociation (CID) or EDD has been shown to correlate with the type of hexuronic acid present in chondroitin sulfate GAGs. The present work examines the effect of charge state and degree of sodium cationization on the CID fragmentation products that can be used to distinguish GlcA and IdoA containing chondroitin sulfate A and dermatan sulfate chains. The cross-ring fragments (2,4)A(n) and (0,2)X(n) formed within the hexuronic acid residues are highly preferential for chains containing GlcA, distinguishing it from IdoA. The diagnostic capability of the fragments requires the selection of a molecular ion and fragment ions with specific ionization characteristics, namely charge state and number of ionizable protons. The ions with the appropriate characteristics display diagnostic properties for all the chondroitin sulfate and dermatan sulfate chains (degree of polymerization of 4-10) studied.

Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry: Mechanistic Studies and Methods for Improving the Structural Identification of Carbohydrates

PubMed Central

Lai, Yin-Hung; Wang, Yi-Sheng

2017-01-01

Although matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is one of the most widely used soft ionization methods for biomolecules, the lack of detailed understanding of ionization mechanisms restricts its application in the analysis of carbohydrates. Structural identification of carbohydrates achieved by MALDI mass spectrometry helps us to gain insights into biological functions and pathogenesis of disease. In this review, we highlight mechanistic details of MALDI, including both ionization and desorption. Strategies to improve the ion yield of carbohydrates are also reviewed. Furthermore, commonly used fragmentation methods to identify the structure are discussed. PMID:28959517

Positive and negative ion mode comparison for the determination of DNA/peptide noncovalent binding sites through the formation of "three-body" noncovalent fragment ions.

PubMed

Brahim, Bessem; Tabet, Jean-Claude; Alves, Sandra

2018-02-01

Gas-phase fragmentation of single strand DNA-peptide noncovalent complexes is investigated in positive and negative electrospray ionization modes.Collision-induced dissociation experiments, performed on the positively charged noncovalent complex precursor ions, have confirmed the trend previously observed in negative ion mode, i.e. a high stability of noncovalent complexes containing very basic peptidic residues (i.e. R > K) and acidic nucleotide units (i.e. Thy units), certainly incoming from the existence of salt bridge interactions. Independent of the ion polarity, stable noncovalent complex precursor ions were found to dissociate preferentially through covalent bond cleavages of the partners without disrupting noncovalent interactions. The resulting DNA fragment ions were found to be still noncovalently linked to the peptides. Additionally, the losses of an internal nucleic fragment producing "three-body" noncovalent fragment ions were also observed in both ion polarities, demonstrating the spectacular salt bridge interaction stability. The identical fragmentation patterns (regardless of the relative fragment ion abundances) observed in both polarities have shown a common location of salt bridge interaction certainly preserved from solution. Nonetheless, most abundant noncovalent fragment ions (and particularly three-body ones) are observed from positively charged noncovalent complexes. Therefore, we assume that, independent of the preexisting salt bridge interaction and zwitterion structures, multiple covalent bond cleavages from single-stranded DNA/peptide complexes rely on an excess of positive charges in both electrospray ionization ion polarities.

The fragmentation of 510 MeV/nucleon iron-56 in polyethylene. I. Fragment fluence spectra

NASA Technical Reports Server (NTRS)

Zeitlin, C.; Miller, J.; Heilbronn, L.; Frankel, K.; Gong, W.; Schimmerling, W.

1996-01-01

The fragmentation of 510 MeV/nucleon iron ions in several thicknesses of polyethylene has been measured. Non-interacting primary beam particles and fragments have been identified and their LETs calculated by measuring ionization energy loss in a stack of silicon detectors. Fluences, normalized to the incident beam intensity and corrected for detector effects, are presented for each fragment charge and target. Histograms of fluence as a function of LET are also presented. Some implications of these data for measurements of the biological effects of heavy ions are discussed.

Pretreatment of low dose radiation reduces radiation-induced apoptosis in mouse lymphoma (EL4) cells.

PubMed

Kim, J H; Hyun, S J; Yoon, M Y; Ji, Y H; Cho, C K; Yoo, S Y

1997-06-01

Induction of an adaptive response to ionizing radiation in mouse lymphoma (EL4) cells was studied by using cell survival fraction and apoptotic nucleosomal DNA fragmentation as biological end points. Cells in early log phase were pre-exposed to low dose of gamma-rays (0.01 Gy) 4 or 20 hrs prior to high dose gamma-ray (4, 8 and 12 Gy for cell survival fraction analysis; 8 Gy for DNA fragmentation analysis) irradiation. Then cell survival fractions and the extent of DNA fragmentation were measured. Significant adaptive response, increase in cell survival fraction and decrease in the extent of DNA fragmentation were induced when low and high dose gamma-ray irradiation time interval was 4 hr. Addition of protein or RNA synthesis inhibitor, cycloheximide or 5,6-dichloro-1-beta-d-ribofuranosylbenzimidazole (DRFB), respectively during adaptation period, the period from low dose gamma-ray irradiation to high dose gamma-ray irradiation, was able to inhibit the induction of adaptive response, which is the reduction of the extent DNA fragmentation in irradiated EL4 cells. These data suggest that the induction of adaptive response to ionizing radiation in EL4 cells required both protein and RNA synthesis.

Fragmentation study of iridoid glycosides including epimers by liquid chromatography-diode array detection/electrospray ionization mass spectrometry and its application in metabolic fingerprint analysis of Gardenia jasminoides Ellis.

PubMed

Zhou, Tingting; Liu, Hua; Wen, Jun; Fan, Guorong; Chai, Yifeng; Wu, Yutian

2010-09-15

A high-performance liquid chromatography-diode array detection/electrospray ionization mass spectrometry (HPLC-DAD/ESI-MS) method was applied to the characterization of ten iridoid glycosides in Gardenia jasminoides Ellis, a traditional Chinese medicine. During the process of structural elucidation, two groups of isomers including two epimers were structurally characterized and differentiated according to their distinctive fragmentation patterns which were closely related to their isomeric differentiations. Subsequently, the major compounds were purified by multi-dimensional chromatography and semi-preparative HPLC and the structure identification was confirmed with NMR techniques. The major fragmentation pathways of iridoid glycosides in Gardenia jasminoides Ellis obtained through the MS data were schemed systematically, which provided the best sensitivity and specificity for characterization of the iridoid glycosides especially the isomers so far. Based on the fragmentation patterns of iridoid glycosides concluded, seven major iridoid glycosides were characterized in rat plasma after intravenous administration of Gardenia jasminoides Ellis. Copyright 2010 John Wiley & Sons, Ltd.

Top-down proteomic identification of Shiga toxin 2 subtypes from Shiga toxin-producing Escherichia coli by matrix-assisted laser desorption ionization-tandem time of flight mass spectrometry.

PubMed

Fagerquist, Clifton K; Zaragoza, William J; Sultan, Omar; Woo, Nathan; Quiñones, Beatriz; Cooley, Michael B; Mandrell, Robert E

2014-05-01

We have analyzed 26 Shiga toxin-producing Escherichia coli (STEC) strains for Shiga toxin 2 (Stx2) production using matrix-assisted laser desorption ionization (MALDI)-tandem time of flight (TOF-TOF) tandem mass spectrometry (MS/MS) and top-down proteomic analysis. STEC strains were induced to overexpress Stx2 by overnight culturing on solid agar supplemented with either ciprofloxacin or mitomycin C. Harvested cells were lysed by bead beating, and unfractionated bacterial cell lysates were ionized by MALDI. The A2 fragment of the A subunit and the mature B subunit of Stx2 were analyzed by MS/MS. Sequence-specific fragment ions were used to identify amino acid subtypes of Stx2 using top-down proteomic analysis using software developed in-house at the U.S. Department of Agriculture (USDA). Stx2 subtypes (a, c, d, f, and g) were identified on the basis of the mass of the A2 fragment and the B subunit as well as from their sequence-specific fragment ions by MS/MS (postsource decay). Top-down proteomic identification was in agreement with DNA sequencing of the full Stx2 operon (stx2) for all strains. Top-down results were also compared to a bioassay using a Vero-d2EGFP cell line. Our results suggest that top-down proteomic identification is a rapid, highly specific technique for distinguishing Stx2 subtypes.

Integrated quantification and identification of aldehydes and ketones in biological samples.

PubMed

Siegel, David; Meinema, Anne C; Permentier, Hjalmar; Hopfgartner, Gérard; Bischoff, Rainer

2014-05-20

The identification of unknown compounds remains to be a bottleneck of mass spectrometry (MS)-based metabolomics screening experiments. Here, we present a novel approach which facilitates the identification and quantification of analytes containing aldehyde and ketone groups in biological samples by adding chemical information to MS data. Our strategy is based on rapid autosampler-in-needle-derivatization with p-toluenesulfonylhydrazine (TSH). The resulting TSH-hydrazones are separated by ultrahigh-performance liquid chromatography (UHPLC) and detected by electrospray ionization-quadrupole-time-of-flight (ESI-QqTOF) mass spectrometry using a SWATH (Sequential Window Acquisition of all Theoretical Fragment-Ion Spectra) data-independent high-resolution mass spectrometry (HR-MS) approach. Derivatization makes small, poorly ionizable or retained analytes amenable to reversed phase chromatography and electrospray ionization in both polarities. Negatively charged TSH-hydrazone ions furthermore show a simple and predictable fragmentation pattern upon collision induced dissociation, which enables the chemo-selective screening for unknown aldehydes and ketones via a signature fragment ion (m/z 155.0172). By means of SWATH, targeted and nontargeted application scenarios of the suggested derivatization route are enabled in the frame of a single UHPLC-ESI-QqTOF-HR-MS workflow. The method's ability to simultaneously quantify and identify molecules containing aldehyde and ketone groups is demonstrated using 61 target analytes from various compound classes and a (13)C labeled yeast matrix. The identification of unknowns in biological samples is detailed using the example of indole-3-acetaldehyde.

Induced in-source fragmentation pattern of certain novel (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides by electrospray mass spectrometry (ESI-MS/MS)

PubMed Central

2013-01-01

Background Collision induced dissociation (CID) in the triple quadrupole mass spectrometer system (QQQ) typically yields more abundant fragment ions than those produced with resonance excitation in the presence of helium gas in the ion trap mass spectrometer system (IT). Detailed product ion spectra can be obtained from one stage MS2 scan using the QQQ. In contrast, generating the same number of fragment ions in the ion trap requires multiple stages of fragmentation (MSn) using CID via in-trap resonance excitation with the associated time penalties and drop in sensitivity. Results The use of in-source fragmentation with electrospray ionization (ESI) followed by product ion scan (MS2) in a triple quadrupole mass spectrometer system, was demonstrated. This process enhances the qualitative power of tandem mass spectrometry to simulate the MS3 of ion trap for a comprehensive study of fragmentation mechanisms. A five pharmacologically significant (1Z, 2E)-N-arylpropanehydrazonoyl chlorides (3a-e) were chosen as model compounds for this study. In this work, detailed fragmentation pathways were elucidated by further dissociation of each fragment ion in the ion spectrum, essentially, by incorporating fragmentor voltage induced dissociation (in-source fragmentation) and isolation of fragments in a quadrupole cell Q1. Subsequently, CID occurs in cell, Q2, and fragment ions are analyzed in Q3 operated in product ion mode this process can be referred to as pseudo-MS3 scan mode. Conclusions This approach allowed unambiguous assignment of all fragment ions using tandem mass spectrometer and provided adequate sensitivity and selectivity. It is beneficial for structure determination of unknown trace components. The data presented in this paper provide useful information on the effect of different substituents on the ionization/fragmentation processes and can be used in the characterization of this important class of compounds. PMID:23351484

Enhanced signal generation for use in the analysis of synthetic pyrethroids using chemical ionization tandem quadrupole ion trap mass spectrometry.

PubMed

Sichilongo, Kwenga

2004-12-01

Synthetic pyrethroids fragment extensively under electron ionization (EI) conditions to give low mass ions, most of them with the same m/z ratios. This fragmentation is primarily due to the labile ester linkage found in these compounds. In this research we established the best gas chromatography (GC) conditions in the EI mode that served as a benchmark in the development of a chemical ionization (CI) protocol for ten selected synthetic pyrethroids. Based on proton affinity data, several reagent gases were evaluated in the positive CI ionization mode. Methanol was found to produce higher average ion counts relative to the other gases evaluated, which led to the development of an optimized method consisting of selective ejection chemical ionization (SECI) and MS/MS. Standard stainless steel ion trap electrodes produced significant degradation of chromatographic performance on late eluting compounds, which was attributed to electrode surface chemistry. A dramatic improvement in signal-to-noise (S/N) ratios was observed when the chromatographically inert Silcosteel coated electrodes were used. The resulting method, that has significant S/N ratio improvements resulting from a combination of septum programmable injections (SPI), optimized CI and inert Silcosteel-coated electrodes, was used to determine instrument detection limits.

Creation of Artificial Ionospheric Layers Using High-Power HF Waves

DTIC Science & Technology

2010-01-30

Program ( HAARP ) transmitter in Gakona, Alaska. The HF- driven ionization process is initiated near the 2nd electron gyroharmonic at 220 km altitude in...the 3.6 MW High-Frequency Active Auroral Program ( HAARP ) transmitter in Gakona, Alaska. The HF-driven ionization process is initiated near the 2nd...Maine. USA. Copyright 2010 by the American Geophysical Union. 0094-8276/I0/2009GLO41895SO5.0O Research Program ( HAARP ) transmitter facility, however

Large-scale metabolite analysis of standards and human serum by laser desorption ionization mass spectrometry from silicon nanopost arrays

DOE PAGES

Korte, Andrew R.; Stopka, Sylwia A.; Morris, Nicholas; ...

2016-07-11

The unique challenges presented by metabolomics have driven the development of new mass spectrometry (MS)-based techniques for small molecule analysis. We have previously demonstrated silicon nanopost arrays (NAPA) to be an effective substrate for laser desorption ionization (LDI) of small molecules for MS. However, the utility of NAPA-LDI-MS for a wide range of metabolite classes has not been investigated. Here we apply NAPA-LDI-MS to the large-scale acquisition of high-resolution mass spectra and tandem mass spectra from a collection of metabolite standards covering a range of compound classes including amino acids, nucleotides, carbohydrates, xenobiotics, lipids, and other classes. In untargeted analysismore » of metabolite standard mixtures, detection was achieved for 374 compounds and useful MS/MS spectra were obtained for 287 compounds, without individual optimization of ionization or fragmentation conditions. Metabolite detection was evaluated in the context of 31 metabolic pathways, and NAPA-LDI-MS was found to provide detection for 63% of investigated pathway metabolites. Individual, targeted analysis of the 20 common amino acids provided detection of 100% of the investigated compounds, demonstrating that improved coverage is possible through optimization and targeting of individual analytes or analyte classes. In direct analysis of aqueous and organic extracts from human serum samples, spectral features were assigned to a total of 108 small metabolites and lipids. Glucose and amino acids were quantitated within their physiological concentration ranges. Finally, the broad coverage demonstrated by this large-scale screening experiment opens the door for use of NAPA-LDI-MS in numerous metabolite analysis applications« less

Large-scale metabolite analysis of standards and human serum by laser desorption ionization mass spectrometry from silicon nanopost arrays

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

Korte, Andrew R.; Stopka, Sylwia A.; Morris, Nicholas

The unique challenges presented by metabolomics have driven the development of new mass spectrometry (MS)-based techniques for small molecule analysis. We have previously demonstrated silicon nanopost arrays (NAPA) to be an effective substrate for laser desorption ionization (LDI) of small molecules for MS. However, the utility of NAPA-LDI-MS for a wide range of metabolite classes has not been investigated. Here we apply NAPA-LDI-MS to the large-scale acquisition of high-resolution mass spectra and tandem mass spectra from a collection of metabolite standards covering a range of compound classes including amino acids, nucleotides, carbohydrates, xenobiotics, lipids, and other classes. In untargeted analysismore » of metabolite standard mixtures, detection was achieved for 374 compounds and useful MS/MS spectra were obtained for 287 compounds, without individual optimization of ionization or fragmentation conditions. Metabolite detection was evaluated in the context of 31 metabolic pathways, and NAPA-LDI-MS was found to provide detection for 63% of investigated pathway metabolites. Individual, targeted analysis of the 20 common amino acids provided detection of 100% of the investigated compounds, demonstrating that improved coverage is possible through optimization and targeting of individual analytes or analyte classes. In direct analysis of aqueous and organic extracts from human serum samples, spectral features were assigned to a total of 108 small metabolites and lipids. Glucose and amino acids were quantitated within their physiological concentration ranges. Finally, the broad coverage demonstrated by this large-scale screening experiment opens the door for use of NAPA-LDI-MS in numerous metabolite analysis applications« less

Negative electrospray ionization mass spectrometry: a method for sequencing and determining linkage position in oligosaccharides from branched hemicelluloses.

PubMed

Quéméner, Bernard; Vigouroux, Jacqueline; Rathahao, Estelle; Tabet, Jean Claude; Dimitrijevic, Aleksandra; Lahaye, Marc

2015-01-01

Xyloglucans of apple, tomato, bilberry and tamarind were hydrolyzed by commercial endo β-1-4-D-endoglucanase. The xylo-gluco-oligosaccharides (XylGos) released were separated on CarboPac PA 200 column in less than 15 min, and, after purification, they were structurally characterized by negative electrospray ionization mass spectrometry using a quadrupole time-of-flight (ESI-Q-TOF), a hybrid linear ion trap (LTQ)/Orbitrap and a hybrid quadrupole Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers. In order to corroborate the fragmentation routes observed on XylGos, some commercial galacto-manno-oligosaccharides (GalMOs) and glucurono-xylo-oligosaccharides were also studied. The fragmentation pathways of the ionized GalMos were similar to those of XylGos ones. The product ion spectra were mainly characterized by prominent double cleavage (D) ions corresponding to the entire inner side chains. The directed fragmentation from the reducing end to the other end was observed for the main glycosylated backbone but also for the side-chains, allowing their complete sequencing. Relevant cross-ring cleavage ions from (0,2)X(j)-type revealed to be diagnostic of the 1-2-linked- glycosyl units from XylGos together with the 1-2-linked glucuronic acid unit from glucuronoxylans. Resonant activation in the LTQ Orbitrap allowed not only determining the type of all linkages but also the O-acetyl group location on fucosylated side-chains. Moreover, the fragmentation of the different side chains using the MS(n) capabilities of the LTQ/Orbitrap analyzer also allowed differentiating terminal arabinosyl and xylosyl substituents inside S and U side-chains of XylGos, respectively. The CID spectra obtained were very informative for distinction of isomeric structures differing only in their substitution pattern. These features together makes the fragmentation in negative ionization mode a relevant and powerful technique useful to highlight the subtle structural changes generally observed during the development of plant organs such as during fruit ripening and for the screening of cell wall mutants with altered hemicellulose structure. Copyright © 2015 John Wiley & Sons, Ltd.

Interaction of excited He and Ne rare gas metastable atoms with the CHF2Cl molecule

NASA Astrophysics Data System (ADS)

Chérid, M.; Ben Arfa, M.; Driss Khodja, M.

2005-06-01

We studied the Penning ionization of the CHF2Cl molecule with He and Ne metastable atoms (He* and Ne*). We measured the electron kinetic energy and the time-of-flight mass spectra; we also determined the branching ratio for the parent ion and charged CHF+2, CHFCl+, HCF+/CF+ and Cl+ fragments. These data led us to discuss the dissociation channels for all the energetically-accessible electronic states of the ionized molecule. We evidenced a marked contrast in the fragment ion proportions for Ne*-CHF2Cl and He*-CHF2Cl systems, and related it to the difference in polarizability and internal energy of the He* and Ne* atoms.

Electrospray ionization tandem mass spectrometry differentiation of N-phosphoryl-[alpha]-, [beta]- and [gamma]-amino acids

NASA Astrophysics Data System (ADS)

Qiang, Liming; Cao, Shuxia; Zhao, Xiaoyang; Mao, Xiangju; Guo, Yanchun; Liao, Xincheng; Zhao, Yufen

2007-10-01

The fragmentation patterns of N-diisopropyloxyphosphoryl-l-[alpha]-Ala (DIPP-l-[alpha]-Ala), N-diisopropyloxyphosphoryl-d-[alpha]-Ala (DIPP-d-[alpha]-Ala), N-diisopropyloxyphosphoryl-[beta]-Ala (DIPP-[beta]-Ala) and N-diisopropyloxyphosphoryl-[gamma]-amino butyric acid (DIPP-[gamma]-Aba) were investigated by electrospray ionization tandem mass spectrometry (ESI-MS/MS). DIPP-d-[alpha]-Ala showed the same fragmentation pathways as DIPP-l-[alpha]-Ala. In the fragmentation of protonated DIPP-[beta]-Ala, the characteristic fragment ion [M + H - 2C3H6 - H2O - CH2CO]+ appeared and could be used to distinguish [beta]-Ala from l-[alpha]-Ala and d-[alpha]-Ala through tandem mass spectra, even though they possess the same molecular weight. In the fragmentation of protonated DIPP-[gamma]-Aba, the break of PN bond occurred and an interesting protonated lactam ion with five-membered ring was generated. Furthermore, in the MS3 spectrum of [M + Na - 2C3H6]+ ion of DIPP-[gamma]-Aba, a strong intensity of unique fragment ion, namely lactam-sodium adduct with five-membered ring, was observed, which could be considered as a mark for [gamma]-amino acids. The stepwise fragmentations of their [M + Na]+ ions and [M - H]- ions showed that they all underwent a PN to PO bond migration through a five-membered or six-membered or even seven-membered ring transition state, respectively, which supported the great affinity of hydroxyl for phosphoryl group.

Re-investigation of the fragmentation of protonated carotenoids by electrospray ionization and nanospray tandem mass spectrometry.

PubMed

Neto, Fausto Carnevale; Guaratini, Thais; Costa-Lotufo, Letícia; Colepicolo, Pio; Gates, Paul J; Lopes, Norberto Peporine

2016-07-15

Carotenoids are polyene isoprenoids with an important role in photosynthesis and photoprotection. Their characterization in biological matrices is a crucial subject for biochemical research. In this work we report the full fragmentation of 16 polyenes (carotenes and xanthophylls) by electrospray ionization tandem mass spectrometry (ESI-CID-MS/MS) and nanospray tandem mass spectrometry (nanoESI-CID-MS/MS). Analyses were carried out on a quadrupole time-of-flight (QTOF) mass spectrometer coupled with a nanoESI source and on a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer with an ESI source. The formulae of the product ions were determined by accurate-mass measurements. It is demonstrated that the fragmentation routes observed for the protonated carotenoids derive essentially from charge-remote fragmentations and pericyclic rearrangements, such as electrocyclic and retro-ene eliminations (assisted or not by a sigmatropic hydrogen shift). All mechanisms are dependent on cis-trans isomerization through the formation of several conjugated polyene carbocation intermediates. Some specific ions for the carotenoid epoxides were justified through formation of cyclic oxonium ions. Complete fragmentation pathways of protonated carotenoids by ESI- and nanoESI-CID-MS/MS provided structural information about functional groups, polyene chain and double bonds, and contribute to identification of carotenoids based on MS/MS fragmentation patterns. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Study of transport of laser-driven relativistic electrons in solid materials

NASA Astrophysics Data System (ADS)

Leblanc, Philippe

With the ultra intense lasers available today, it is possible to generate very hot electron beams in solid density materials. These intense laser-matter interactions result in many applications which include the generation of ultrashort secondary sources of particles and radiation such as ions, neutrons, positrons, x-rays, or even laser-driven hadron therapy. For these applications to become reality, a comprehensive understanding of laser-driven energy transport including hot electron generation through the various mechanisms of ionization, and their subsequent transport in solid density media is required. This study will focus on the characterization of electron transport effects in solid density targets using the state-of- the-art particle-in-cell code PICLS. A number of simulation results will be presented on the topics of ionization propagation in insulator glass targets, non-equilibrium ionization modeling featuring electron impact ionization, and electron beam guiding by the self-generated resistive magnetic field. An empirically derived scaling relation for the resistive magnetic in terms of the laser parameters and material properties is presented and used to derive a guiding condition. This condition may prove useful for the design of future laser-matter interaction experiments.

Demonstration of Laser Induced Acoustic Desoprtion - Chemical Ionization Mass Spectrometry (LIAD-CIMS) for Fragment-Free Measurements of Organic Aerosol Molecular Composition

NASA Astrophysics Data System (ADS)

Browne, E. C.; Abdelhamid, A.; Berry, J.; Alton, M.

2017-12-01

Organic compounds account for a significant portion of fine atmospheric aerosol. Current analytical techniques have provided insights on organic aerosol (OA) sources, composition, and chemical modification pathways. Despite this knowledge, large uncertainties remain and hinder our understanding of aerosol impacts on climate, air quality, and health. Measuring OA composition is challenging due to the complex chemical composition and the wide variation in the properties (e.g., vapor pressure, solubility, reactivity) of organic compounds. In many current measurement techniques, the ability to chemically resolve and quantify OA components is complicated by molecular decomposition, matrix effects, and/or preferential ionization mechanisms. Here, we utilize a novel desorption technique, laser induced acoustic desorption (LIAD), that generates fragment-free, neutral gas-phase molecules. We couple LIAD with a high-resolution chemical ionization mass spectrometer (CIMS) to provide molecular composition OA measurements. Through a series of laboratory experiments, we demonstrate the ability of this technique to measure large, thermally labile species without fragmentation/thermal decomposition. We discuss quantification and detection limits of this technique. We compare LIAD-CIMS measurements with thermal desorption-CIMS measurements using off-line measurements of ambient aerosol collected in Boulder, CO. Lastly, we discuss future development for on-line measurements of OA using LIAD-CIMS.

Laser-driven acceleration of electrons in a partially ionized plasma channel.

PubMed

Rowlands-Rees, T P; Kamperidis, C; Kneip, S; Gonsalves, A J; Mangles, S P D; Gallacher, J G; Brunetti, E; Ibbotson, T; Murphy, C D; Foster, P S; Streeter, M J V; Budde, F; Norreys, P A; Jaroszynski, D A; Krushelnick, K; Najmudin, Z; Hooker, S M

2008-03-14

The generation of quasimonoenergetic electron beams, with energies up to 200 MeV, by a laser-plasma accelerator driven in a hydrogen-filled capillary discharge waveguide is investigated. Injection and acceleration of electrons is found to depend sensitively on the delay between the onset of the discharge current and the arrival of the laser pulse. A comparison of spectroscopic and interferometric measurements suggests that injection is assisted by laser ionization of atoms or ions within the channel.

Photoionization and Photofragmentation of Carbon Fullerene Molecular Ions

NASA Astrophysics Data System (ADS)

Baral, Kiran Kumar

Cross sections are reported for single and double photoionization accompanied by the loss of as many as seven pairs of C atoms of C60 + and C70+ fullerene molecular ions in the photon energy range 18 eV to 150 eV. These measurements were performed at the Advanced Light Source (ALS) by merging a mass-selected ion beam with a beam of monochromatized synchrotron radiation. Threshold energies were determined for the formation of doubly and triply charged fragment ions from parent ions C60+ and C70+. The energy dependences of cross-sections for direct photoionization yielding C60 2+ and C702+ are compared with those for forming different doubly and triply charged fullerene fragment ions. Two-dimensional product ion scans were measured and quantified at four discrete photon energies: 35 eV, 65 eV, 105 eV and 140 eV, in the vacuum ultraviolet region, providing a comprehensive mapping of the product channels involving single ionization of fullerene ions C60+ and C 70+ accompanied by fragmentation. Since fullerenes are composed of even numbers of carbon atoms, the fragmentation occurs by the loss of differing numbers of carbon atom pairs. In addition to pure ionization, fragmentation product channels become relatively more important at higher photon energies.

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source

NASA Astrophysics Data System (ADS)

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H]+ was observed in the case of individual alkanes (C5-C19) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. [Figure not available: see fulltext.

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source.

PubMed

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H] + was observed in the case of individual alkanes (C 5 -C 19 ) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. Graphical Abstract ᅟ.

Tandem mass spectrometry of coprogen and deferoxamine hydroxamic siderophores.

PubMed

Simionato, Ana V C; de Souza, Gezimar D; Rodrigues-Filho, Edson; Glick, James; Vouros, Paul; Carrilho, Emanuel

2006-01-01

Mechanisms of fragmentation of hydroxamic siderophores are proposed comparing deuterated and nondeuterated samples. Standard siderophores (e.g. deferoxamine and coprogen) were directly injected into both ion trap and linear quadrupole mass spectrometers with electrospray ionization (ESI). Four and two fragmentation steps were carried out for deferoxamine and coprogen (analyzed by positive and negative ESI, respectively). Deferoxamine cleavages occurred in both peptide and hydroxamic bonds while the coprogen fragmentation pattern is more elaborate, since it contains Fe(III) in its structure.

Differentiation of isomeric 2-aryldimethyltetrahydro-5-quinolinones by electron ionization and electrospray ionization mass spectrometry.

PubMed

Kumar, Ch Dinesh; Chary, V Naresh; Dinesh, A; Reddy, P S; Srinivas, K; Gayatri, G; Sastry, G N; Prabhakar, S

2011-10-15

A series of isomeric 2-aryl-6,6-dimethyltetrahydro-5-quinolinones (set I) and 2-aryl-7,7-dimethyltetrahydro-5-quinolinones (set II) were studied under positive ion electron ionization (EI) and electrospray ionization (ESI) techniques. Under EI conditions, the molecular ions were found to be less stable in set I isomers, and they resulted in abundant fragment ions, i.e., [M-CH(3)](+), [M-CO](+.), [M-HCO](+), [M-(CH(3),CO)](+), and [M-(CH(3),CH(2)O)](+), when compared with set II isomers. In addition, the set I isomers showed specific fragment ions corresponding to [M-OH](+) and [M-OCH(3)](+). The retro-Diels-Alder (RDA) product ion was always higher in set II isomers. The ESI mass spectra produced [M + H](+) ions, and their decomposition showed favorable loss of CH(3) radical, CH(4) and C(2)H(6) molecules in set I isomers. The set II isomers, however, showed predominant RDA product ions, and specific loss of H(2)O. The selectivity in EI and ESI was attributed to the instability of set I isomers by the presence of a gem-dimethyl group at the α-position, and it was supported by the data from model compounds without a gem-dimethyl group. Density functional theory (DFT) calculations successfully corroborated the fragmentation pathways for diagnostic ions. This study revealed the effect of a gem-dimethyl group located at the α-position to the carbonyl having aromatic/unsaturated carbon on the other side of the carbonyl group. Copyright © 2011 John Wiley & Sons, Ltd.

Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.

PubMed

Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin

2015-02-01

We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright © 2015 John Wiley & Sons, Ltd.

Resonance-assisted decay of nondispersive wave packets.

PubMed

Wimberger, Sandro; Schlagheck, Peter; Eltschka, Christopher; Buchleitner, Andreas

2006-07-28

We present a quantitative semiclassical theory for the decay of nondispersive electronic wave packets in driven, ionizing Rydberg systems. Statistically robust quantities are extracted combining resonance-assisted tunneling with subsequent transport across chaotic phase space and a final ionization step.

Battery-Powered RF Pre-Ionization System for the Caltech Magnetohydrodynamically-Driven Jet Experiment: RF Discharge Properties and MHD-Driven Jet Dynamics

NASA Astrophysics Data System (ADS)

Chaplin, Vernon H.

This thesis describes investigations of two classes of laboratory plasmas with rather different properties: partially ionized low pressure radiofrequency (RF) discharges, and fully ionized high density magnetohydrodynamically (MHD)-driven jets. An RF pre-ionization system was developed to enable neutral gas breakdown at lower pressures and create hotter, faster jets in the Caltech MHD-Driven Jet Experiment. The RF plasma source used a custom pulsed 3 kW 13.56 MHz RF power amplifier that was powered by AA batteries, allowing it to safely float at 4-6 kV with the cathode of the jet experiment. The argon RF discharge equilibrium and transport properties were analyzed, and novel jet dynamics were observed. Although the RF plasma source was conceived as a wave-heated helicon source, scaling measurements and numerical modeling showed that inductive coupling was the dominant energy input mechanism. A one-dimensional time-dependent fluid model was developed to quantitatively explain the expansion of the pre-ionized plasma into the jet experiment chamber. The plasma transitioned from an ionizing phase with depressed neutral emission to a recombining phase with enhanced emission during the course of the experiment, causing fast camera images to be a poor indicator of the density distribution. Under certain conditions, the total visible and infrared brightness and the downstream ion density both increased after the RF power was turned off. The time-dependent emission patterns were used for an indirect measurement of the neutral gas pressure. The low-mass jets formed with the aid of the pre-ionization system were extremely narrow and collimated near the electrodes, with peak density exceeding that of jets created without pre-ionization. The initial neutral gas distribution prior to plasma breakdown was found to be critical in determining the ultimate jet structure. The visible radius of the dense central jet column was several times narrower than the axial current channel radius, suggesting that the outer portion of the jet must have been force free, with the current parallel to the magnetic field. The studies of non-equilibrium flows and plasma self-organization being carried out at Caltech are relevant to astrophysical jets and fusion energy research.

Cross sections for direct and dissociative ionization of NH3 and CS2 by electron impact

NASA Technical Reports Server (NTRS)

Rao, M. V. V. S.; Srivastava, S. K.

1991-01-01

A crossed electron beam-molecular beam collision geometry is used to measure cross sections for the production of positive ions by electron impact on NH3 and CS2. Ionization cross-section data for NH3 and the values of various cross sections are presented, as well as ionization efficiency curves for CS2. Considerable differences are found between the various results on NH3. The present values are close to the data of Djuric et al. (1981). The semiempirical calculations of Hare and Meath (1987) differ considerably in the absolute values of cross sections. Discrepancies were observed in comparisons of cross sections of other fragment ions resulting from the ionization and dissociate ionization of NH3.

Scaling Relations of Starburst-driven Galactic Winds

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

Tanner, Ryan; Cecil, Gerald; Heitsch, Fabian, E-mail: rytanner@augusta.edu

2017-07-10

Using synthetic absorption lines generated from 3D hydrodynamical simulations, we explore how the velocity of a starburst-driven galactic wind correlates with the star formation rate (SFR) and SFR density. We find strong correlations for neutral and low ionized gas, but no correlation for highly ionized gas. The correlations for neutral and low ionized gas only hold for SFRs below a critical limit set by the mass loading of the starburst, above which point the scaling relations flatten abruptly. Below this point the scaling relations depend on the temperature regime being probed by the absorption line, not on the mass loading.more » The exact scaling relation depends on whether the maximum or mean velocity of the absorption line is used. We find that the outflow velocity of neutral gas can be up to five times lower than the average velocity of ionized gas, with the velocity difference increasing for higher ionization states. Furthermore, the velocity difference depends on both the SFR and mass loading of the starburst. Thus, absorption lines of neutral or low ionized gas cannot easily be used as a proxy for the outflow velocity of the hot gas.« less

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

NASA Astrophysics Data System (ADS)

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

2012-11-01

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

Fragmentation dynamics of ionized neon trimer inside helium nanodroplets: a theoretical study.

PubMed

Bonhommeau, David; Viel, Alexandra; Halberstadt, Nadine

2004-06-22

We report a theoretical study of the fragmentation dynamics of Ne(3) (+) inside helium nanodroplets, following vertical ionization of the neutral neon trimer. The motion of the neon atoms is treated classically, while transitions between the electronic states of the ionic cluster are treated quantum mechanically. A diatomics-in-molecules description of the potential energy surfaces is used, in a minimal basis set consisting of three effective p orbitals on each neon atom for the missing electron. The helium environment is modeled by a friction force acting on the neon atoms when their speed exceeds the Landau velocity. A reasonable range of values for the corresponding friction coefficient is obtained by comparison with existing experimental measurements. (c) 2004 American Institute of Physics.

Structural characterization of trace stilbene glycosides in Lysidice brevicalyx Wei using liquid chromatography/diode-array detection/electrospray ionization tandem mass spectrometry.

PubMed

Hu, Youcai; Qu, Jing; Liu, Yuanyan; Yu, Shishan; Li, Jianbei; Zhang, Jinlan; Du, Dan

2010-01-01

The mass fragmentation patterns of stilbene glycosides isolated from the genus Lysidice were investigated by negative ion electrospray ionization tandem mass spectrometry, and the influence of collision energy on their fragmentation behavior is discussed. It is found that the presence of the Y(0)(-) and B(0)(-) ions in the MS(2) spectra is characteristic for 1-->6 linked diglycosyl stilbenes, while the Y(0)(-), Y(1)(-), and Z(1)(-) ions are representative ions of 1-->2 linked diglycosyl stilbenes. These results indicate that ESI-MS(n) in the negative ion mode can be used to differentiate 1-->6 and 1-->2 linked diglycosyl stilbenes. Based on the fragmentation rules, 9 new trace constituents were identified or tentatively characterized in a fraction of Lysidice brevicalyx by using HPLC/HRMS and HPLC-DAD/ESI-MS(n). The results of the present study can assist in on-line structural identification of analogous constituents and targeted isolation of novel compounds from crude plant extracts.

Avoiding Misannotation of In-Source Fragmentation Products as Cellular Metabolites in Liquid Chromatography–Mass Spectrometry-Based Metabolomics

DOE PAGES

Xu, Yi-Fan; Lu, Wenyun; Rabinowitz, Joshua D.

2015-01-15

Liquid chromatography–mass spectrometry (LC-MS) technology allows for rapid quantitation of cellular metabolites, with metabolites identified by mass spectrometry and chromatographic retention time. Recently, with the development of rapid scanning high-resolution high accuracy mass spectrometers and the desire for high throughput screening, minimal or no chromatographic separation has become increasingly popular. Furthermore, when analyzing complex cellular extracts, however, the lack of chromatographic separation could potentially result in misannotation of structurally related metabolites. Here, we show that, even using electrospray ionization, a soft ionization method, in-source fragmentation generates unwanted byproducts of identical mass to common metabolites. For example, nucleotide-triphosphates generate nucleotide-diphosphates, andmore » hexose-phosphates generate triose-phosphates. We also evaluated yeast intracellular metabolite extracts and found more than 20 cases of in-source fragments that mimic common metabolites. Finally and accordingly, chromatographic separation is required for accurate quantitation of many common cellular metabolites.« less

Laser mass spectrometry of chemical warfare agents using ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Weickhardt, C.; Grun, C.; Grotemeyer, J.

1998-12-01

Fast relaxation processes in excited molecules such as IC, ISC, and fragmentation are observed in many environmentally and technically relevant substances. They cause severe problems to resonance ionization mass spectrometry because they reduce the ionization yield and lead to mass spectra which do not allow the identification of the compound. By the use of ultrashort laser pulses these problems can be overcome and the advantages of REMPI over conventional ionization techniques in mass spectrometry can be regained. This is demonstrated using soil samples contaminated with a chemical warfare agent.

Very low-molecular-mass fragments of albumin in the plasma of patients with focal segmental glomerulosclerosis.

PubMed

Hellin, Joan Lopez; Bech-Serra, Joan J; Moctezuma, Enrique Lara; Chocron, Sara; Santin, Sheila; Madrid, Alvaro; Vilalta, Ramon; Canals, Francesc; Torra, Roser; Meseguer, Anna; Nieto, Jose L

2009-11-01

Primary focal segmental glomerulosclerosis (FSGS) is a glomerular disease that frequently does not respond to treatment and progresses to kidney failure. FSGS can be of either genetic origin, caused by mutations in slit diaphragm proteins, such as podocin, or idiopathic origin of unknown cause. Case series. Children with FSGS (aged 3-18 years); 15 with idiopathic and 11 with genetic forms of FSGS. Genetic versus idiopathic forms. Differentially expressed proteins in the plasma proteome, detected using 2-dimensional electrophoresis and identified using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, Western blot, and liquid chromatography electron spray ionization tandem mass spectrometry for fragmentation and identification of the peptides. We found 3 very low-molecular-mass (9.2, 6.9, and 4.7 kDa; isoelectric point, 5.7) spots that were present in pooled samples from patients with genetic FSGS, but missing in patients with idiopathic FSGS and healthy individuals. Spots were identified using mass spectrometry as fragments of albumin, 2 of them apparently containing peptides from both C- and N-terminal parts of the whole protein. Proteomic analyses were carried out on all genetic patients individually; of these, 10 of 11 patients had > or =1 albumin fragment detected in the pool. We did not find an evident relationship between type of mutation or clinical status of patients and albumin fragments observed. Very low-molecular-weight albumin fragments also can be produced by other diseases. We describe for the first time the presence of very low-molecular-mass albumin fragments in plasma of patients with FSGS with podocyte protein mutations that are absent in patients with idiopathic FSGS or healthy individuals. Additional studies are necessary to determine whether these fragments could be potential biomarkers to distinguish between genetic and idiopathic forms of FSGS.

High-quality electron beams from beam-driven plasma accelerators by wakefield-induced ionization injection.

PubMed

Martinez de la Ossa, A; Grebenyuk, J; Mehrling, T; Schaper, L; Osterhoff, J

2013-12-13

We propose a new and simple strategy for controlled ionization-induced trapping of electrons in a beam-driven plasma accelerator. The presented method directly exploits electric wakefields to ionize electrons from a dopant gas and capture them into a well-defined volume of the accelerating and focusing wake phase, leading to high-quality witness bunches. This injection principle is explained by example of three-dimensional particle-in-cell calculations using the code OSIRIS. In these simulations a high-current-density electron-beam driver excites plasma waves in the blowout regime inside a fully ionized hydrogen plasma of density 5×10(17)cm-3. Within an embedded 100  μm long plasma column contaminated with neutral helium gas, the wakefields trigger ionization, trapping of a defined fraction of the released electrons, and subsequent acceleration. The hereby generated electron beam features a 1.5 kA peak current, 1.5  μm transverse normalized emittance, an uncorrelated energy spread of 0.3% on a GeV-energy scale, and few femtosecond bunch length.

Photoionization and heating of a supernova-driven turbulent interstellar medium

NASA Astrophysics Data System (ADS)

Barnes, J. E.; Wood, Kenneth; Hill, Alex S.; Haffner, L. M.

2014-06-01

The diffuse ionized gas (DIG) in galaxies traces photoionization feedback from massive stars. Through three-dimensional photoionization simulations, we study the propagation of ionizing photons, photoionization heating and the resulting distribution of ionized and neutral gas within snapshots of magnetohydrodynamic simulations of a supernova-driven turbulent interstellar medium. We also investigate the impact of non-photoionization heating on observed optical emission line ratios. Inclusion of a heating term which scales less steeply with electron density than photoionization is required to produce diagnostic emission line ratios similar to those observed with the Wisconsin Hα Mapper. Once such heating terms have been included, we are also able to produce temperatures similar to those inferred from observations of the DIG, with temperatures increasing to above 15 000 K at heights |z| ≳ 1 kpc. We find that ionizing photons travel through low-density regions close to the mid-plane of the simulations, while travelling through diffuse low-density regions at large heights. The majority of photons travel small distances (≲100 pc); however some travel kiloparsecs and ionize the DIG.

Electron impact fragmentation of thymine: partial ionization cross sections for positive fragments

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Mahon, Francis; Barrett, Gerard; Gradziel, Marcin L.

2014-06-01

We have measured mass spectra for positive ions for low-energy electron impact on thymine using a reflectron time-of-flight mass spectrometer. Using computer controlled data acquisition, mass spectra have been acquired for electron impact energies up to 100 eV in steps of 0.5 eV. Ion yield curves for most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. The ion yield curves have been normalized by comparing the sum of the ion yields to the average of calculated total ionization cross sections. Appearance energies have been determined. The nearly equal appearance energies of 83 u and 55 u observed in the present work strongly indicate that near threshold the 55 u ion is formed directly by the breakage of two bonds in the ring, rather than from a successive loss of HNCO and CO from the parent ion. Likewise 54 u is not formed by CO loss from 82 u. The appearance energies are in a number of cases consistent with the loss of one or more hydrogen atoms from a heavier fragment, but 70 u is not formed by hydrogen loss from 71 u.

Fragmentation of alpha-Radical Cations of Arginine-Containing Peptides

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

Laskin, Julia; Yang, Zhibo; Ng, Dominic C.

2010-04-01

Fragmentation pathways of peptide radical cations, M+, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes [salen = N,N´-ethylenebis (salicylideneaminato)]. Subsequent hydrogen abstraction from the -carbon of the side chain followed by Ca-C bond cleavage results in the loss of a neutral side chain and formation of an a-radical cation with the radical site localized on the a-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of a-radicals when the basic arginine side chain wasmore » present in the sequence. In contrast, proton-driven fragmentation dominates CID spectra of a-radicals produced via the loss of the arginine side chain. Our results suggest that in most cases radical migration precedes fragmentation of large peptide radical cations.« less

Amino and Acetamide Functional Group Effects on the Ionization and Fragmentation of Sugar Chains in Positive-Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Yamagaki, Tohru; Sugahara, Kohtaro; Watanabe, Takehiro

2014-01-01

To elucidate the influence of amino (-NH2) and acetamide (-NHCOCH3, -NAc) groups in sugar chains on their ionization and fragmentation, cycloamyloses (cyclodextrins, CyDs) and lacto-oligosaccharide are analyzed by MALDI TOF/TOF and ESI Q-TOF mass spectrometry. CyD derivatives substituted by amino or acetamide groups are ideal analytes to extract the function group effects, which are amino-CyD with one hexosamine (HexNH2) and acetamide-CyD with one N-acetyl hexosamine (HexNAc). Interestingly, the relative ion intensities and isotope-like patterns in their product ion spectra depend on the functional groups and ion forms of sugar chains. Consequently, the results indicate that a proton (H+) localizes on the amino group of the amino sugar, and that the proton (H+) induces their fragmentation. Sodium cation (Na+) attachment is independent from amino group and exerts no influence on their fragmentation patterns in amino group except for mono- and disaccharide fragment ions because there is the possibility of the reducing end effect. In contrast, a sodium cation localizes much more frequently on the acetamide group in acetamide-CyDs because the chemical species with HexNAc are stable. Thus, their ions with HexNAc are abundant. These results are consistent with the fragmentation of lacto-neo- N-tetraose and maltotetraose, suggesting that a sodium cation generally localizes much more frequently on the acetamide group in sugar chains.

Resonance ionization laser ion sources for on-line isotope separators (invited).

PubMed

Marsh, B A

2014-02-01

A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

Gas chromatography-mass spectrometric studies of O-alkyl O-2-(N,N-dialkylamino) ethyl alkylphosphonites(phosphonates) for chemical weapons convention verification.

PubMed

Saeidian, Hamid; Babri, Mehran; Ramezani, Atefeh; Ashrafi, Davood; Sarabadani, Mansour; Naseri, Mohammad Taghi

2013-01-01

The electron ionization (EI) mass spectra of a series of O-alkyl O-2-(N,N-dialkylaminolethyl alkylphosphonites(phosphonates), which are precursors of nerve agents, were studied for Chemical Weapons Convention (CWC) verification. General El fragmentation pathways were constructed and discussed. Proposed fragment structures were confirmed through analyzing fragment ions of deuterated analogs and density functional theory (DFT) calculations. The observed fragment ions are due to different fragmentation pathways such as hydrogen and McLafferty+1 rearrangements, alkene, amine and alkoxy elimination by alpha- or beta-cleavage process. Fragment ions distinctly allow unequivocal identification of the interested compounds including those of isomeric compounds. The presence and abundance of fragment ions were found to depend on the size and structure of the alkyl group attached to nitrogen, phosphorus and oxygen atoms.

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

PubMed

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

2017-08-04

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

Propagation of a laser-driven relativistic electron beam inside a solid dielectric.

PubMed

Sarkisov, G S; Ivanov, V V; Leblanc, P; Sentoku, Y; Yates, K; Wiewior, P; Chalyy, O; Astanovitskiy, A; Bychenkov, V Yu; Jobe, D; Spielman, R B

2012-09-01

Laser probe diagnostics: shadowgraphy, interferometry, and polarimetry were used for a comprehensive characterization of ionization wave dynamics inside a glass target induced by a laser-driven, relativistic electron beam. Experiments were done using the 50-TW Leopard laser at the University of Nevada, Reno. We show that for a laser flux of ∼2 × 10(18) W/cm2 a hemispherical ionization wave propagates at c/3 for 10 ps and has a smooth electron-density distribution. The maximum free-electron density inside the glass target is ∼2 × 10(19) cm-3, which corresponds to an ionization level of ∼0.1%. Magnetic fields and electric fields do not exceed ∼15 kG and ∼1 MV/cm, respectively. The electron temperature has a hot, ringlike structure with a maximum of ∼0.7 eV. The topology of the interference phase shift shows the signature of the "fountain effect", a narrow electron beam that fans out from the propagation axis and heads back to the target surface. Two-dimensional particle-in-cell (PIC) computer simulations demonstrate radial spreading of fast electrons by self-consistent electrostatic fields driven by laser. The very low ionization observed after the laser heating pulse suggests a fast recombination on the sub-ps time scale.

Multiplicity distributions of shower particles and target fragments in 84 Kr 36-emulsion interactions at 1 GeV per nucleon

NASA Astrophysics Data System (ADS)

Singh, M. K.; Soma, A. K.; Pathak, Ramji; Singh, V.

2014-03-01

This article focuses on multiplicity distributions of shower particles and target fragments for interaction of 84 Kr 36 with NIKFI BR-2 nuclear emulsion target at kinetic energy of 1 GeV per nucleon. Experimental multiplicity distributions of shower particles, grey particles, black particles and heavily ionization particles are well described by multi-component Erlang distribution of multi-source thermal model. We have observed a linear correlation in multiplicities for the above mentioned particles or fragments. Further experimental studies have shown a saturation phenomenon in shower particle multiplicity with the increase of target fragment multiplicity.

Sequential and direct ionic excitation in the strong-field ionization of 1-butene molecules.

PubMed

Schell, Felix; Boguslavskiy, Andrey E; Schulz, Claus Peter; Patchkovskii, Serguei; Vrakking, Marc J J; Stolow, Albert; Mikosch, Jochen

2018-05-18

We study the Strong-Field Ionization (SFI) of the hydrocarbon 1-butene as a function of wavelength using photoion-photoelectron covariance and coincidence spectroscopy. We observe a striking transition in the fragment-associated photoelectron spectra: from a single Above Threshold Ionization (ATI) progression for photon energies less than the cation D0-D1 gap to two ATI progressions for a photon energy greater than this gap. For the first case, electronically excited cations are created by SFI populating the ground cationic state D0, followed by sequential post-ionization excitation. For the second case, direct sub-cycle SFI to the D1 excited cation state contributes significantly. Our experiments access ionization dynamics in a regime where strong-field and resonance-enhanced processes can interplay.

Laser-induced electron dynamics including photoionization: A heuristic model within time-dependent configuration interaction theory.

PubMed

Klinkusch, Stefan; Saalfrank, Peter; Klamroth, Tillmann

2009-09-21

We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H(2) when calculated nonperturbatively by TD-CIS.

Selectable fragmentation warhead

DOEpatents

Bryan, Courtney S.; Paisley, Dennis L.; Montoya, Nelson I.; Stahl, David B.

1993-01-01

A selectable fragmentation warhead capable of producing a predetermined number of fragments from a metal plate, and accelerating the fragments toward a target. A first explosive located adjacent to the plate is detonated at selected number of points by laser-driven slapper detonators. In one embodiment, a smoother-disk and a second explosive, located adjacent to the first explosive, serve to increase acceleration of the fragments toward a target. The ability to produce a selected number of fragments allows for effective destruction of a chosen target.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy.

PubMed

Chatterley, Adam S; Lackner, Florian; Neumark, Daniel M; Leone, Stephen R; Gessner, Oliver

2016-06-07

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10(13) and 2.2 × 10(14) W cm(-2). The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br(++). However, the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br(+), and Br(++), respectively. Transient molecular ion features assigned to DBE(+) and DBE(++) are observed, with dynamics linked to the production of Br(+) products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE(+) ions on a shallow potential energy surface. The appearance of Br(+) ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE(+) ionic species. Dicationic Br(++) products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy

DOE PAGES

Chatterley, Adam S.; Lackner, Florian; Neumark, Daniel M.; ...

2016-05-11

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10 13 and 2.2 × 10 14 W cm -2. The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br ++. However,more » the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br +, and Br ++, respectively. Transient molecular ion features assigned to DBE + and DBE ++ are observed, with dynamics linked to the production of Br + products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE + ions on a shallow potential energy surface. The appearance of Br + ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE + ionic species. Dicationic Br ++ products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.« less

Detection Identification and Quantification of Keto-Hydroperoxides in Low-Temperature Oxidation.

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

Hansen, Nils; Moshammer, Kai; Jasper, Ahren W.

2017-07-01

Keto-hydroperoxides are reactive partially oxidized intermediates that play a central role in chain-branching reactions during the low-temperature oxidation of hydrocarbons. In this Perspective, we outline how these short lived species can be detected, identified, and quantified using integrated experimental and theoretical approaches. The procedures are based on direct molecular-beam sampling from reactive environments, followed by mass spectrometry with single-photon ionization, identification of fragmentation patterns, and theoretical calculations of ionization thresholds, fragment appearance energies, and photoionization cross sections. Using the oxidation of neo-pentane and tetrahydrofuran as examples, the individual steps of the experimental approaches are described in depth together with amore » detailed description of the theoretical efforts. For neo-pentane, the experimental data are consistent with the calculated ionization and fragment appearance energies of the keto-hydroperoxide, thus adding confidence to the analysis routines and the employed levels of theory. For tetrahydrofuran, multiple keto-hydroperoxide isomers are possible due to the presence of nonequivalent O 2 addition sites. Despite this additional complexity, the experimental data allow for the identification of two to four keto-hydroperoxides. Mole fraction profiles of the keto-hydroperoxides, which are quantified using calculated photoionization cross sections, are provided together with estimated uncertainties as function of the temperature of the reactive mixture and can serve as validation targets for chemically detailed mechanisms.« less

Fragmentation of molecular tributyltin chloride

NASA Astrophysics Data System (ADS)

Osmekhin, S.; Caló, A.; Kisand, V.; Nõmmiste, E.; Kotilainen, H.; Aksela, H.; Aksela, S.

2008-06-01

Fragmentation of tributyltin chloride (TBTCl) vapour has been studied experimentally by means of time-of-flight mass spectrometry at the photon energy range of 9-25 eV of synchrotron radiation, at 21.22 eV of HeI as well as with 500 eV electron beam excitation. Branching ratios of the tributyltin chloride fragments taken with HeI and synchrotron radiation have been presented first time. Calculations based on density functional theory (DFT) were carried out for TBTCl and the ionization energies obtained were used to predict the dissociation pathways creating the observed ions.

Application of a multivariate normal distribution methodology to the dissociation of doubly ionized molecules: The DMDS (CH3 -SS-CH3 ) case.

PubMed

Varas, Lautaro R; Pontes, F C; Santos, A C F; Coutinho, L H; de Souza, G G B

2015-09-15

The ion-ion-coincidence mass spectroscopy technique brings useful information about the fragmentation dynamics of doubly and multiply charged ionic species. We advocate the use of a matrix-parameter methodology in order to represent and interpret the entire ion-ion spectra associated with the ionic dissociation of doubly charged molecules. This method makes it possible, among other things, to infer fragmentation processes and to extract information about overlapped ion-ion coincidences. This important piece of information is difficult to obtain from other previously described methodologies. A Wiley-McLaren time-of-flight mass spectrometer was used to discriminate the positively charged fragment ions resulting from the sample ionization by a pulsed 800 eV electron beam. We exemplify the application of this methodology by analyzing the fragmentation and ionic dissociation of the dimethyl disulfide (DMDS) molecule as induced by fast electrons. The doubly charged dissociation was analyzed using the Multivariate Normal Distribution. The ion-ion spectrum of the DMDS molecule was obtained at an incident electron energy of 800 eV and was matrix represented using the Multivariate Distribution theory. The proposed methodology allows us to distinguish information among [CH n SH n ] + /[CH 3 ] + (n = 1-3) fragment ions in the ion-ion coincidence spectra using ion-ion coincidence data. Using the momenta balance methodology for the inferred parameters, a secondary decay mechanism is proposed for the [CHS] + ion formation. As an additional check on the methodology, previously published data on the SiF 4 molecule was re-analyzed with the present methodology and the results were shown to be statistically equivalent. The use of a Multivariate Normal Distribution allows for the representation of the whole ion-ion mass spectrum of doubly or multiply ionized molecules as a combination of parameters and the extraction of information among overlapped data. We have successfully applied this methodology to the analysis of the fragmentation of the DMDS molecule. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Vacuum ultraviolet photofragmentation of octadecane: photoionization mass spectrometric and theoretical investigation.

PubMed

Xu, Jing; Sang, Pengpeng; Zhao, Lianming; Guo, Wenyue; Qi, Fei; Xing, Wei; Yan, Zifeng

The photoionization and fragmentation of octadecane were investigated with infrared laser desorption/tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (IRLD/VUV PIMS) and theoretical calculations. Mass spectra of octadecane were measured at various photon energies. The fragment ions were gradually detected with the increase of photon energy. The main fragment ions were assigned to radical ions (C n H 2 n +1 + , n  = 4-11) and alkene ions (C n H 2 n + , n  = 5-10). The ionization energy of the precursor and appearance energy of ionic fragments were obtained by measuring the photoionization efficiency spectrum. Possible formation pathways of the fragment ions were discussed with the help of density functional theory calculations.

Extreme ionization of Xe clusters driven by ultraintense laser fields

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

Heidenreich, Andreas; Last, Isidore; Jortner, Joshua

We applied theoretical models and molecular dynamics simulations to explore extreme multielectron ionization in Xe{sub n} clusters (n=2-2171, initial cluster radius R{sub 0}=2.16-31.0 A ring ) driven by ultraintense infrared Gaussian laser fields (peak intensity I{sub M}=10{sup 15}-10{sup 20} W cm{sup -2}, temporal pulse length {tau}=10-100 fs, and frequency {nu}=0.35 fs{sup -1}). Cluster compound ionization was described by three processes of inner ionization, nanoplasma formation, and outer ionization. Inner ionization gives rise to high ionization levels (with the formation of (Xe{sup q+}){sub n} with q=2-36), which are amenable to experimental observation. The cluster size and laser intensity dependence of themore » inner ionization levels are induced by a superposition of barrier suppression ionization (BSI) and electron impact ionization (EII). The BSI was induced by a composite field involving the laser field and an inner field of the ions and electrons, which manifests ignition enhancement and screening retardation effects. EII was treated using experimental cross sections, with a proper account of sequential impact ionization. At the highest intensities (I{sub M}=10{sup 18}-10{sup 20} W cm{sup -2}) inner ionization is dominated by BSI. At lower intensities (I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2}), where the nanoplasma is persistent, the EII contribution to the inner ionization yield is substantial. It increases with increasing the cluster size, exerts a marked effect on the increase of the (Xe{sup q+}){sub n} ionization level, is most pronounced in the cluster center, and manifests a marked increase with increasing the pulse length (i.e., becoming the dominant ionization channel (56%) for Xe{sub 2171} at {tau}=100 fs). The EII yield and the ionization level enhancement decrease with increasing the laser intensity. The pulse length dependence of the EII yield at I{sub M}=10{sup 15}-10{sup 16} W cm{sup -2} establishes an ultraintense laser pulse length control mechanism of extreme ionization products.« less

Visualizing and Steering Dissociative Frustrated Double Ionization of Hydrogen Molecules

NASA Astrophysics Data System (ADS)

Zhang, Wenbin; Yu, Zuqing; Gong, Xiaochun; Wang, Junping; Lu, Peifen; Li, Hui; Song, Qiying; Ji, Qinying; Lin, Kang; Ma, Junyang; Li, Hanxiao; Sun, Fenghao; Qiang, Junjie; Zeng, Heping; He, Feng; Wu, Jian

2017-12-01

We experimentally visualize the dissociative frustrated double ionization of hydrogen molecules by using few-cycle laser pulses in a pump-probe scheme, in which process the tunneling ionized electron is recaptured by one of the outgoing nuclei of the breaking molecule. Three internuclear distances are recognized to enhance the dissociative frustrated double ionization of molecules at different instants after the first ionization step. The recapture of the electron can be further steered to one of the outgoing nuclei as desired by using phase-controlled two-color laser pulses. Both the experimental measurements and numerical simulations suggest that the Rydberg atom is favored to emit to the direction of the maximum of the asymmetric optical field. Our results on the one hand intuitively visualize the dissociative frustrated double ionization of molecules, and on the other hand open the possibility to selectively excite the heavy fragment ejected from a molecule.

Multi-stage Mass Spectrometry of Poly(vinyl pyrrolidone) and Its Vinyl Succinimide Copolymer Formed upon Exposure to Sodium Hypochlorite

PubMed Central

Fouquet, Thierry; Torimura, Masaki; Sato, Hiroaki

2016-01-01

The degradation routes of poly(vinyl pyrrolidone) (PVP) exposed to sodium hypochlorite (bleach) have been previously investigated using chemical analyses such as infrared spectroscopy. So far, no reports have proposed mass spectrometry (MS) as an alternative tool despite its capability to provide molecular and structural information using its single stage electrospray (ESI) or matrix assisted laser desorption ionization (MALDI) and multi stage (MSn) configurations, respectively. The present study thus reports on the characterization of PVP after its exposure to bleach by high resolution MALDI spiralTOF-MS and Kendrick mass defect analysis providing clues as to the formation of a vinyl pyrrolidone/vinyl succinimide copolymeric degradation product. A thorough investigation of the fragmentation pathways of PVP adducted with sodium and proton allows one main route to be described—namely the release of the pyrrolidone pendant group in a charge remote and charge driven mechanism, respectively. Extrapolating this fragmentation pathway, the oxidation of vinyl pyrrolidone into vinyl succinimide hypothesized from the single stage MS is validated by the detection of an alternative succinimide neutral loss in lieu of the pyrrolidone release in the ESI-MSn spectra of the aged PVP sample. It constitutes an example of application of multi-stage mass spectrometry for the characterization of the degradation of polymeric samples at a molecular level. PMID:27800293

Bound-Electron Nonlinearity Beyond the Ionization Threshold.

PubMed

Wahlstrand, J K; Zahedpour, S; Bahl, A; Kolesik, M; Milchberg, H M

2018-05-04

We present absolute space- and time-resolved measurements of the ultrafast laser-driven nonlinear polarizability in argon, krypton, xenon, nitrogen, and oxygen up to ionization fractions of a few percent. These measurements enable determination of the strongly nonperturbative bound-electron nonlinear polarizability well beyond the ionization threshold, where it is found to remain approximately quadratic in the laser field, a result normally expected at much lower intensities where perturbation theory applies.

Bound-Electron Nonlinearity Beyond the Ionization Threshold

NASA Astrophysics Data System (ADS)

Wahlstrand, J. K.; Zahedpour, S.; Bahl, A.; Kolesik, M.; Milchberg, H. M.

2018-05-01

We present absolute space- and time-resolved measurements of the ultrafast laser-driven nonlinear polarizability in argon, krypton, xenon, nitrogen, and oxygen up to ionization fractions of a few percent. These measurements enable determination of the strongly nonperturbative bound-electron nonlinear polarizability well beyond the ionization threshold, where it is found to remain approximately quadratic in the laser field, a result normally expected at much lower intensities where perturbation theory applies.

Sodiation as a tool for enhancing the diagnostic value of MALDI-TOF/TOF-MS spectra of complex astaxanthin ester mixtures from Haematococcus pluvialis.

PubMed

Weesepoel, Yannick; Vincken, Jean-Paul; Pop, Raluca Maria; Liu, Kun; Gruppen, Harry

2013-07-01

The microalga Haematococcus pluvialis produces the pigment astaxanthin mainly in esterified form with a multitude of fatty acids, which results in a complex mixture of carotenol mono- and diesters. For rapid fingerprinting of these esters, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF/TOF-MS) might be an alternative to traditional chromatographic separation combined with MS. Investigation of ionization and fragmentation of astaxanthin mono- and diester palmitate standards in MALDI-TOF/TOF-MS showed that sodium adduct parent masses [M + Na](+) gave much simpler MS(2) spectra than radical / protonated [M](+●) / [M + H](+) parents. [M + Na](+) fragments yielded diagnostic polyene-specific eliminations and fatty acid neutral losses, whereas [M](+●) / [M + H](+) fragmentation resulted in a multitude of non-diagnostic daughters. For diesters, a benzonium fragment, formed by polyene elimination, was required for identification of the second fatty acid attached to the astaxanthin backbone. Parents were forced into [M + Na](+) ionization by addition of sodium acetate, and best signal-to-noise ratios were obtained in the 0.1 to 1.0 mM range. This method was applied to fingerprinting astaxanthin esters in a crude H. pluvialis extract. Prior to MALDI-TOF/TOF-MS, the extract was fractionated by normal phase Flash chromatography to obtain fractions enriched in mono- and diesters and to remove pheophytin a, which compromised monoester signals. All 12 types of all-trans esterified esters found in LC were identified with MALDI-TOF/TOF-MS, with the exception of two minor monoesters. Copyright © 2013 John Wiley & Sons, Ltd.

Improvement in ionization efficiency of direct analysis in real time-mass spectrometry (DART-MS) by corona discharge.

PubMed

Sekimoto, Kanako; Sakakura, Motoshi; Kawamukai, Takatomo; Hike, Hiroshi; Shiota, Teruhisa; Usui, Fumihiko; Bando, Yasuhiko; Takayama, Mitsuo

2016-08-02

Herein it is shown that a combination of direct analysis in real time (DART) with a corona discharge system consisting of only a needle electrode easily improves DART ionization efficiency. Positive and negative DC corona discharges led to a formation of abundant excited helium atoms as well as the reactant ions H3O(+)(H2O)n and O2˙(-) in the DART analyte ionization area. These phenomena resulted in an increase in the absolute intensities of (de)protonated analytes by a factor of 2-20 over conventional DART. The other analyte ions detected in this corona-DART system (i.e., molecular ions, fragment ions, oxygenated (de)protonated analytes, dehydrogenated deprotonated analytes, and negative ion adducts) were quite similar to those obtained from DART alone. This indicates a lack of side reactions due to the corona discharge. The change in the relative intensities of individual analyte-related ions due to the combination of a corona discharge system with DART suggests that there is no effect of the abundant excited helium in the analyte ionization area on the fragmentation processes or enhancement of oxidation due to hydroxyl radicals HO˙. Furthermore, it was found that the corona-DART combination can be applied to the highly sensitive analysis of n-alkanes, in which the alkanes are ionized as positive ions via hydride abstraction and oxidation, independent of the type of alkane or the mass spectrometer used.

Determination of patulin in apple juice by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

PubMed

Sewram, V; Nair, J J; Nieuwoudt, T W; Leggott, N L; Shephard, G S

2000-11-03

An HPLC-MS-MS method with selected reaction monitoring (SRM) for the determination of patulin in apple juice samples is described. Mass spectrometric detection was accomplished following atmospheric pressure chemical ionization (APCI) in both positive and negative ion modes. Collision induced dissociation (CID) of the protonated molecular ion led initially to the loss of H2O (fragment m/z 137). At higher energies CO is lost from both the protonated parent molecule (fragment m/z 127) and the dehydrated molecular ion (fragment m/z 109). In contrast, CID of the deprotonated molecular ion led initially to the fragment at m/z 109 corresponding to the loss of either CO2 or acetaldehyde, followed at higher CID energy by the loss of H2O (fragment m/z 135) and CO (fragment m/z 125) from the deprotonated molecular ion. Detection in the negative ion mode proved superior and a linear response was observed over the injected range from 6 to 200 ng patulin. Apple juice samples spiked with patulin between 10 and 135 microg/l were analyzed following liquid-liquid extraction with ethyl acetate and clean up with sodium carbonate. Utilizing reversed-phase HPLC with acetonitrile-water (10:90) at 0.5 ml/min, levels down to 10 microg/l were readily quantified and a detection limit of 4 microg/l was attainable at a signal-to-noise (SIN) ratio of 4. The MS data for the spiked samples compared well to the UV data and when plotted against each other displayed a correlation coefficient (R) of 0.99.

Method and apparatus for plasma source ion implantation

DOEpatents

Conrad, J.R.

1988-08-16

Ion implantation into surfaces of three-dimensional targets is achieved by forming an ionized plasma about the target within an enclosing chamber and applying a pulse of high voltage between the target and the conductive walls of the chamber. Ions from the plasma are driven into the target object surfaces from all sides simultaneously without the need for manipulation of the target object. Repetitive pulses of high voltage, typically 20 kilovolts or higher, causes the ions to be driven deeply into the target. The plasma may be formed of a neutral gas introduced into the evacuated chamber and ionized therein with ionizing radiation so that a constant source of plasma is provided which surrounds the target object during the implantation process. Significant increases in the surface hardness and wear characteristics of various materials are obtained with ion implantation in this manner. 7 figs.

Method and apparatus for plasma source ion implantation

DOEpatents

Conrad, John R.

1988-01-01

Ion implantation into surfaces of three-dimensional targets is achieved by forming an ionized plasma about the target within an enclosing chamber and applying a pulse of high voltage between the target and the conductive walls of the chamber. Ions from the plasma are driven into the target object surfaces from all sides simultaneously without the need for manipulation of the target object. Repetitive pulses of high voltage, typically 20 kilovolts or higher, causes the ions to be driven deeply into the target. The plasma may be formed of a neutral gas introduced into the evacuated chamber and ionized therein with ionizing radiation so that a constant source of plasma is provided which surrounds the target object during the implantation process. Significant increases in the surface hardness and wear characteristics of various materials are obtained with ion implantation in this manner.

Association of amino acids embedded in helium droplets detected by mass spectrometry

NASA Astrophysics Data System (ADS)

Lalanne, Matthieu R.; Achazi, Georg; Reichwald, Sebastian; Lindinger, Albrecht

2015-12-01

Amino acids were embedded in helium droplets. The electron impact ionization allows for detecting positively charged glycine, valine, histidine, tryptophan and their principal fragments. Monomers and polymers with up to four amino acids are reported. Heterodimers of tryptophan and valine or histidine are observed as well as heterodimers of included fragments. The ability of these associations of molecules to form complexes with water is examined.

Total Kinetic Energy and Fragment Mass Distribution of Neutron-Induced Fission of U-233

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

Higgins, Daniel James; Schmitt, Kyle Thomas; Mosby, Shea Morgan

Properties of fission in U-233 were studied at the Los Alamos Neutron Science Center (LANSCE) at incident neutron energies from thermal to 40 MeV at both the Lujan Neutron Scattering Center flight path 12 and at WNR flight path 90-Left from Dec 2016 to Jan 2017. Fission fragments are observed in coincidence using a twin ionization chamber with Frisch grids. The average total kinetic energy (TKE) released from fission and fragment mass distributions are calculated from observations of energy deposited in the detector and conservation of mass and momentum. Accurate experimental measurements of these parameters are necessary to better understandmore » the fission process and obtain data necessary for calculating criticality. The average TKE released from fission has been well characterized for several isotopes at thermal neutron energy, however, few measurements have been made at fast neutron energies. This experiment expands on previous successful experiments using an ionization chamber to measure TKE and fragment mass distributions of U-235, U-238, and Pu-239. This experiment requires the full spectrum of neutron energies and can therefore only be performed at a small number of facilities in the world. The required full neutron energy spectrum is obtained by combining measurements from WNR 90L and Lujan FP12 at LANSCE.« less

Differentiation of three pairs of aconite alkaloid isomers from Aconitum nagarum var. lasiandrum by electrospray ionization tandem mass spectrometry.

PubMed

Li, Rui; Wu, Zhijun; Zhang, Fan; Ding, Lisheng

2006-01-01

Three pairs of isomers of aconite alkaloids from Aconitum nagarum var. lasiandrum have been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS) employing ion-trap and quadrupole time-of-flight mass spectrometers in positive mode. Based on the differences of their fragmentation pathways and special fragment ions, three pairs of isomers of aconite alkaloids were differentiated. In addition, fragmentation laws of some veatchines and the discrepancy of fragmentation mechanisms between veatchine-type and aconitine-type alkaloid were also concluded. In the case of veatchines, a radical would be formed by homolysis of C18--C4 or C18--H bonds, followed by elimination of a series of C(2)H(2) and C(2)H(4). Moreover, the retro-Diels-Alder (RDA) reaction occurred in the E-ring and double-electron transfer triggered by the positive charge on C1 led to the formation of diagnostic ions at m/z 216. With regard to aconitine-type alkaloids, the N-substituent is not eliminated easily. Although there is no carbonyl group on some aconitine-type alkaloids, with hydroxyl and methoxyl on C15 and C16 respectively, CO was readily eliminated through tautomerization.

Duration of an intense laser pulse can determine the breakage of multiple chemical bonds

PubMed Central

Xie, Xinhua; Lötstedt, Erik; Roither, Stefan; Schöffler, Markus; Kartashov, Daniil; Midorikawa, Katsumi; Baltuška, Andrius; Yamanouchi, Kaoru; Kitzler, Markus

2015-01-01

Control over the breakage of a certain chemical bond in a molecule by an ultrashort laser pulse has been considered for decades. With the availability of intense non-resonant laser fields it became possible to pre-determine femtosecond to picosecond molecular bond breakage dynamics by controlled distortions of the electronic molecular system on sub-femtosecond time scales using field-sensitive processes such as strong-field ionization or excitation. So far, all successful demonstrations in this area considered only fragmentation reactions, where only one bond is broken and the molecule is split into merely two moieties. Here, using ethylene (C2H4) as an example, we experimentally investigate whether complex fragmentation reactions that involve the breakage of more than one chemical bond can be influenced by parameters of an ultrashort intense laser pulse. We show that the dynamics of removing three electrons by strong-field ionization determines the ratio of fragmentation of the molecular trication into two respectively three moieties. We observe a relative increase of two-body fragmentations with the laser pulse duration by almost an order of magnitude. Supported by quantum chemical simulations we explain our experimental results by the interplay between the dynamics of electron removal and nuclear motion. PMID:26271602

Ionizing potential waves and high-voltage breakdown streamers.

NASA Technical Reports Server (NTRS)

Albright, N. W.; Tidman, D. A.

1972-01-01

The structure of ionizing potential waves driven by a strong electric field in a dense gas is discussed. Negative breakdown waves are found to propagate with a velocity proportional to the electric field normal to the wavefront. This causes a curved ionizing potential wavefront to focus down into a filamentary structure, and may provide the reason why breakdown in dense gases propagates in the form of a narrow leader streamer instead of a broad wavefront.

Laser separation of lithium isotopes by double resonance enhanced multiphoton ionization of Li/sub 2/

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

Balz, J.G.; Bernheim, R.A.; Gold, L.P.

1987-01-01

Multiphoton ionization spectra of /sup 7/Li/sub 2/, /sup 6/Li/sub 2/, and /sup 7/Li/sup 6/Li vapors have been measured in the 570--650 nm region using a single, low resolution, multimode cw dye laser. A number of wavelengths provide selective multiphoton ionization of one isotopic species demonstrating the possibility of efficient laser-driven isotopic separation in lithium in this wavelength region.

Bound and continuum energy distributions of nuclear fragments resulting from tunneling ionization of molecules

NASA Astrophysics Data System (ADS)

Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

2018-03-01

We present the theory of tunneling ionization of molecules with both electronic and nuclear motion treated quantum mechanically. The theory provides partial rates for ionization into the different final states of the molecular ion, including both bound vibrational and dissociative channels. The exact results obtained for a one-dimensional model of H2 and D2 are compared with two approximate approaches, the weak-field asymptotic theory and the Born-Oppenheimer approximation. The validity ranges and compatibility of the approaches are identified formally and illustrated by the calculations. The results quantify that at typical field strengths considered in strong-field physics, it is several orders of magnitude more likely to ionize into bound vibrational ionic channels than into the dissociative channel.

Electron-impact dissociative excitation and ionization of N{sub 2}D{sup +}

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

Fogle, M.; Bahati, E. M.; Bannister, M. E.

Absolute cross sections for electron-impact dissociation of N{sub 2}D{sup +} producing N{sub 2}{sup +}, ND{sup +}, and N{sup +} ion fragments were measured in the 5- to 100-eV range using a crossed electron-ion beams technique. In the 5- to 20-eV region, in which dissociative excitation (DE) is the principal contributing mechanism, N{sub 2}{sup +} production dominates. The N{sub 2}{sup +} + D dissociation channel shows a large resonant-like structure in the DE cross section, as observed previously in electron impact dissociation of triatomic dihydride species [M. Fogle, E. M. Bahati, M. E. Bannister, S. H. M. Deng, C. R. Vane,more » R. D. Thomas, and V. Zhaunerchyk, Phys. Rev. A 82, 042720 (2010)]. In the dissociative ionization (DI) region, 20- to 100-eV, N{sub 2}{sup +}, ND{sup +}, and N{sup +} ion fragment production are comparable. The observance of the ND{sup +} and N{sup +} ion fragments indicate breaking of the N - N bond along certain dissociation channels.« less

Collision-induced dissociation analysis of negative atmospheric ion adducts in atmospheric pressure corona discharge ionization mass spectrometry.

PubMed

Sekimoto, Kanako; Takayama, Mitsuo

2013-05-01

Collision-induced dissociation (CID) experiments were performed on atmospheric ion adducts [M + R](-) formed between various types of organic compounds M and atmospheric negative ions R(-) [such as O2(-), HCO3(-), COO(-)(COOH), NO2(-), NO3(-), and NO3(-)(HNO3)] in negative-ion mode atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. All of the [M + R](-) adducts were fragmented to form deprotonated analytes [M - H](-) and/or atmospheric ions R(-), whose intensities in the CID spectra were dependent on the proton affinities of the [M - H](-) and R(-) fragments. Precursor ions [M + R](-) for which R(-) have higher proton affinities than [M - H](-) formed [M - H](-) as the dominant product. Furthermore, the CID of the adducts with HCO3(-) and NO3(-)(HNO3) led to other product ions such as [M + HO](-) and NO3(-), respectively. The fragmentation behavior of [M + R](-) for each R(-) observed was independent of analyte type (e.g., whether the analyte was aliphatic or aromatic, or possessed certain functional groups).

Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies.

PubMed

Desmazières, Bernard; Legros, Véronique; Giuliani, Alexandre; Buchmann, William

2014-01-15

Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8eV up to 10.6eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the ionization energy of the solvent. As commercial APPI sources typically use krypton lamps with energy fixed at 10eV and 10.6eV, the study of the ionization of polymers over a wavelength range allowed to confirm and refine the previously proposed ionization mechanisms. Moreover, the APPI source can efficiently be used as an interface between size exclusion chromatography or reverse phase liquid chromatography and MS for the study of synthetic oligomers. However, the photoionization at fixed wavelength of polymer standards with different molecular weights showed that it was difficult to obtain intact ionized oligomers with molecular weights above a few thousands. Copyright © 2013 Elsevier B.V. All rights reserved.

Applications of Quantum Theory of Atomic and Molecular Scattering to Problems in Hypersonic Flow

NASA Technical Reports Server (NTRS)

Malik, F. Bary

1995-01-01

The general status of a grant to investigate the applications of quantum theory in atomic and molecular scattering problems in hypersonic flow is summarized. Abstracts of five articles and eleven full-length articles published or submitted for publication are included as attachments. The following topics are addressed in these articles: fragmentation of heavy ions (HZE particles); parameterization of absorption cross sections; light ion transport; emission of light fragments as an indicator of equilibrated populations; quantum mechanical, optical model methods for calculating cross sections for particle fragmentation by hydrogen; evaluation of NUCFRG2, the semi-empirical nuclear fragmentation database; investigation of the single- and double-ionization of He by proton and anti-proton collisions; Bose-Einstein condensation of nuclei; and a liquid drop model in HZE particle fragmentation by hydrogen.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization.

PubMed

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed. Graphical Abstract ᅟ.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization

NASA Astrophysics Data System (ADS)

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed.

Fast Determination of Ingredients in Solid Pharmaceuticals by Microwave-Enhanced In-Source Decay of Microwave Plasma Torch Mass Spectrometry.

PubMed

Su, Rui; Wang, Xinchen; Hou, Changming; Yang, Meiling; Huang, Keke; Chen, Huanwen

2017-09-01

Rapid qualitative and quantitative analysis of solid samples (e.g., pharmaceutical preparations) by using a small and low-resolution mass spectrometer without MS/MS function is still a challenge in ambient pressure ionization mass spectrometric analysis. Herein, a practically efficient method termed microwave-enhanced in-source decay (MEISD) using microwave plasma torch desorption ionization coupled with time-of-flight mass spectrometry (MPTDI-TOF MS) was developed for fast analysis of pharmaceutical tablets using a miniature TOF mass spectrometer without tandem mass function. The intensity of ISD fragmentation was evaluated under different microwave power values. Several factors, including desorption distance and time that might affect the signal intensity and fragmentation, were systematically investigated. It was observed that both the protonated molecular ions and major fragment ions from the active ingredients in tablets could be found in the full-scan mass spectra in positive ion mode, which were comparable to those obtained by a commercial LTQ-XL ion trap mass spectrometer. The structures of the ingredients could be elucidated in detail using the MEISD method, which promotes our understanding of the desorption/ionization processes in microwave plasma torch (MPT). Quantitative analysis of 10 tablets was achieved by full-scan MPTDI-TOF MS with low limit of detection (LOD, 0.763 mg/g), acceptable relative standard deviation (RSD < 7.33%, n =10), and 10 s for each tablet, showing promising applications in high throughput screening of counterfeit drugs. Graphical Abstract ᅟ.

Fast Determination of Ingredients in Solid Pharmaceuticals by Microwave-Enhanced In-Source Decay of Microwave Plasma Torch Mass Spectrometry

NASA Astrophysics Data System (ADS)

Su, Rui; Wang, Xinchen; Hou, Changming; Yang, Meiling; Huang, Keke; Chen, Huanwen

2017-09-01

Rapid qualitative and quantitative analysis of solid samples (e.g., pharmaceutical preparations) by using a small and low-resolution mass spectrometer without MS/MS function is still a challenge in ambient pressure ionization mass spectrometric analysis. Herein, a practically efficient method termed microwave-enhanced in-source decay (MEISD) using microwave plasma torch desorption ionization coupled with time-of-flight mass spectrometry (MPTDI-TOF MS) was developed for fast analysis of pharmaceutical tablets using a miniature TOF mass spectrometer without tandem mass function. The intensity of ISD fragmentation was evaluated under different microwave power values. Several factors, including desorption distance and time that might affect the signal intensity and fragmentation, were systematically investigated. It was observed that both the protonated molecular ions and major fragment ions from the active ingredients in tablets could be found in the full-scan mass spectra in positive ion mode, which were comparable to those obtained by a commercial LTQ-XL ion trap mass spectrometer. The structures of the ingredients could be elucidated in detail using the MEISD method, which promotes our understanding of the desorption/ionization processes in microwave plasma torch (MPT). Quantitative analysis of 10 tablets was achieved by full-scan MPTDI-TOF MS with low limit of detection (LOD, 0.763 mg/g), acceptable relative standard deviation (RSD < 7.33%, n =10), and 10 s for each tablet, showing promising applications in high throughput screening of counterfeit drugs. [Figure not available: see fulltext.

A velocity-map imaging study of methyl non-resonant multiphoton ionization from the photodissociation of CH3I in the A-band

PubMed Central

Poullain, Sonia Marggi; Chicharro, David V.; Rubio-Lago, Luis; García-Vela, Alberto

2017-01-01

Chemical reaction dynamics and, particularly, photodissociation in the gas phase are generally studied using pump–probe schemes where a first laser pulse induces the process under study and a second one detects the produced fragments. Providing an efficient detection of ro-vibrationally state-selected photofragments, the resonance enhanced multiphoton ionization (REMPI) technique is, without question, the most popular approach used for the probe step, while non-resonant multiphoton ionization (NRMPI) detection of the products is scarce. The main goal of this work is to test the sensitivity of the NRMPI technique to fragment vibrational distributions arising from molecular photodissociation processes. We revisit the well-known process of methyl iodide photodissociation in the A-band at around 280 nm, using the velocity-map imaging technique in conjunction with NRMPI of the methyl fragment. The detection wavelength, carefully selected to avoid any REMPI transition, was scanned between 325 and 335 nm seeking correlations between the different observables—the product vibrational, translational and angular distributions—and the excitation wavelength of the probe laser pulse. The experimental results have been discussed on the base of quantum dynamics calculations of photofragment vibrational populations carried out on available ab initio potential-energy surfaces using a four-dimensional model. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320907

Isolation of the endosperm-specific LPAAT gene promoter from coconut (Cocos nucifera L.) and its functional analysis in transgenic rice plants.

PubMed

Xu, Li; Ye, Rongjian; Zheng, Yusheng; Wang, Zhekui; Zhou, Peng; Lin, Yongjun; Li, Dongdong

2010-09-01

As one of the key tropical crops, coconut (Cocos nucifera L.) is a member of the monocotyledonous family Aracaceae (Palmaceae). In this study, we amplified the upstream region of an endosperm-specific expression gene, Lysophosphatidyl acyltransferase (LPAAT), from the coconut genomic DNA by chromosome walking. In this sequence, we found several types of promoter-related elements including TATA-box, CAAT-box and Skn1-motif. In order to further examine its function, three different 5'-deletion fragments were inserted into pBI101.3, a plant expression vector harboring the LPAAT upstream sequence, leading to pBI101.3-L1, pBI101.3-L2 and pBI101.3-L3, respectively. We obtained transgenic plants of rice by Agrobacterium-mediated callus transformation and plant regeneration and detected the expression of gus gene by histochemical staining and fluorometric determination. We found that gus gene driven by the three deletion fragments was specifically expressed in the endosperm of rice seeds, but not in the empty vector of pBI101.3 and other tissues. The highest expression level of GUS was at 15 DAF in pBI101.3-L3 and pBI101.3-L2 transgenic lines, while the same level was detected at 10 DAF in pBI101.3-L1. The expression driven by the whole fragment was up to 1.76- and 2.8-fold higher than those driven by the -817 bp and -453 bp upstream fragments, and 10.7-fold higher than that driven by the vector without the promoter. Taken together, our results strongly suggest that these promoter fragments from coconut have a significant potential in genetically improving endosperm in main crops.

Modeling X-ray Absorbers in AGNs with MHD-Driven Accretion-Disk Winds

NASA Astrophysics Data System (ADS)

Fukumura, Keigo; Kazanas, D.; Shrader, C. R.; Tombesi, F.; Contopoulos, J.; Behar, E.

2013-04-01

We have proposed a systematic view of the observed X-ray absorbers, namely warm absorbers (WAs) in soft X-ray and highly-ionized ultra-fast outflows (UFOs), in the context of magnetically-driven accretion-disk wind models. While potentially complicated by variability and thermal instability in these energetic outflows, in this simplistic model we have calculated 2D kinematic field as well as density and ionization structure of the wind with density profile of 1/r corresponding to a constant column distribution per decade of ionization parameter. In particular we show semi-analytically that the inner layer of the disk-wind manifests itself as the strongly-ionized fast outflows while the outer layer is identified as the moderately-ionized absorbers. The computed characteristics of these two apparently distinct absorbers are consistent with X-ray data (i.e. a factor of ~100 difference in column and ionization parameters as well as low wind velocity vs. near-relativistic flow). With the predicted contour curves for these wind parameters one can constrain allowed regions for the presence of WAs and UFOs.The model further implies that the UFO's gas pressure is comparable to that of the observed radio jet in 3C111 suggesting that the magnetized disk-wind with density profile of 1/r is a viable agent to help sustain such a self-collimated jet at small radii.

The size and shape of Gum's nebula

NASA Technical Reports Server (NTRS)

Johnson, H. M.

1971-01-01

The ionizing light of the supernova which produced the Gum nebula is now fossilized in the still live, though failing, H II region. The main body of the nebula suggests a hollow center or shell form, with a characteristic radius of about half the distance to the outlying fragments. The edges of the main body patches are typically sharp and often bright. The structure of the Gum nebula appears to be dependent on the event of ionization and possibly on the details of heating. It is not now an unstructured ambient medium, as it may have been before the recent ionization. Several hypotheses are presented for a structured ambient medium.

Impact of impurities on zonal flow driven by trapped electron mode turbulence

NASA Astrophysics Data System (ADS)

Guo, Weixin; Wang, Lu; Zhuang, Ge

2017-12-01

The impact of impurities on the generation of zonal flow (ZF) driven by collisonless trapped electron mode turbulence in deuterium (D)-tritium (T) plasmas is investigated. An expression for ZF growth rate with impurities is derived by balancing the ZF potential shielded by polarization effects and the ZF modulated radial turbulent current. Then, it is shown that the maximum normalized ZF growth rate is reduced by the presence of fully ionized non-trace light impurities with relatively flat density profile, and slightly reduced by highly ionized trace tungsten, while the maximum normalized ZF growth rate can be enhanced by fully ionized non-trace light impurities with relatively steep density profile. In particular, the effects of high temperature helium from D-T reaction on ZF depend on the temperature ratio between electrons and high temperature helium. The possible relevance of our findings to recent experimental results and future burning plasmas is also discussed.

An integrated experimental and theoretical reaction path search: analyses of the multistage reaction of an ionized diethylether dimer involving isomerization, proton transfer, and dissociation.

PubMed

Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

2018-05-30

An ionization-induced multistage reaction of an ionized diethylether (DEE) dimer involving isomerization, proton transfer, and dissociation is investigated by combining infrared (IR) spectroscopy, tandem mass spectrometry, and a theoretical reaction path search. The vertically-ionized DEE dimer isomerizes to a hydrogen-bonded cluster of protonated DEE and the [DEE-H] radical through barrierless intermolecular proton transfer from the CH bond of the ionized moiety. This isomerization process is confirmed by IR spectroscopy and the theoretical reaction path search. The multiple dissociation pathways following the isomerization are analyzed by tandem mass spectrometry. The isomerized cluster dissociates stepwise into a [protonated DEE-acetaldehyde (AA)] cluster, protonated DEE, and protonated AA. The structure of the fragment ion is also analyzed by IR spectroscopy. The reaction map of the multistage processes is revealed through a harmony of these experimental and theoretical methods.

Qualitative analysis of seized synthetic cannabinoids and synthetic cathinones by gas chromatography triple quadrupole tandem mass spectrometry.

PubMed

Gwak, Seongshin; Arroyo-Mora, Luis E; Almirall, José R

2015-02-01

Designer drugs are analogues or derivatives of illicit drugs with a modification of their chemical structure in order to circumvent current legislation for controlled substances. Designer drugs of abuse have increased dramatically in popularity all over the world for the past couple of years. Currently, the qualitative seized-drug analysis is mainly performed by gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) in which most of these emerging designer drug derivatives are extensively fragmented not presenting a molecular ion in their mass spectra. The absence of molecular ion and/or similar fragmentation pattern among these derivatives may cause the equivocal identification of unknown seized-substances. In this study, the qualitative identification of 34 designer drugs, mainly synthetic cannabinoids and synthetic cathinones, were performed by gas chromatography-triple quadrupole-tandem mass spectrometry with two different ionization techniques, including electron ionization (EI) and chemical ionization (CI) only focusing on qualitative seized-drug analysis, not from the toxicological point of view. The implementation of CI source facilitates the determination of molecular mass and the identification of seized designer drugs. Developed multiple reaction monitoring (MRM) mode may increase sensitivity and selectivity in the analysis of seized designer drugs. In addition, CI mass spectra and MRM mass spectra of these designer drug derivatives can be used as a potential supplemental database along with EI mass spectral database. Copyright © 2014 John Wiley & Sons, Ltd.

Ionization Cross Sections and Dissociation Channels of the DNA Sugar-Phosphate Backbone by Electron Collisions

NASA Technical Reports Server (NTRS)

Dateo, Christopher; Huo, Winifred M.; Fletcher, Graham D.

2004-01-01

It has been suggested that the genotoxic effects of ionizing radiation in living cells are not caused by the highly energetic incident radiation, but rather are induced by less energetic secondary species generated, the most abundant of which are free electrons.' The secondary electrons will further react to cause DNA damage via indirect and direct mechanisms. Detailed knowledge of these mechanisms is ultimately important for the development of global models of cellular radiation damage. We are studying one possible mechanism for the formation cf DNA strand breaks involving dissociative ionization of the DNA sugar-phosphate backbone induced by secondary electron co!lisions. We will present ionization cross sections at electron collision energies between threshold and 10 KeV using the improved binary encounter dipole (iBED) formulation' Preliminary results of the possible dissociative ionization pathways will be presented. It is speculated that radical fragments produced from the dissociative ionization can further react, providing a possible mechanism for double strand breaks and base damage.

Giant plasmon excitation in single and double ionization of C60 by fast highly charged Si and O ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Tribedi, L. C.

2007-09-01

Se have investigated single and double ionization of C60 molecule in collisions with 2.33 MeV/u Siq+ (q=6-14) and 3.125 MeV/u Oq+ (q=5-8) projectiles. The projectile charge state dependence of the single and double ionization yields of C60 are then compared to those for an ion-atom collision system using Ne gas as a target. A large difference between the gas and the cluster target behaviour was partially explained in terms of a model based on collective excitation namely the giant dipole plasmon resonance (GDPR). The qualitative agreement between the data and GDPR model prediction for single and double ionization signifies the importance of single and double plasmon excitations in the ionization process. A large deviation of the GDPR model for triple and quadruple ionization from the experimental data imply the importance of the other low impact parameter processes such as evaporation, fragmentation and a possible solid-like dynamical screening.

Hydrogen rearrangements in the fragmentation of anthracene by low-energy electron impact

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Dunne, Melissa; Gradziel, Marcin L.

2018-02-01

We have measured mass spectra for positive ions produced by low-energy electron impact on anthracene using a reflectron time-of-flight mass spectrometer. The electron impact energy has been varied from 0 to 100 eV in steps of 0.5 eV. Ion yield curves of most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. Appearance energies for all these ions have been determined, and we report the first direct measurement of the triple ionization energy of anthracene at 45.5±0.5 eV. The groups of fragments containing 8-13 carbon atoms provide evidence for hydrogen rearrangements during the fragmentation, involving retention or loss of one or two additional hydrogen atoms. Groups of fragments with 6 and 7 carbon atoms clearly show the presence of doubly-charged fragments. The smaller fragments with 1-4 carbon atoms all show broadened peaks, and these fragments may be partly or mostly due to energetic charge-separation fragmentations of doubly-charged anthracene.

Ecological impacts of tropical forest fragmentation: how consistent are patterns in species richness and nestedness?

PubMed

Hill, Jane K; Gray, Michael A; Khen, Chey Vun; Benedick, Suzan; Tawatao, Noel; Hamer, Keith C

2011-11-27

Large areas of tropical forest now exist as remnants scattered across agricultural landscapes, and so understanding the impacts of forest fragmentation is important for biodiversity conservation. We examined species richness and nestedness among tropical forest remnants in birds (meta-analysis of published studies) and insects (field data for fruit-feeding Lepidoptera (butterflies and moths) and ants). Species-area relationships were evident in all four taxa, and avian and insect assemblages in remnants typically were nested subsets of those in larger areas. Avian carnivores and nectarivores and predatory ants were more nested than other guilds, implying that the sequential loss of species was more predictable in these groups, and that fragmentation alters the trophic organization of communities. For butterflies, the ordering of fragments to achieve maximum nestedness was by fragment area, suggesting that differences among fragments were driven mainly by extinction. In contrast for moths, maximum nestedness was achieved by ordering species by wing length; species with longer wings (implying better dispersal) were more likely to occur at all sites, including low diversity sites, suggesting that differences among fragments were driven more strongly by colonization. Although all four taxa exhibited high levels of nestedness, patterns of species turnover were also idiosyncratic, and thus even species-poor sites contributed to landscape-scale biodiversity, particularly for insects.

Ecological impacts of tropical forest fragmentation: how consistent are patterns in species richness and nestedness?

PubMed Central

Hill, Jane K.; Gray, Michael A.; Khen, Chey Vun; Benedick, Suzan; Tawatao, Noel; Hamer, Keith C.

2011-01-01

Large areas of tropical forest now exist as remnants scattered across agricultural landscapes, and so understanding the impacts of forest fragmentation is important for biodiversity conservation. We examined species richness and nestedness among tropical forest remnants in birds (meta-analysis of published studies) and insects (field data for fruit-feeding Lepidoptera (butterflies and moths) and ants). Species–area relationships were evident in all four taxa, and avian and insect assemblages in remnants typically were nested subsets of those in larger areas. Avian carnivores and nectarivores and predatory ants were more nested than other guilds, implying that the sequential loss of species was more predictable in these groups, and that fragmentation alters the trophic organization of communities. For butterflies, the ordering of fragments to achieve maximum nestedness was by fragment area, suggesting that differences among fragments were driven mainly by extinction. In contrast for moths, maximum nestedness was achieved by ordering species by wing length; species with longer wings (implying better dispersal) were more likely to occur at all sites, including low diversity sites, suggesting that differences among fragments were driven more strongly by colonization. Although all four taxa exhibited high levels of nestedness, patterns of species turnover were also idiosyncratic, and thus even species-poor sites contributed to landscape-scale biodiversity, particularly for insects. PMID:22006967

Is forest fragmentation driven by the spatial configuration of land quality? The case of western Oregon.

Treesearch

Ralph J. Alig; David J. Lewis; Jennifer J. Swenson

2005-01-01

We investigated spatial configuration of economic returns, to enhance models of forest fragmentation for western Oregon and western Washington. Drawing from spatial land rent theory, economic drivers of forest fragmentation at the landscape level include land quality comprised of attributes such as soil fertility or the distance of urban plots to amenities. We included...

Characterization of aromatic organosulfur model compounds relevant to fossil fuels by using atmospheric pressure chemical ionization with CS2 and high-resolution tandem mass spectrometry.

PubMed

Tang, Weijuan; Sheng, Huaming; Jin, Chunfen; Riedeman, James S; Kenttämaa, Hilkka I

2016-04-15

The chemistry of desulfurization involved in processing crude oil is greatly dependent on the forms of sulfur in the oil. Sulfur exists in different chemical bonding environments in fossil fuels, including those in thiophenes and benzothiophenes, thiols, sulfides, and disulfides. In this study, the fragmentation behavior of the molecular ions of 17 aromatic organosulfur compounds with various functionalities was systematically investigated by using high-resolution tandem mass spectrometry. Multiple-stage tandem mass spectrometric experiments were carried out using a linear quadrupole ion trap (LQIT) equipped with an atmospheric pressure chemical ionization (APCI) source. (+)APCI/CS2 was used to generate stable dominant molecular ions for all the compounds studied except for three sulfides that also showed abundant fragment ions. The LQIT coupled with an orbitrap mass spectrometer was used for elemental composition analysis, which facilitated the identification of the neutral molecules lost during fragmentation. The characteristic fragment ions generated in MS(2) and MS(3) experiments provide clues for the chemical bonding environment of sulfur atoms in the examined compounds. Upon collision-induced dissociation (CID), the molecular ions can lose the sulfur atom in a variety of ways, including as S (32 Da), HS(•) (33 Da), H2 S (34 Da), CS (44 Da), (•) CHS (45 Da) and CH2 S (46 Da). These neutral fragments are not only indicative of the presence of sulfur, but also of the type of sulfur present in the compound. Generally, losses of HS(•) and H2 S were found to be associated with compounds containing saturated sulfur functionalities, while losses of S, CS and (•) CHS were more common for heteroaromatic sulfur compounds. High-resolution tandem mass spectrometry with APCI/CS2 ionization is a viable approach to determining the types of organosulfur compounds. It can potentially be applied to analysis of complex mixtures, which is beneficial to improving the desulfurization process of fossil fuels. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

Energy and charge transfer in ionized argon coated water clusters.

PubMed

Kočišek, J; Lengyel, J; Fárník, M; Slavíček, P

2013-12-07

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H2O)n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar(+) and water occurs above the threshold; at higher electron energies above ~28 eV, an excitonic transfer process between Ar(+)* and water opens leading to new products Ar(n)H(+) and (H2O)(n)H(+). On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H2O)(n)H2(2+) and (H2O)(n)(2+) ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent.

Distinguishing between relaxation pathways by combining dissociative ionization pump probe spectroscopy and ab initio calculations: a case study of cytosine.

PubMed

Kotur, Marija; Weinacht, Thomas C; Zhou, Congyi; Kistler, Kurt A; Matsika, Spiridoula

2011-05-14

We present a general method for tracking molecular relaxation along different pathways from an excited state down to the ground state. We follow the excited state dynamics of cytosine pumped near the S(0)-S(1) resonance using ultrafast laser pulses in the deep ultraviolet and probed with strong field near infrared pulses which ionize and dissociate the molecules. The fragment ions are detected via time of flight mass spectroscopy as a function of pump probe delay and probe pulse intensity. Our measurements reveal that different molecular fragments show different timescales, indicating that there are multiple relaxation pathways down to the ground state. We interpret our measurements with the help of ab initio electronic structure calculations of both the neutral molecule and the molecular cation for different conformations en route to relaxation back down to the ground state. Our measurements and calculations show passage through two seams of conical intersections between ground and excited states and demonstrate the ability of dissociative ionization pump probe measurements in conjunction with ab initio electronic structure calculations to track molecular relaxation through multiple pathways.

DFT-Supported Threshold Ionization Study of Chromium Biphenyl Complexes: Unveiling the Mechanisms of Substituent Influence on Redox Properties of Sandwich Compounds.

PubMed

Ketkov, Sergey Yu; Tzeng, Sheng-Yuan; Wu, Pei-Ying; Markin, Gennady V; Tzeng, Wen-Bih

2017-10-04

High-resolution mass-analyzed threshold ionization (MATI) spectra of (η 6 -Ph 2 ) 2 Cr and (η 6 -Ph 2 )(η 6 -PhMe)Cr demonstrate that the Ph groups work as electron donors, decreasing the ionization energy of the gas-phase bisarene complexes. In contrast to electrochemical data, a close similarity of the Ph and Me group effects on the oxidation of free sandwich molecules has been revealed. However, DFT calculations testify for the opposite shifts of the electron density caused by the Me and Ph substituents in the neutral complexes, the latter behaving as an electron-accepting fragment. On the contrary, in the bisarene cations, the Ph group becomes a stronger donor than methyl. This change provides the similar substituent effects observed with the MATI experiment. On the other hand, the well-documented opposite influence of the Me and Ph fragments on the redox potential of the (η 6 -arene) 2 Cr +/0 couple in solution appears to be a result of solvation effects but not intramolecular interactions as shown for the first time in this work. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

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

Shukla, Anil; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry. Singly as well as multiply charged clusters were formed with the general formulae, (HCOOLi)nLi+, (HCOOLi)nLimm+, (HCOOLi)nHCOO- and (HCOOLi)n(HCOO)mm-. Several magic number cluster ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)3Li+ being the most abundant and stable cluster ions. Fragmentations of singly charged clusters proceed first by the loss of a dimer unit ((HCOOLi)2) followed by sequential loss of monomer units (HCOOLi). In the case ofmore » positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)3Li+ at higher collision energies which later fragments to dimer and monomer ions in lower abundance. Quantum mechanical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Transfer Ionization Studies for Proton on He - new Inside into the World of Correlation

NASA Astrophysics Data System (ADS)

Schmidt-Böcking, Horst

2005-04-01

Correlated many-particle dynamics in Coulombic systems, which is one of the unsolved fundamental problems in AMO-physics, can now be experimentally approached with so far unprecedented completeness and precision. The recent development of the COLTRIMS technique (COLd Target Recoil Ion Momentum Spectroscopy) provides a coincident multi-fragment imaging technique for eV and sub-eV fragment detection. In its completeness it is as powerful as the bubble chamber in high energy physics. In recent benchmark experiments quasi snapshots (duration as short an atto-sec) of the correlated dynamics between electrons and nuclei has been made for atomic and molecular objects. This new imaging technique has opened a powerful observation window into the hidden world of many-particle dynamics. Recent transfer ionization studies will be presented and the direct observation of correlated electron pairs will be discussed.

Absolute total and partial dissociative cross sections of pyrimidine at electron and proton intermediate impact velocities

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

Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Sigaud, Lucas

Absolute total non-dissociative and partial dissociative cross sections of pyrimidine were measured for electron impact energies ranging from 70 to 400 eV and for proton impact energies from 125 up to 2500 keV. MOs ionization induced by coulomb interaction were studied by measuring both ionization and partial dissociative cross sections through time of flight mass spectrometry and by obtaining the branching ratios for fragment formation via a model calculation based on the Born approximation. The partial yields and the absolute cross sections measured as a function of the energy combined with the model calculation proved to be a useful toolmore » to determine the vacancy population of the valence MOs from which several sets of fragment ions are produced. It was also a key point to distinguish the dissociation regimes induced by both particles. A comparison with previous experimental results is also presented.« less

Elucidating the mass spectrum of the retronecine alkaloid using DFT calculations.

PubMed

Modesto-Costa, Lucas; Martinez, Sabrina T; Pinto, Angelo C; Vessecchi, Ricardo; Borges, Itamar

2018-06-23

Pyrrolizidine alkaloids are natural molecules playing important roles in different biochemical processes in nature and in humans. In this work, the electron ionization mass spectrum (EI-MS) of retronecine, an alkaloid molecule found in plants, is investigated computationally. Its mass spectrum can be characterized by three main fragment ions having the following m/z ratios: 111, 94 and 80. In order to rationalize the mass spectrum, minima and transition state geometries were computed using density functional theory (DFT). It was showed that the dissociation process includes an aromatization of the originally five-membered ring of retronecine converted into a six-membered ring compound. A fragmentation pathway mechanism involving dissociation activation barriers that are easily overcome by the initial ionization energy was found. From the computed quantum chemical geometric, atomic charges and energetic parameters, the abundance of each ion in the mass spectrum of retronecine was discussed. This article is protected by copyright. All rights reserved.

Characterization of polymethoxylated flavones in Fructus aurantii by liquid chromatography with atmospheric pressure chemical ionization combined with tandem mass spectrometry.

PubMed

Zhou, Da-Yong; Chen, De-Liang; Xu, Qing; Xue, Xing-Ya; Zhang, Fei-Fang; Liang, Xin-Miao

2007-04-11

Atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was operated in positive mode (PI) to characterize polymethoxylated flavonoids (PMFs) through its specific radical cations by collision-induced dissociation (CID). The fragments of [M + H - n x 15]+ produced by loss of one or more methyl group from the protonated molecule, as well as [M + H - 29]+, [M + H - 31]+, [M + H - 33]+, [M + H - 43]+, [M + H - 46]+, and [M + H - 61]+ fragment ions were detected, which were diagnostic for the polymethoxylated species, and could be adopted to form the multiple MS (MS(n)) "fingerprint" of PMFs. Based on this "fingerprint", 29 PMFs were screened out from extracts of Fructus aurantii, among which two of them were identified as sinensetin and tangeretin. It was proved that the PI was suitable for structural characterization of PMFs by APCI-MS(n).

Accurate Mass Fragment Library for Rapid Analysis of Pesticides on Produce Using Ambient Pressure Desorption Ionization with High-Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Kern, Sara E.; Lin, Lora A.; Fricke, Frederick L.

2014-08-01

U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]+) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]+ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]+ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The minimal sample preparation and absence of chromatography has shortened the analysis time to about 15 min per sample, and the simplicity and robustness of the technique make it ideal for rapid screening.

On fragmentation of turbulent self-gravitating discs in the long cooling time regime

NASA Astrophysics Data System (ADS)

Rice, Ken; Nayakshin, Sergei

2018-03-01

It has recently been suggested that in the presence of driven turbulence discs may be much less stable against gravitational collapse than their non-turbulent analogues, due to stochastic density fluctuations in turbulent flows. This mode of fragmentation would be especially important for gas giant planet formation. Here, we argue, however, that stochastic density fluctuations due to turbulence do not enhance gravitational instability and disc fragmentation in the long cooling time limit appropriate for planet forming discs. These fluctuations evolve adiabatically and dissipate away by decompression faster than they could collapse. We investigate these issues numerically in two dimensions via shearing box simulations with driven turbulence and also in three dimensions with a model of instantaneously applied turbulent velocity kicks. In the former setting turbulent driving leads to additional disc heating that tends to make discs more, rather than less, stable to gravitational instability. In the latter setting, the formation of high-density regions due to convergent velocity kicks is found to be quickly followed by decompression, as expected. We therefore conclude that driven turbulence does not promote disc fragmentation in protoplanetary discs and instead tends to make the discs more stable. We also argue that sustaining supersonic turbulence is very difficult in discs that cool slowly.

Coincidence and covariance data acquisition in photoelectron and -ion spectroscopy. I. Formal theory

NASA Astrophysics Data System (ADS)

Mikosch, Jochen; Patchkovskii, Serguei

2013-10-01

We derive a formal theory of noisy Poisson processes with multiple outcomes. We obtain simple, compact expressions for the probability distribution function of arbitrarily complex composite events and its moments. We illustrate the utility of the theory by analyzing properties of coincidence and covariance photoelectron-photoion detection involving single-ionization events. The results and techniques introduced in this work are directly applicable to more general coincidence and covariance experiments, including multiple ionization and multiple-ion fragmentation pathways.

The production of CO(+) (B2Sigma +) from dissociative photoionization excitation of CO2

NASA Technical Reports Server (NTRS)

Wu, C. Y. R.; Judge, D. L.

1986-01-01

The dissociative photoionization excitation process in CO2 is studied. In contrast to previous studies, attention is focused on the vibrational and rotational levels produced in fragment ions, partial cross-section measurements for producing such fragment ions in a specific quantum state, and the mechanisms that govern the dissociative ionization excitation processes. The partial fluorescence cross section for the production of CO(+) (B2Sigma +) from CO2 over a wide wavelength range was measured. It is concluded that the production of the CO(+) (B2Sigma +) fragment near the threshold is through a direct dissociative photoionization process.

Structural characterization and identification of biflavones in Selaginella tamariscina by liquid chromatography-diode-array detection/electrospray ionization tandem mass spectrometry.

PubMed

Zhang, Yi-Xuan; Li, Qiu-Yue; Yan, Li-Li; Shi, Yue

2011-08-15

Biflavonoids, a special class of flavonoids, are widely distributed in gymnosperm plants and have various biological activities. They are also major bioactive ingredients in Selaginella tamariscina. In this work, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) to study the fragmentation behavior of three main types of biflavonoids using seven biflavonoid reference compounds and analyze the biflavonoids in Selaginella tamariscina. The most useful fragmentations in terms of structural identification are those involving the C-ring cleavage of biflavonoids. For amentoflavone-type biflavonoids (containing flavonoid parts I and II), fragmentation on the flavonoid part II at positions 1/3 and 0/4 are the primary pathways, whereas the chances are greater for C-ring cleavage fragmentation occurring on flavonoid part I at positions 1/3 and 1/4 for robustaflavone-type biflavonoids. However, the predominant diagnostic ions of the specific C-O-C-connected hinokiflavone-type biflavonoids are a series of ions resulting from the rupture of the connective C-O bond. Based on the fragmentation patterns of these reference compounds, 17 biflavonoids were identified in an extract of Selaginella tamariscina, three of which have not been previously reported as constituents of this plant. This study provides a powerful approach for the online structural elucidation and identification of different types of biflavonoids and positional isomers from Selaginella tamariscina and other biflavonoids distributed in related plants and prescriptions. Copyright © 2011 John Wiley & Sons, Ltd.

Fragmentation dynamics of ionized neon clusters (Ne(n), n=3-14) embedded in helium nanodroplets.

PubMed

Bonhommeau, David; Halberstadt, Nadine; Viel, Alexandra

2006-01-14

We report a theoretical study of the nonadiabatic fragmentation dynamics of ionized neon clusters embedded in helium nanodroplets for cluster sizes up to n=14 atoms. The dynamics of the neon atoms is modeled using the molecular dynamics with quantum transitions method of Tully [J. Chem. Phys. 93, 1061 (1990)] with the nuclei treated classically and transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model to which induced dipole-induced dipole interactions are added. The effect of the spin-orbit interaction is also discussed. The helium environment is modeled by a friction force acting on charged atoms whose speed exceeds the critical Landau velocity. The dependence of the fragment size distribution on the friction strength and on the initial nanodroplet size is investigated. By comparing with the available experimental data obtained for Ne3+ and Ne4+, a reasonable value for the friction coefficient, the only parameter of the model, is deduced. This value is then used to predict the effect of the helium environment on the dissociation dynamics of larger neon clusters, n=5-14. The results show stabilization of larger fragments than in the gas phase, but fragmentation is not completely caged. In addition, two types of dynamics are characterized for Ne4+: fast and explosive, therefore leaving no time for friction to cool down the process when dynamics starts on one of the highest electronic states, and slower, therefore leading to some stabilization by helium when it starts on one of the lowest electronic states.

Dissociation Behavior of a TEMPO-Active Ester Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS) in Negative ESI-MS.

PubMed

Hage, Christoph; Ihling, Christian H; Götze, Michael; Schäfer, Mathias; Sinz, Andrea

2017-01-01

We have synthesized a homobifunctional amine-reactive cross-linking reagent, containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy) and a benzyl group (Bz), termed TEMPO-Bz-linker, to derive three-dimensional structural information of proteins. The aim for designing this novel cross-linker was to facilitate the mass spectrometric analysis of cross-linked products by free radical initiated peptide sequencing (FRIPS). In an initial study, we had investigated the fragmentation behavior of TEMPO-Bz-derivatized peptides upon collision activation in (+)-electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) experiments. In addition to the homolytic NO-C bond cleavage FRIPS pathway delivering the desired odd-electron product ions, an alternative heterolytic NO-C bond cleavage, resulting in even-electron product ions mechanism was found to be relevant. The latter fragmentation route clearly depends on the protonation of the TEMPO-Bz-moiety itself, which motivated us to conduct (-)-ESI-MS, CID-MS/MS, and MS 3 experiments of TEMPO-Bz-cross-linked peptides to further clarify the fragmentation behavior of TEMPO-Bz-peptide molecular ions. We show that the TEMPO-Bz-linker is highly beneficial for conducting FRIPS in negative ionization mode as the desired homolytic cleavage of the NO-C bond is the major fragmentation pathway. Based on characteristic fragments, the isomeric amino acids leucine and isoleucine could be discriminated. Interestingly, we observed pronounced amino acid side chain losses in cross-linked peptides if the cross-linked peptides contain a high number of acidic amino acids. Graphical Abstract ᅟ.

Multiple product pathways in photodissociation of nitromethane at 213 nm

NASA Astrophysics Data System (ADS)

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

2016-02-01

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π* transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X 2Π, A 2Σ+), and O(3PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 2B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O(3PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A 2Σ+) fragment, which was detected by ionization spectroscopy via the Rydberg ←A 2Σ+ transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π* transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

Multiple product pathways in photodissociation of nitromethane at 213 nm.

PubMed

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi; Kohguchi, Hiroshi

2016-02-14

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π(*) transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X (2)Π, A (2)Σ(+)), and O((3)PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 (2)B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O((3)PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A (2)Σ(+)) fragment, which was detected by ionization spectroscopy via the Rydberg ← A (2)Σ(+) transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π(*) transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.

Exploration of the fragmentation of laser shock-melted aluminum using x-ray backlighting

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

Zhang, Lin, E-mail: zhanglinbox@263.net, E-mail: zhanglinbox@caep.cn; Li, Ying-Hua; Li, Xue-Mei

The fragmentation of shock-melted metal material is an important scientific problem in shock physics and is suitable for experimentally investigating by the laser-driven x-ray backlighting technique. This letter reports on the exploration of laser shock-melted aluminum fragmentation by means of x-ray backlighting at the SGII high energy facility in China. High-quality and high-resolution radiographs with negligible motion blur were obtained and these images enabled analysis of the mass distribution of the fragmentation product.

Top-Down Hydrogen-Deuterium Exchange Analysis of Protein Structures Using Ultraviolet Photodissociation.

PubMed

Brodie, Nicholas I; Huguet, Romain; Zhang, Terry; Viner, Rosa; Zabrouskov, Vlad; Pan, Jingxi; Petrotchenko, Evgeniy V; Borchers, Christoph H

2018-03-06

Top-down hydrogen-deuterium exchange (HDX) analysis using electron capture or transfer dissociation Fourier transform mass spectrometry (FTMS) is a powerful method for the analysis of secondary structure of proteins in solution. The resolution of the method is a function of the degree of fragmentation of backbone bonds in the proteins. While fragmentation is usually extensive near the N- and C-termini, electron capture (ECD) or electron transfer dissociation (ETD) fragmentation methods sometimes lack good coverage of certain regions of the protein, most often in the middle of the sequence. Ultraviolet photodissociation (UVPD) is a recently developed fast-fragmentation technique, which provides extensive backbone fragmentation that can be complementary in sequence coverage to the aforementioned electron-based fragmentation techniques. Here, we explore the application of electrospray ionization (ESI)-UVPD FTMS on an Orbitrap Fusion Lumos Tribrid mass spectrometer to top-down HDX analysis of proteins. We have incorporated UVPD-specific fragment-ion types and fragment-ion mixtures into our isotopic envelope fitting software (HDX Match) for the top-down HDX analysis. We have shown that UVPD data is complementary to ETD, thus improving the overall resolution when used as a combined approach.

Regiones Extendidas de gas ionizado en radiogalaxias FR II. Estudio espectroscópico y cinemático.

NASA Astrophysics Data System (ADS)

Reynaldi, V.; Feinstein, C.

The EELR are regions of highly-excited ionized gas that extend throughout the outskirts of their host galaxies. Concerning FR II radio galaxies, alignment between optical and radio structures were found for several sources. We investigate the ionizing mechanisms of these regions through long-slit spectroscopic analysis. Photoionization models, where both the AGN and a mixed intergalactic medium may explain the ionization state of the regions are studied. But also the shock-ionization model is tested since it can provide a local budget of ionizing photons created by expanding radiative shock waves driven by the radio jet. Throughout this work we discuss spectroscopic and kinematical results obtained with GMOS/Gemini. FULL TEXT IN SPANISH

Slow Photoelectron Spectroscopy and State-Selected Unimolecular Decomposition of Ionized DNA Bases Analogues

NASA Astrophysics Data System (ADS)

Mahjoub, Ahmed; Hochlaf, Majdi; Poisson, Lionel; Garcia, Gustavo A.; Nahon, Laurent

2013-06-01

We studied the single-photon ionization of gas-phase 2-Piperidone (DNA basis analogue) and of its dimer using vacuum-ultraviolet (VUV) synchrotron radiation coupled to a velocity map imaging electron/ion coincidence spectrometer The slow photoelectron spectrum (SPES) of the monomer is dominated by the vibrational transitions to the ground state. These spectra are assigned with the help of theoretical calculations dealing with the equilibrium geometries, electronic-state patterns and evolutions, harmonic and anharmonic wavenumbers. After its formation, dimer is subject of intramolecular isomerization, H transfer and then unimolecular fragmentation processes. The near threshold photofragmentation pattern of the cationic 2-Piperidone cation and its dimer has been recorded. The experimental method yields the fragment intensity as a function of the internal energy deposited into the parent cation. In parallel, ab initio studies on ionic and neutral fragmentation products have been performed with the aim of determining the isomers of the ionic products observed experimentally as well as of their neutral counterparts. L. Nahon, N. De Oliveria,J. F. Gil,B. Pilette,O. Marcouillé, B. La garde and F. Polack Journal of Synchrotron Radiation {19}(4), 508-520; 2012

Quantitation of lysergic acid diethylamide in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry.

PubMed

Cui, Meng; McCooeye, Margaret A; Fraser, Catharine; Mester, Zoltán

2004-12-01

A quantitative method was developed for analysis of lysergic acid diethylamide (LSD) in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry (AP MALDI-ITMS). Following solid-phase extraction of LSD from urine samples, extracts were analyzed by AP MALDI-ITMS. The identity of LSD was confirmed by fragmentation of the [M + H](+) ion using tandem mass spectrometry. The quantification of LSD was achieved using stable-isotope-labeled LSD (LSD-d(3)) as the internal standard. The [M + H](+) ion fragmented to produce a dominant fragment ion, which was used for a selected reaction monitoring (SRM) method for quantitative analysis of LSD. SRM was compared with selected ion monitoring and produced a wider linear range and lower limit of quantification. For SRM analysis of samples of LSD spiked in urine, the calibration curve was linear in the range of 1-100 ng/mL with a coefficient of determination, r(2), of 0.9917. This assay was used to determine LSD in urine samples and the AP MALDI-MS results were comparable to the HPLC/ ESI-MS results.

Spatial Characterization of Polycyclic Aromatic Hydrocarbons in 2008 TC3 Samples

NASA Astrophysics Data System (ADS)

Sabbah, Hassan; Morrow, A.; Zare, R. N.; Jenniskens, P.

2009-09-01

Hassan Sabbah1, Amy L. Morrow1, Richard N. Zare1 and Petrus Jenniskens2 1Stanford University, Stanford, California 94305, 2 SETI Institute, Carl Sagan Center, 515 North Whisman Road, Mountain View, California 94043, USA. In October 2006 a small asteroid (2-3 meters) was observed in outer space. On October 7, 2008, it entered the Earth's atmosphere creating a fireball over Northern Sudan. Some 280 meteorites were collected by the University of Khartoum. In order to explore the existence of organic materials, specifically polycyclic aromatic hydrocarbons (PAHs), we applied two-step laser desorption laser ionization mass spectrometry (L2MS) to some selected fragments. This technique consists of desorbing with a pulsed infrared laser beam the solid materials into a gaseous phase with no fragmentation followed by resonance enhanced multiphoton ionization to analyze the PAH content. L2MS was already applied to an array of extraterrestrial objects including interplanetary dust particles IDPs, carbonaceous chondrites and comet coma particles. Moreover, spatial resolution of PAHs in 2008 TC3 samples was achieved to explore the heterogeneity within individual fragments. The results of these studies and their contribution to understanding the formation of this asteroid will be discussed.

Determination of red blood cell fatty acid profiles: Rapid and high-confident analysis by chemical ionization-gas chromatography-tandem mass spectrometry.

PubMed

Schober, Yvonne; Wahl, Hans Günther; Renz, Harald; Nockher, Wolfgang Andreas

2017-01-01

Cellular fatty acid (FA) profiles have been acknowledged as biomarkers in various human diseases. Nevertheless, common FA analysis by gas chromatography mass spectrometry (GC-MS) requires long analysis time. Hence, there is a need for feasible methods for high throughput analysis in clinical studies. FA was extracted from red blood cells (RBC) and derivatized to fatty acid methyl esters (FAME). A method using gas chromatography tandem mass spectrometry (GC-MS/MS) with ammonia-induced chemical ionization (CI) was developed for the analysis of FA profiles in human RBC. We compared this method with classical single GC-MS using electron impact ionization (EI). The FA profiles of 703 RBC samples were determined by GC-MS/MS. In contrast to EI ammonia-induced CI resulted in adequate amounts of molecular ions for further fragmentation of FAME. Specific fragments for confident quantification and fragmentation were determined for 45 FA. The GC-MS/MS method has a total run time of 9min compared to typical analysis times of up to 60min in conventional GC-MS. Intra and inter assay variations were <10% for all FA analyzed. Analysis of RBC FA composition revealed an age-dependent increase of the omega-3 eicosapentaenoic and docosahexaenoic acid, and a decline of the omega-6 linoleic acid with a corresponding rise of the omega-3 index. The combination of ammonia-induced CI and tandem mass spectrometry after GC separation allows for high-throughput, robust and confident analysis of FA profiles in the clinical laboratory. Copyright © 2016. Published by Elsevier B.V.

Pulsed, high-current, in-line reversal electron attachment detector

NASA Technical Reports Server (NTRS)

Bernius, Mark T.; Chutjian, Ara

1989-01-01

A new, pulsed, high-current, in-line reversal electron attachment ionizer/detector is described. The ionizer is capable of delivering a beam of electrons into an electrostatic mirror field to form a planar wall of electrons having zero kinetic energy. Electron attachment to a molecular target at the reversal point produces either parent or fragment negative ions through a zero-energy (s-wave) state. The atomic or molecular ion is pulsed out of the attachment region approximately 2 microsec after the electrons are pulsed off, and focused onto the entrance plane of a quadrupole mass analyzer. The sensitivity of the apparatus is preliminarily assessed, and its higher-energy behavior with regard to molecular attachment and ionization is described.

TRIGGERED STAR FORMATION SURROUNDING WOLF-RAYET STAR HD 211853

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

Liu Tie; Wu Yuefang; Zhang Huawei

The environment surrounding Wolf-Rayet (W-R) star HD 211853 is studied in molecular, infrared, as well as radio, and H I emission. The molecular ring consists of well-separated cores, which have a volume density of 10{sup 3} cm{sup -3} and kinematic temperature {approx}20 K. Most of the cores are under gravitational collapse due to external pressure from the surrounding ionized gas. From the spectral energy distribution modeling toward the young stellar objects, the sequential star formation is revealed on a large scale in space spreading from the W-R star to the molecular ring. A small-scale sequential star formation is revealed towardmore » core 'A', which harbors a very young star cluster. Triggered star formations are thus suggested. The presence of the photodissociation region, the fragmentation of the molecular ring, the collapse of the cores, and the large-scale sequential star formation indicate that the 'collect and collapse' process functions in this region. The star-forming activities in core 'A' seem to be affected by the 'radiation-driven implosion' process.« less

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

Ren, Xueguang, E-mail: xue.g.ren@ptb.de; Pflüger, Thomas; Weyland, Marvin

The ionization and fragmentation of methane induced by low-energy (E{sub 0} = 66 eV) electron-impact is investigated using a reaction microscope. The momentum vectors of all three charged final state particles, two outgoing electrons, and one fragment ion, are detected in coincidence. Compared to the earlier study [Xu et al., J. Chem. Phys. 138, 134307 (2013)], considerable improvements to the instrumental mass and energy resolutions have been achieved. The fragment products CH{sub 4}{sup +}, CH{sub 3}{sup +}, CH{sub 2}{sup +}, CH{sup +}, and C{sup +} are clearly resolved. The binding energy resolution of ΔE = 2.0 eV is a factormore » of three better than in the earlier measurements. The fragmentation channels are investigated by measuring the ion kinetic energy distributions and the binding energy spectra. While being mostly in consistence with existing photoionization studies the results show differences including missing fragmentation channels and previously unseen channels.« less

Mercury-induced fragmentation of n-decane and n-undecane in positive mode ion mobility spectrometry.

PubMed

Gunzer, F

2015-09-21

Ion mobility spectrometry is a well-known technique for trace gas analysis. Using soft ionization techniques, fragmentation of analytes is normally not observed, with the consequence that analyte spectra of single substances are quite simple, i.e. showing in general only one peak. If the concentration is high enough, an extra cluster peak involving two analyte molecules can often be observed. When investigating n-alkanes, different results regarding the number of peaks in the spectra have been obtained in the past using this spectrometric technique. Here we present results obtained when analyzing n-alkanes (n-hexane to n-undecane) with a pulsed electron source, which show no fragmentation or clustering at all. However, when investigating a mixture of mercury and an n-alkane, a situation quite typical in the oil and gas industry, a strong fragmentation and cluster formation involving these fragments has been observed exclusively for n-decane and n-undecane.

TWO-STAGE FRAGMENTATION FOR CLUSTER FORMATION: ANALYTICAL MODEL AND OBSERVATIONAL CONSIDERATIONS

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

Bailey, Nicole D.; Basu, Shantanu, E-mail: nwityk@uwo.ca, E-mail: basu@uwo.ca

2012-12-10

Linear analysis of the formation of protostellar cores in planar magnetic interstellar clouds shows that molecular clouds exhibit a preferred length scale for collapse that depends on the mass-to-flux ratio and neutral-ion collision time within the cloud. We extend this linear analysis to the context of clustered star formation. By combining the results of the linear analysis with a realistic ionization profile for the cloud, we find that a molecular cloud may evolve through two fragmentation events in the evolution toward the formation of stars. Our model suggests that the initial fragmentation into clumps occurs for a transcritical cloud onmore » parsec scales while the second fragmentation can occur for transcritical and supercritical cores on subparsec scales. Comparison of our results with several star-forming regions (Perseus, Taurus, Pipe Nebula) shows support for a two-stage fragmentation model.« less

Gas chromatography coupled to atmospheric pressure ionization mass spectrometry (GC-API-MS): review.

PubMed

Li, Du-Xin; Gan, Lin; Bronja, Amela; Schmitz, Oliver J

2015-09-03

Although the coupling of GC/MS with atmospheric pressure ionization (API) has been reported in 1970s, the interest in coupling GC with atmospheric pressure ion source was expanded in the last decade. The demand of a "soft" ion source for preserving highly diagnostic molecular ion is desirable, as compared to the "hard" ionization technique such as electron ionization (EI) in traditional GC/MS, which fragments the molecule in an extensive way. These API sources include atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), atmospheric pressure laser ionization (APLI), electrospray ionization (ESI) and low temperature plasma (LTP). This review discusses the advantages and drawbacks of this analytical platform. After an introduction in atmospheric pressure ionization the review gives an overview about the history and explains the mechanisms of various atmospheric pressure ionization techniques used in combination with GC such as APCI, APPI, APLI, ESI and LTP. Also new developments made in ion source geometry, ion source miniaturization and multipurpose ion source constructions are discussed and a comparison between GC-FID, GC-EI-MS and GC-API-MS shows the advantages and drawbacks of these techniques. The review ends with an overview of applications realized with GC-API-MS. Copyright © 2015. Published by Elsevier B.V.

Kinetics of a Migration-Driven Aggregation-Fragmentation Process

NASA Astrophysics Data System (ADS)

Zhuang, You-Yi; Lin, Zhen-Quan; Ke, Jian-Hong

2003-08-01

We propose a reversible model of the migration-driven aggregation-fragmentation process with the symmetric migration rate kernels K(k;j)=K^'(k;j)=λ kj^v and the constant aggregation rates I1, I2 and fragmentation rates J1, J2. Based on the mean-field theory, we investigate the evolution behavior of the aggregate size distributions in several cases with different values of index υ. We find that the fragmentation reaction plays a more important role in the kinetic behaviors of the system than the aggregation and migration. When J1=0 and J2 =0, the aggregate size distributions ak(t) and bk(t) obey the conventional scaling law, while when J1>0 and J2>0, they obey the modified scaling law with an exponential scaling function. The total mass of either species remains conserved. The project supported by National Natural Science Foundation of China under Grant Nos. 10275048 and 10175008, and Natural Science Foundation of Zhejiang Province of China under Grant No. 102067

The fragmentation of 510 MeV/nucleon iron-56 in polyethylene. II. Comparisons between data and a model

NASA Technical Reports Server (NTRS)

Zeitlin, C.; Heilbronn, L.; Miller, J.; Schimmerling, W.; Townsend, L. W.; Tripathi, R. K.; Wilson, J. W.

1996-01-01

The results of a Monte Carlo model for calculating fragment fluences and LET spectra are compared to data taken with 600 MeV/nucleon iron ions incident on an accelerator beamline configured for irradiation of biological samples, with no target and with 2, 5 and 8 cm of polyethylene. The model uses a multi-generation nuclear fragmentation code, coupled with a formulation of ionization energy loss based on the Bethe-Bloch equation. In the region where the data are reliable and the experimental acceptance is well understood, many of the features of the experimental spectra are well replicated by the model. To obtain good agreement with the experimental data, the model must allow for at least two generations of fragment production in the target.

A novel informatics concept for high-throughput shotgun lipidomics based on the molecular fragmentation query language

PubMed Central

2011-01-01

Shotgun lipidome profiling relies on direct mass spectrometric analysis of total lipid extracts from cells, tissues or organisms and is a powerful tool to elucidate the molecular composition of lipidomes. We present a novel informatics concept of the molecular fragmentation query language implemented within the LipidXplorer open source software kit that supports accurate quantification of individual species of any ionizable lipid class in shotgun spectra acquired on any mass spectrometry platform. PMID:21247462

Silver-gold alloy nanoparticles as tunable substrates for systematic control of ion-desorption efficiency and heat transfer in surface-assisted laser desorption/ionization.

PubMed

Lai, Samuel Kin-Man; Cheng, Yu-Hong; Tang, Ho-Wai; Ng, Kwan-Ming

2017-08-09

Systematically controlling heat transfer in the surface-assisted laser desorption/ionization (SALDI) process and thus enhancing the analytical performance of SALDI-MS remains a challenging task. In the current study, by tuning the metal contents of Ag-Au alloy nanoparticle substrates (AgNPs, Ag55Au45NPs, Ag15Au85NPs and AuNPs, ∅: ∼2.0 nm), it was found that both SALDI ion-desorption efficiency and heat transfer can be controlled in a wide range of laser fluence (21.3 mJ cm -2 to 125.9 mJ cm -2 ). It was discovered that ion detection sensitivity can be enhanced at any laser fluence by tuning up the Ag content of the alloy nanoparticle, whereas the extent of ion fragmentation can be reduced by tuning up the Au content. The enhancement effect of Ag content on ion desorption was found to be attributable to the increase in laser absorption efficiency (at 355 nm) with Ag content. Tuning the laser absorption efficiency by changing the metal composition was also effective in controlling the heat transfer from the NPs to the analytes. The laser-induced heating of Ag-rich alloy NPs could be balanced or even overridden by increasing the Au content of NPs, resulting in the reduction of the fragmentation of analytes. In the correlation of experimental measurement with molecular dynamics simulation, the effect of metal composition on the dynamics of the ion desorption process was also elucidated. Upon increasing the Ag content, it was also found that phase transition temperatures, such as melting, vaporization and phase explosion temperature, of NPs could be reduced. This further enhanced the desorption of analyte ions via phase-transition-driven desorption processes. The significant cooling effect on the analyte ions observed at high laser fluence was also determined to be originated from the phase explosion of the NPs. This study revealed that the development of alloy nanoparticles as SALDI substrates can constitute an effective means for the systematic control of ion-desorption efficiency and the extent of heat transfer, which could potentially enhance the analytical performance of SALDI-MS.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

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

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

PubMed Central

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; Fang, Yigang; Kostko, Oleg

2017-01-01

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion–molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2)n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion–molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM. PMID:28484019

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

PubMed

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

2017-05-23

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Ionization and dissociation of molecular ion beams by intense ultrafast laser pulses

NASA Astrophysics Data System (ADS)

Ben-Itzhak, Itzik

2007-06-01

Laser-induced dissociation and ionization of a diatomic molecular-ion beam were simultaneously measured using coincidence 3D momentum imaging, with direct separation of the two processes even where the fragment kinetic energy is the same for both processes. We mainly focus on the fundamental H2^+ molecule in 7-135 fs laser pulses having 10^13-10^15 W/cm^2 peak intensity. At high intensities the kinetic energy release (KER) distribution following ionization of H2^+ was measured to be broad and structureless. Its centroid shifts toward higher energies as the laser intensity is increased indicating that ionization shifts to smaller internuclear distances. In contrast, a surprising structure is observed near the ionization threshold, which we call above threshold Coulomb explosion (ATCE) [1]. The angular distributions of the two H^+ fragments are strongly peaked along the laser polarization, and the angular distribution is described well by [cos^2θ]^n, where n is the number of photons predicted by our ATCE model [1]. Our data indicates that n varies with the laser wavelength as predicted by the model. The KER and angular distributions of H2^+ dissociation change dramatically with decreasing pulse width over the 7-135 fs range in contrast to the reported trend for longer pulses. Others contributing to this work: A.M. Sayler, P.Q. Wang, J. McKenna, B. Gaire, Nora G. Johnson, E. Parke, K.D. Carnes, and B.D. Esry. Thank are due to Professor Zenghu Chang for providing the intense laser beams and Dr. Charles Fehrenbach for his help with the ion beams. [1] B.D. Esry, A.M. Sayler, P.Q. Wang, K.D. Carnes, and I. Ben-Itzhak, Phys. Rev. Lett. 97, 013003 (2006).

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE PAGES

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; ...

2017-05-08

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Time-dependent quantum chemistry of laser driven many-electron molecules

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

Nguyen-Dang, Thanh-Tung; Couture-Bienvenue, Étienne; Viau-Trudel, Jérémy

2014-12-28

A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied tomore » calculate the detailed, sub-cycle electronic dynamics of BeH{sub 2}, treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10{sup 15} W/cm{sup 2}), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.« less

Fragment-Based Drug Discovery of Potent Protein Kinase C Iota Inhibitors.

PubMed

Kwiatkowski, Jacek; Liu, Boping; Tee, Doris Hui Ying; Chen, Guoying; Ahmad, Nur Huda Binte; Wong, Yun Xuan; Poh, Zhi Ying; Ang, Shi Hua; Tan, Eldwin Sum Wai; Ong, Esther Hq; Nurul Dinie; Poulsen, Anders; Pendharkar, Vishal; Sangthongpitag, Kanda; Lee, May Ann; Sepramaniam, Sugunavathi; Ho, Soo Yei; Cherian, Joseph; Hill, Jeffrey; Keller, Thomas H; Hung, Alvin W

2018-05-24

Protein kinase C iota (PKC-ι) is an atypical kinase implicated in the promotion of different cancer types. A biochemical screen of a fragment library has identified several hits from which an azaindole-based scaffold was chosen for optimization. Driven by a structure-activity relationship and supported by molecular modeling, a weakly bound fragment was systematically grown into a potent and selective inhibitor against PKC-ι.

Gas Flows in Dual Active Galactic Nuclei

NASA Astrophysics Data System (ADS)

Mueller Sanchez, Francisco; Comerford, Julia M.; Davies, Richard; Treister, Ezequiel; Privon, George C.; Nevin, Becky

2018-06-01

Dual Active Galactic Nuclei (AGN) are the Rosetta stone to understand the role of galaxy mergers in triggering nuclear activity and regulating black hole (BH) and galaxy growth. But very little is known about the physical processes required to effectively trigger AGN activity and regulate the growth of the two BHs. The work I will present here characterizes for the first time the properties of the stars, gas (molecular, ionized, and highly-ionized) and dust in all the confirmed dual AGN at z < 0.05, using Keck/OSIRIS, VLT/SINFONI, SOFIA/FORCAST, and HST data. I will focus on the interplay between the several complex processes observed in dual AGN, using as an example the prototypical merger system NGC 6240: vigorous star formation, two AGNs, outflowing winds of ionized gas, rippling dust and gas lanes, and tidal tails. In this galaxy, we observe for the first time a dual outflow of different species of gas: an AGN-driven outflow of highly-ionized gas to the northeast and a starburst-driven outflow of ionized hydrogen to the northwest. This shows that stellar feedback and supermassive black hole feedback can work in tandem to regulate the stellar growth of a galaxy after a merger event. These results open a new door to studies of dual AGN and AGN pairs in general, and enable dual AGN to be used, for the first time, for studies of galaxy evolution.

Molecular Data for a Biochemical Model of DNA Radiation Damage: Electron Impact Ionization and Dissociative Ionization of DNA Bases and Sugar-Phosphate Backbone

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Fletcher, Graham D.

2004-01-01

As part of the database for building up a biochemical model of DNA radiation damage, electron impact ionization cross sections of sugar-phosphate backbone and DNA bases have been calculated using the improved binary-encounter dipole (iBED) model. It is found that the total ionization cross sections of C3'- and C5'-deoxyribose-phospate, two conformers of the sugar-phosphate backbone, are close to each other. Furthermore, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 10%. Of the four DNA bases, the ionization cross section of guanine is the largest, then in decreasing order, adenine, thymine, and cytosine. The order is in accordance with the known propensity of oxidation of the bases by ionizing radiation. Dissociative ionization (DI), a process that both ionizes and dissociates a molecule, is investigated for cytosine. The DI cross section for the formation of H and (cytosine-Hl)(+), with the cytosine ion losing H at the 1 position, is also reported. The threshold of this process is calculated to be 17.1 eV. Detailed analysis of ionization products such as in DI is important to trace the sequential steps in the biochemical process of DNA damage.

C-I···π Halogen Bonding Driven Supramolecular Helix of Bilateral N-Amidothioureas Bearing β-Turns.

PubMed

Cao, Jinlian; Yan, Xiaosheng; He, Wenbin; Li, Xiaorui; Li, Zhao; Mo, Yirong; Liu, Maili; Jiang, Yun-Bao

2017-05-17

We report the first example of C-I···π halogen bonding driven supramolecular helix in highly dilute solution of micromolar concentration, using alanine based bilateral I-substituted N-amidothioureas that contain helical fragments, the β-turn structures. The halogen bonding interactions afford head-to-tail linkages that help to propagate the helicity of the helical fragments. In support of this action of the halogen bonding, chiral amplification was observed in the supramolecular helix formed in acetonitrile solution. The present finding provides alternative tools in the design of self-assembling macromolecules.

Peptides Labeled with Pyridinium Salts for Sensitive Detection and Sequencing by Electrospray Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Waliczek, Mateusz; Kijewska, Monika; Rudowska, Magdalena; Setner, Bartosz; Stefanowicz, Piotr; Szewczuk, Zbigniew

2016-11-01

Mass spectrometric analysis of trace amounts of peptides may be problematic due to the insufficient ionization efficiency resulting in limited sensitivity. One of the possible ways to overcome this problem is the application of ionization enhancers. Herein we developed new ionization markers based on 2,4,6-triphenylpyridinium and 2,4,6-trimethylpyridinium salts. Using of inexpensive and commercially available pyrylium salt allows selective derivatization of primary amino groups, especially those sterically unhindered, such as ɛ-amino group of lysine. The 2,4,6-triphenylpyridinium modified peptides generate in MS/MS experiments an abundant protonated 2,4,6-triphenylpyridinium ion. This fragment is a promising reporter ion for the multiple reactions monitoring (MRM) analysis. In addition, the fixed positive charge of the pyridinium group enhances the ionization efficiency. Other advantages of the proposed ionization enhancers are the simplicity of derivatization of peptides and the possibility of convenient incorporation of isotopic labels into derivatized peptides.

Laser-driven relativistic electron beam interaction with solid dielectric

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

Sarkisov, G. S.; Ivanov, V. V.; Leblanc, P.

2012-07-30

The multi-frames shadowgraphy, interferometry and polarimetry diagnostics with sub-ps time resolution were used for an investigation of ionization wave dynamics inside a glass target induced by laser-driven relativistic electron beam. Experiments were done using the 50 TW Leopard laser at the UNR. For a laser flux of {approx}2 Multiplication-Sign 10{sup 18}W/cm{sup 2} a hemispherical ionization wave propagates at c/3. The maximum of the electron density inside the glass target is {approx}2 Multiplication-Sign 10{sup 19}cm{sup -3}. Magnetic and electric fields are less than {approx}15 kG and {approx}1 MV/cm, respectively. The electron temperature has a maximum of {approx}0.5 eV. 2D interference phasemore » shift shows the 'fountain effect' of electron beam. The very low ionization inside glass target {approx}0.1% suggests a fast recombination at the sub-ps time scale. 2D PIC-simulations demonstrate radial spreading of fast electrons by self-consistent electrostatic fields.« less

A Miniaturized Linear Wire Ion Trap with Electron Ionization and Single Photon Ionization Sources

NASA Astrophysics Data System (ADS)

Wu, Qinghao; Tian, Yuan; Li, Ailin; Andrews, Derek; Hawkins, Aaron R.; Austin, Daniel E.

2017-05-01

A linear wire ion trap (LWIT) with both electron ionization (EI) and single photon ionization (SPI) sources was built. The SPI was provided by a vacuum ultraviolet (VUV) lamp with the ability to softly ionize organic compounds. The VUV lamp was driven by a pulse amplifier, which was controlled by a pulse generator, to avoid the detection of photons during ion detection. Sample gas was introduced through a leak valve, and the pressure in the system is shown to affect the signal-to-noise ratio and resolving power. Under optimized conditions, the limit of detection (LOD) for benzene was 80 ppbv using SPI, better than the LOD using EI (137 ppbv). System performance was demonstrated by distinguishing compounds in different classes from gasoline.

Ionization waves of arbitrary velocity driven by a flying focus

NASA Astrophysics Data System (ADS)

Palastro, J. P.; Turnbull, D.; Bahk, S.-W.; Follett, R. K.; Shaw, J. L.; Haberberger, D.; Bromage, J.; Froula, D. H.

2018-03-01

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. We present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionization wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.

A 310-bp minimal promoter mediates smooth muscle cell-specific expression of telokin.

PubMed

Smith, A F; Bigsby, R M; Word, R A; Herring, B P

1998-05-01

A cell-specific promoter located in an intron of the smooth muscle myosin light chain kinase gene directs transcription of telokin exclusively in smooth muscle cells. Transgenic mice were generated in which a 310-bp rabbit telokin promoter fragment, extending from -163 to +147, was used to drive expression of simian virus 40 large T antigen. Smooth muscle-specific expression of the T-antigen transgene paralleled that of the endogenous telokin gene in all smooth muscle tissues except uterus. The 310-bp promoter fragment resulted in very low levels of transgene expression in uterus; in contrast, a transgene driven by a 2.4-kb fragment (-2250 to +147) resulted in high levels of transgene expression in uterine smooth muscle. Telokin expression levels correlate with the estrogen status of human myometrial tissues, suggesting that deletion of an estrogen response element (ERE) may account for the low levels of transgene expression driven by the 310-bp rabbit telokin promoter in uterine smooth muscle. Experiments in A10 smooth muscle cells directly showed that reporter gene expression driven by the 2.4-kb, but not 310-bp, promoter fragment could be stimulated two- to threefold by estrogen. This stimulation was mediated through an ERE located between -1447 and -1474. Addition of the ERE to the 310-bp fragment restored estrogen responsiveness in A10 cells. These data demonstrate that in addition to a minimal 310-bp proximal promoter at least one distal cis-acting regulatory element is required for telokin expression in uterine smooth muscle. The distal element may include an ERE between -1447 and -1474.

Fragment-based discovery of a potent NAMPT inhibitor.

PubMed

Korepanova, Alla; Longenecker, Kenton L; Pratt, Steve D; Panchal, Sanjay C; Clark, Richard F; Lake, Marc; Gopalakrishnan, Sujatha M; Raich, Diana; Sun, Chaohong; Petros, Andrew M

2017-12-12

NAMPT expression is elevated in many cancers, making this protein a potential target for anticancer therapy. We have carried out both NMR based and TR-FRET based fragment screens against human NAMPT and identified six novel binders with a range of potencies. Co-crystal structures were obtained for two of the fragments bound to NAMPT while for the other four fragments force-field driven docking was employed to generate a bound pose. Based on structural insights arising from comparison of the bound fragment poses to that of bound FK866 we were able to synthetically elaborate one of the fragments into a potent NAMPT inhibitor. Copyright © 2017 Elsevier Ltd. All rights reserved.

The potential of combining ion trap/MS/MS and TOF/MS for identification of emerging contaminants

USGS Publications Warehouse

Ferrer, I.; Furlong, E.T.; Heine, C.E.; Thurman, E.M.

2002-01-01

The use of a method combining ion trap tandem mass spectrometry (MS/MS) and time of flight mass spectrometry (TOF/MS) for identification of emerging contaminates was discussed. The two tools together complemented each other in sensitivity, fragmentation and accurate mass determination. Liquid chromatography/electrospray ionization/ion-trap tandem mass spectrometry (LC/ESI/MS/MS), in positive ion mode of operation, was used to separate and identify specific compounds. Diagnostic fragment ions were obtained for a polyethyleneglycol(PEG) homolog by ion trap MS/MS, and fragments were measured by TOF/MS. It was observed that the combined method gave an exact mass measurement that differed from the calculated mass.

Top-Down Proteomic Identification of Shiga Toxin 2 Subtypes from Shiga Toxin-Producing Escherichia coli by Matrix-Assisted Laser Desorption Ionization–Tandem Time of Flight Mass Spectrometry

PubMed Central

Zaragoza, William J.; Sultan, Omar; Woo, Nathan; Quiñones, Beatriz; Cooley, Michael B.; Mandrell, Robert E.

2014-01-01

We have analyzed 26 Shiga toxin-producing Escherichia coli (STEC) strains for Shiga toxin 2 (Stx2) production using matrix-assisted laser desorption ionization (MALDI)–tandem time of flight (TOF-TOF) tandem mass spectrometry (MS/MS) and top-down proteomic analysis. STEC strains were induced to overexpress Stx2 by overnight culturing on solid agar supplemented with either ciprofloxacin or mitomycin C. Harvested cells were lysed by bead beating, and unfractionated bacterial cell lysates were ionized by MALDI. The A2 fragment of the A subunit and the mature B subunit of Stx2 were analyzed by MS/MS. Sequence-specific fragment ions were used to identify amino acid subtypes of Stx2 using top-down proteomic analysis using software developed in-house at the U.S. Department of Agriculture (USDA). Stx2 subtypes (a, c, d, f, and g) were identified on the basis of the mass of the A2 fragment and the B subunit as well as from their sequence-specific fragment ions by MS/MS (postsource decay). Top-down proteomic identification was in agreement with DNA sequencing of the full Stx2 operon (stx2) for all strains. Top-down results were also compared to a bioassay using a Vero-d2EGFP cell line. Our results suggest that top-down proteomic identification is a rapid, highly specific technique for distinguishing Stx2 subtypes. PMID:24584253

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

PubMed

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

Characterization of ZnO Nanoparticles using Superconducting Tunnel Junction Cryodetection Mass Spectrometry

NASA Astrophysics Data System (ADS)

Plath, Logan D.; Wang, Zongyu; Yan, Jiajun; Matyjaszewski, Krzysztof; Bier, Mark E.

2017-06-01

Zinc oxide (ZnO) nanoparticles coated with either n-octylamine (OA) or α-amino poly(styrene- co-acrylonitrile) (PSAN) ligands (L) have been analyzed using laser desorption/ionization and matrix assisted laser desorption/ionization (MALDI) time-of-flight (TOF) superconducting tunnel junction (STJ) cryodetection mass spectrometry. STJ cryodetection has the advantage of high m/ z detection and allows for the determination of average molecular weights and dispersities for 500-600 kDa ZnO-L nanoparticles. The ability to detect the relative energies deposited into the STJs has allowed for investigation of ZnO-L metastable fragmentation. ZnO-L precursor ions gain enough internal energy during the MALDI process to undergo metastable fragmentation in the flight tube. These fragments produced a lower energy peak, which was assigned as ligand-stripped ZnO cores whereas the individual ligands were at too low of an energy to be observed. From these STJ energy resolved peaks, the average weight percentage of inorganic material making up the nanoparticle was determined, where ZnO-OA and ZnO-PSAN nanoparticles are comprised of 62% and 68% wt ZnO, respectively. In one example, grafting densities were calculated based on the metastable fragmentation of ligands from the core to be 16 and 1.1 nm-2 for ZnO-OA and ZnO-PSAN, respectively, and compared with values determined by thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). [Figure not available: see fulltext.

Current Status and Future Challenges in Risk-Based Radiation Engineering

NASA Technical Reports Server (NTRS)

Pellish, Jonathan A.

2017-01-01

This presentation covers the basis and challenges for radiation effects in electronic systems. The three main types of radiation effects in electronics are: 1) total ionizing dose (TID), 2) total non-ionizing dose (TNID) / displacement damage dose (DDD), and 3) single-event effect (SEE). Some content on relevant examples of effects, current concerns, and possible environmental model-driven solutions are also included.

Nuclear Fission Investigation with Twin Ionization Chamber

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

Zeynalova, O.; Zeynalov, Sh.; Nazarenko, M.

2011-11-29

The purpose of the present paper was to report the recent results, obtained in development of digital pulse processing mathematics for prompt fission neutron (PFN) investigation using twin ionization chamber (TIC) along with fast neutron time-of-flight detector (ND). Due to well known ambiguities in literature (see refs. [4, 6, 9 and 11]), concerning a pulse induction on TIC electrodes by FF ionization, we first presented detailed mathematical analysis of fission fragment (FF) signal formation on TIC anode. The analysis was done using Ramo-Shockley theorem, which gives relation between charged particle motion between TIC electrodes and so called weighting potential. Weightingmore » potential was calculated by direct numerical solution of Laplace equation (neglecting space charge) for the TIC geometry and ionization, caused by FF. Formulae for grid inefficiency (GI) correction and digital pulse processing algorithms for PFN time-of-flight measurements and pulse shape analysis are presented and discussed.« less

A combined thermal dissociation and electron impact ionization source for RIB generation

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

Alton, G.D.; Williams, C.

1995-12-31

The probability for simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecular feed materials with conventional, hot-cathode, electron-impact ion sources is low and consequently, the ion beams from these sources often appear as mixtures of several molecular sideband beams. This fragmentation process leads to dilution of the intensity of the species of interest for RIB applications where beam intensity is at a premium. We have conceived an ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high ionization efficiency characteristics of an electron impact ionization source that will, in principle, overcome thismore » handicap. The source concept will be evaluated as a potential candidate for use for RIB generation at the Holifield Radioactive Ion Beam Facility (HRIBF), now under construction at the Oak Ridge National Laboratory. The design features and principles of operation of the source are described in this article.« less

Drawing a different picture with pencil lead as matrix-assisted laser desorption/ionization matrix for fullerene derivatives.

PubMed

Nye, Leanne C; Hungerbühler, Hartmut; Drewello, Thomas

2018-02-01

Inspired by reports on the use of pencil lead as a matrix-assisted laser desorption/ionization matrix, paving the way towards matrix-free matrix-assisted laser desorption/ionization, the present investigation evaluates its usage with organic fullerene derivatives. Currently, this class of compounds is best analysed using the electron transfer matrix trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB), which was employed as the standard here. The suitability of pencil lead was additionally compared to direct (i.e. no matrix) laser desorption/ionization-mass spectrometry. The use of (DCTB) was identified as the by far gentler method, producing spectra with abundant molecular ion signals and much reduced fragmentation. Analytically, pencil lead was found to be ineffective as a matrix, however, appears to be an extremely easy and inexpensive method for producing sodium and potassium adducts.

Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

PubMed

Li, Ping; Bu, Yuxiang

2004-11-22

The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 eV, respectively, where ionization is mainly localized on the glycinamide fragment. Like that ionized glycinamide-formamide complex, the proton transfer in the ionized complex is characterized by a single-well potential, implying that the proton initially attached to amide N4 in the glycinamide fragment cannot be transferred to carbonyl O13 in the formic acid fragment at the geometry of the optimized complex. Copyright 2004 American Institute of Physics.

Multiple product pathways in photodissociation of nitromethane at 213 nm

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

Sumida, Masataka; Kohge, Yasunori; Yamasaki, Katsuyoshi

2016-02-14

In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π{sup *} transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH{sub 3}, NO(X {sup 2}Π, A {sup 2}Σ{sup +}), and O({sup 3}P{sub J}) photofragments. The rotationally state-resolved scattering distribution of the CH{sub 3} fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH{sub 3} fragment indicated the production of themore » NO{sub 2} counter-product in the electronic excited state, wherein 1 {sup 2}B{sub 2} was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O({sup 3}P{sub J}) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A {sup 2}Σ{sup +}) fragment, which was detected by ionization spectroscopy via the Rydberg ←A {sup 2}Σ{sup +} transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH{sub 3} + NO{sub 2},CH{sub 3} + NO + O,CH{sub 3}O + NO, and CH{sub 3}NO + O, following the π → π{sup *} transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.« less

Loss of H2 and CO from protonated aldehydes in electrospray ionization mass spectrometry.

PubMed

Neta, Pedatsur; Simón-Manso, Yamil; Liang, Yuxue; Stein, Stephen E

2014-09-15

Electrospray ionization mass spectrometry (ESI-MS) of many protonated aldehydes shows loss of CO as a major fragmentation pathway. However, we find that certain aldehydes undergo loss of H2 followed by reaction with water in the collision cell. This complicates interpretation of tandem mass (MS/MS) spectra and affects multiple reaction monitoring (MRM) results. 3-Formylchromone and other aldehydes were dissolved in acetonitrile/water/formic acid and studied by ESI-MS to record their MS(2) and MS(n) spectra in several mass spectrometers (QqQ, QTOF, ion trap (IT), and Orbitrap HCD). Certain product ions were found to react with water and the rate of reaction was determined in the IT instrument using zero collision energy and variable activation times. Theoretical calculations were performed to help with the interpretation of the fragmentation mechanism. Protonated 3-formylchromones and 3-formylcoumarins undergo loss of H2 as a major fragmentation route to yield a ketene cation, which reacts with water to form a protonated carboxylic acid. In general, protonated aldehydes which contain a vicinal group that forms a hydrogen bridge with the formyl group undergo significant loss of H2. Subsequent losses of CO and C3O are also observed. Theoretical calculations suggest mechanistic details for these losses. Loss of H2 is a major fragmentation channel for protonated 3-formychromones and certain other aldehydes and it is followed by reaction with water to produce a protonated carboxylic acid, which undergoes subsequent fragmentation. This presents a problem for reference libraries and raises concerns about MRM results. Published in 2014. This article is a U.S. Government work and is in the public domain in the USA.

Total and dissociative photoionization cross sections of N2 from threshold to 107 eV

NASA Technical Reports Server (NTRS)

Samson, James A. R.; Masuoka, T.; Pareek, P. N.; Angel, G. C.

1986-01-01

The absolute cross sections for the production of N(+) and N2(+) were measured from the dissociative ionization threshold of 115 A. In addition, the absolute photoabsorption and photoionization cross sections were tabulated between 114 and 796 A. The ionization efficiencies were also given at several discrete wave lengths between 660 and 790 A. The production of N(+) fragment ions are discussed in terms of the doubly excited N2(+) states with binding energies in the range of 24 to 44 eV.

Attosecond control of dissociative ionization of O{sub 2} molecules

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

Siu, W.; Kelkensberg, F.; Gademann, G.

We demonstrate that dissociative ionization of O{sub 2} can be controlled by the relative delay between an attosecond pulse train (APT) and a copropagating infrared (IR) field. Our experiments reveal a dependence of both the branching ratios between a range of electronic states and the fragment angular distributions on the extreme ultraviolet (XUV) to IR time delay. The observations go beyond adiabatic propagation of dissociative wave packets on IR-induced quasistatic potential energy curves and are understood in terms of an IR-induced coupling between electronic states in the molecular ion.

Total and dissociative photoionization cross sections of N2 from threshold to 107 eV

NASA Technical Reports Server (NTRS)

Samson, James A. R.; Masuoka, T.; Pareek, P. N.; Angel, G. C.

1987-01-01

The absolute cross sections for the production of N(+) and N2(+) have been measured from the dissociative ionization threshold to 115 A. In addition, the absolute photoabsorption and photoionization cross sections are tabulated between 114 and 796 A. The ionization efficiencies are also given at several discrete wavelengths between 660 and 790 A. The production of N(+) fragment ions are discussed in terms of the doubly excited N2(+) states with binding energies in the range 24 to 44 eV.

Development of a gas cell-based laser ion source for RIKEN PALIS

NASA Astrophysics Data System (ADS)

Sonoda, T.; Wada, M.; Tomita, H.; Sakamoto, C.; Takatsuka, T.; Noto, T.; Iimura, H.; Matsuo, Y.; Kubo, T.; Shinozuka, T.; Wakui, T.; Mita, H.; Naimi, S.; Furukawa, T.; Itou, Y.; Schury, P.; Miyatake, H.; Jeong, S.; Ishiyama, H.; Watanabe, Y.; Hirayama, Y.

2013-04-01

We developed a prototype laser ionization gas cell with a beam extraction system. This device is for use of PArasitic Laser Ion-Source (PALIS), which will be implemented into RIKEN's fragment separator, BigRIPS as a part of SLOWRI. Off-line resonant laser ionization for stable Co, Cu, Fe, Ni, Ti, Nb, Sn, In and Pd inside the gas cell, ion extraction and transport to the high-vacuum region via SPIG and QMS have been confirmed (Sonoda et al, Nucl Instrum Meth B 295:1, 2013).

QTAIM charge density study of natural cinnamic acids

NASA Astrophysics Data System (ADS)

González Moa, María J.; Mandado, Marcos; Mosquera, Ricardo A.

2006-06-01

B3LYP/6-311++G(2d,2p) 6d ionization potentials and O-H bond dissociation energies of natural cinnamic acids are consistent with an important antioxidant activity. The QTAIM analysis indicates that: (i) the benzene ring and the propenoic acid fragment of cinnamic acids behave as independent π systems; (ii) the ionization process consists in a loss of nearly 1 a.u. of π electron density by the atoms involved in HOMO accompanied by a reorganization of σ electron density that is mostly provided by the remaining atoms.

Absolute photoionization cross sections of furanic fuels: 2-ethylfuran, 2-acetylfuran and furfural.

PubMed

Smith, Audrey R; Meloni, Giovanni

2015-11-01

Absolute photoionization cross sections of the molecules 2-ethylfuran, 2-acetylfuran and furfural, including partial ionization cross sections for the dissociative ionized fragments, are measured for the first time. These measurements are important because they allow fuel quantification via photoionization mass spectrometry and the development of quantitative kinetic modeling for the complex combustion of potential fuels. The experiments are carried out using synchrotron photoionization mass spectrometry with an orthogonal time-of-flight spectrometer used for mass analysis at the Advanced Light Source of Lawrence Berkeley National Laboratory. The CBS-QB3 calculations of adiabatic ionization energies and appearance energies agree well with the experimental results. Several bond dissociation energies are also derived and presented. Copyright © 2015 John Wiley & Sons, Ltd.

Corona discharge ionization of paracetamol molecule: Peak assignment

NASA Astrophysics Data System (ADS)

Bahrami, H.; Farrokhpour, H.

2015-01-01

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

In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

2016-07-01

We propose detecting a fragment ion (Ph2As+) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH+) of DA, DC, DPAH, and BDPAO could produce Ph2As+ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As+ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH+ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As+.

Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

PubMed

Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

2014-05-06

A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

Establishment of a Charge Reversal Derivatization Strategy to Improve the Ionization Efficiency of Limaprost and Investigation of the Fragmentation Patterns of Limaprost Derivatives Via Exclusive Neutral Loss and Survival Yield Method

NASA Astrophysics Data System (ADS)

Sun, Dong; Meng, Xiangjun; Ren, Tianming; Fawcett, John Paul; Wang, Hualu; Gu, Jingkai

2018-04-01

Sensitivity is generally an issue in bioassays of prostaglandins and their synthetic analogs due to their extremely low concentration in vivo. To improve the ionization efficiency of limaprost, an oral prostaglandin E1 (PGE1) synthetic analog, we investigated a charge reversal derivatization strategy in electrospray ionization mass spectrometry (ESI-MS). We established that the cholamine derivative exhibits much greater signal intensity in the positive-ion mode compared with limaprost in the negative ion mode. Collision-induced dissociation (CID) involved exclusive neutral mass loss and positive charge migration to form stable cationic product ions with the positive charge on the limaprost residue rather than on the modifying group. This has the effect of maintaining the efficiency and specificity of multiple reaction monitoring (MRM) and avoiding cross talk. CID fragmentation patterns of other limaprost derivatives allowed us to relate the dissociation tendency of different neutral leaving groups to an internal energy distribution scale based on the survival yield method. Knowledge of the energy involved in the production of stabilized positive ions will potentially assist the selection of suitable derivatization reagents for the analysis of a wide variety of lipid acids. [Figure not available: see fulltext.

Prompt fission neutron emission in the reaction 235U(n,f)

NASA Astrophysics Data System (ADS)

Göök, Alf; Hambsch, Franz-Josef; Oberstedt, Stephan

2018-03-01

Experimental activities at JRC-Geel on prompt fission neutron (PFN) emission in response to OECD/NEA nuclear data requests are presented in this contribution. Specifically, on-going investigations of PFN emission from the reaction 235U(n,f) in the region of the resolved resonances, taking place at the GELINA facility, are presented. The focus of this contribution lies on studies of PFN correlations with fission fragment properties. The experiment employs a scintillation detector array for neutron detection, while fission fragment properties are determined via the double kinetic energy technique using a position sensitive twin ionization chamber. This setup allows us to study several correlations between properties of neutron and fission fragments simultaneously. Results on PFN correlations with fission fragment properties from the present study differ significantly from earlier studies on this reaction, induced by thermal neutrons.

Fragmentation of D- and L-enantiomers of amino acids through interaction with 3He2+ ions

NASA Astrophysics Data System (ADS)

Smirnov, O. V.; Basalaev, A. A.; Boitsov, V. M.; Vyaz'min, S. Yu.; Orbeli, A. L.; Dubina, M. V.

2014-11-01

The relative cross section of processes attendant on the capture of an electron by 12-keV 3He2+ ions are measured by time-of-flight mass spectrometry for leucine (C6H13NO2), methionine (C5H11NO2S), and glutmic acid (C5H9NO4) molecules. No differences between the formation relative cross sections of different fragment ions for the D- and L-enantiomeric forms of the amino acids are revealed. The spectrum of glutamic acid fragments taken at temperatures above 110°C is explained by decomposition of the acid with the formation of pyroglutamic acid (C5H7NO3) and water. The results are compared with published data on fragmentation of the same molecules via electron-impact ionization.

Red Geyser: A New Class of Galaxy with Large-scale AGN-driven Winds

NASA Astrophysics Data System (ADS)

Roy, Namrata; Bundy, Kevin; Cheung, Edmond; MaNGA Team

2018-01-01

A new class of quiescent (non-star-forming) galaxies harboring possible AGN-driven winds have been discovered using the spatially resolved optical spectroscopy from the ongoing SDSS-IV MaNGA (Sloan Digital Sky Survey-IV Mapping Nearby Galaxies at Apache Point Observatory) survey. These galaxies named "red geysers" constitute 5%-10% of the local quiescent galaxy population and are characterized by narrow bisymmetric ionized gas emission patterns. These enhanced patterns are seen in equivalent width maps of Hα, [OIII] and other strong emission lines. They are co-aligned with the ionized gas velocity gradients but significantly misaligned with stellar velocity gradients. They also show very high gas velocity dispersions (~200 km/s). Considering these observations in light of models of the gravitational potential, Cheung et al. argued that red geysers host large-scale AGN-driven winds of ionized gas that may play a role in suppressing star formation at late times. In this work, we test the hypothesis that AGN activity is ultimately responsible for the red geyser phenomenon. We compare the nuclear radio activity of the red geysers to a matched control sample of galaxies of similar stellar mass, redshift, rest frame NUV–r color and axis ratio. and additionally, control for the presence of ionized gas. We have used 1.4 GHz radio continuum data from the VLA FIRST Survey to stack the radio flux from the red geyser sample and control sample. We find that the red geysers have a higher average radio flux than the control galaxies at > 3σ significance. Our sample is restricted to rest-frame NUV–r color > 5, thus ruling out possible radio emission due to star formation activity. We conclude that red geysers are associated with more active AGN, supporting a feedback picture in which episodic AGN activity drives large-scale but relatively weak ionized winds in many in many early-type galaxies.

Collision-induced dissociation of aminophospholipids (PE, MMPE, DMPE, PS): an apparently known fragmentation process revisited.

PubMed

Pittenauer, Ernst; Rehulka, Pavel; Winkler, Wolfgang; Allmaier, Günter

2015-07-01

A new type of low-mass substituted 4-oxazolin product ions of [M + H](+) precursor ions of aminophospholipids (glycerophosphatidylethanolamine, glycerophosphatidyl-N-methylethanolamine, glycerophosphatidyl-N,N-dimethylethanolamine, glycerophosphatidylserine) resulting from high-energy collision-induced dissociation (matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry) and low-energy collision-induced dissociation (e.g., electrospray ionization quadrupole reflectron time-of-flight mass spectrometry) with accurate mass determination is described; these were previously misidentified as CHO-containing radical cationic product ions. The mechanism for the formation of these ions is proposed to be via rapid loss of water followed by cyclization to an 11-membered-ring transition state for the sn-1 fatty acid substituent and to a ten-membered-ring transition state for the sn-2 fatty acid substituent, and via final loss of monoacylglycerol phosphate, leading to substituted 4-oxazolin product ions. The minimum structural requirement for this interesting skeletal rearrangement fragmentation is an amino group linked to at least one hydrogen atom (i.e., ethanolamine, N-methylethanolamine, serine). Therefore, N,N-dimethylethanolamine derivates do not exhibit this type of fragmentation. The analytical value of these product ions is given by the fact that by post source decay and particularly high-energy collision-induced dissociation achieved via matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry, the sn-2-related substituted 4-oxazolin product ion is always significantly more abundant than the sn-1-related one, which is quite helpful for detailed structural analysis of complex lipids. All other important product ions found are described in detail (following our previously published glycerophospholipid product ion nomenclature; Pittenauer and Allmaier, Int. J. Mass. Spectrom. 301:90-1012, 2011).

Analysis of antioxidants in insulation cladding of copper wire: a comparison of different mass spectrometric techniques (ESI-IT, MALDI-RTOF and RTOF-SIMS).

PubMed

Schnöller, Johannes; Pittenauer, Ernst; Hutter, Herbert; Allmaier, Günter

2009-12-01

Commercial copper wire and its polymer insulation cladding was investigated for the presence of three synthetic antioxidants (ADK STAB AO412S, Irganox 1010 and Irganox MD 1024) by three different mass spectrometric techniques including electrospray ionization-ion trap-mass spectrometry (ESI-IT-MS), matrix-assisted laser desorption/ionization reflectron time-of-flight (TOF) mass spectrometry (MALDI-RTOF-MS) and reflectron TOF secondary ion mass spectrometry (RTOF-SIMS). The samples were analyzed either directly without any treatment (RTOF-SIMS) or after a simple liquid/liquid extraction step (ESI-IT-MS, MALDI-RTOF-MS and RTOF-SIMS). Direct analysis of the copper wire itself or of the insulation cladding by RTOF-SIMS allowed the detection of at least two of the three antioxidants but at rather low sensitivity as molecular radical cations and with fairly strong fragmentation (due to the highly energetic ion beam of the primary ion gun). ESI-IT- and MALDI-RTOF-MS-generated abundant protonated and/or cationized molecules (ammoniated or sodiated) from the liquid/liquid extract. Only ESI-IT-MS allowed simultaneous detection of all three analytes in the extract of insulation claddings. The latter two so-called 'soft' desorption/ionization techniques exhibited intense fragmentation only by applying low-energy collision-induced dissociation (CID) tandem MS on a multistage ion trap-instrument and high-energy CID on a tandem TOF-instrument (TOF/RTOF), respectively. Strong differences in the fragmentation behavior of the three analytes could be observed between the different CID spectra obtained from either the IT-instrument (collision energy in the very low eV range) or the TOF/RTOF-instrument (collision energy 20 keV), but both delivered important structural information. Copyright 2009 John Wiley & Sons, Ltd.

Fragmentation mechanisms for methane induced by 55 eV, 75 eV, and 100 eV electron impact.

PubMed

Wei, B; Zhang, Y; Wang, X; Lu, D; Lu, G C; Zhang, B H; Tang, Y J; Hutton, R; Zou, Y

2014-03-28

The fragmentation of CH4 (2+) dications following 55 eV, 75 eV, and 100 eV electron impact double ionization of methane was studied using a cold target recoil-ion momentum spectroscopy. From the measured momentum of each recoil ion, the momentum of the neutral particles has been deduced and the kinetic energy release distribution for the different fragmentation channels has been obtained. The doubly charged molecular ions break up into three or more fragments in one or two-step processes, resulting in different signatures in the data. We observed the fragmentation of CH4 (2+) dications through different mechanisms according to the momentum of the neutral particles. For example, our result shows that there are three reaction channels to form CH2 (+), H(+), and H, one synchronous concerted reaction channel and two two-step reaction channels. For even more complicated fragmentation processes of CH4 (2+) dications, the fragmentation mechanism can still be identified in the present measurements. The slopes of the peak in the ion-ion coincidence spectra were also estimated here, as they are also related to the fragmentation mechanism.

Coherent control of alkali cluster fragmentation dynamics

NASA Astrophysics Data System (ADS)

Lindinger, Albrecht; Lupulescu, Cosmin; Bartelt, Andreas; Vajda, Štefan; Wöste, Ludger

2003-06-01

Metal clusters exhibit extraordinary chemical and catalytic properties, which sensitively depend upon their size. This behavior makes them interesting candidates for the real-time analysis of ultrafast photo-induced processes—ultimately leading to coherent control scenarii. We have performed transient multi-photon ionization experiments on small alkali clusters of different size in order to probe their wave packet dynamics, structural reorientations, charge transfers and dissociative events in different vibrationally excited electronic states including their ground state. The observed processes were highly dependent on the irradiated pulse parameters, like its phase, amplitude and duration; an emphasis to employ a feedback control system for generating the optimum pulse shapes. Their spectral and temporal behavior reflects interesting properties about the investigated system and the irradiated photochemical process. We present first the vibrational dynamics of bound, dissociated, and pre-dissociated electronically excited states of alkali dimers and trimers. The scheme for observing the wave packet dynamics in the electronic ground state using stimulated Raman-pumping is shown. Since the employed pulse parameters significantly influence the efficiency of the irradiated dynamic pathways photo-induced fragmentation experiments on bifurcating reaction channels were carried out. In these experiments different branching ionization and fragmentation pathways of electronically excited Na 2K were investigated. By employing an evolutionary algorithm for optimizing the phase and amplitude of the applied laser field, the yield of the resulting parent or fragment ions could significantly be influenced and interesting features could be concluded from the obtained optimum pulse shapes revealing the characteristic molecular oscillation period. Moreover, the influence on the optimal pulse shape due to fragmentation from larger clusters into NaK is obtained. The substructure of the optimal pulse shape thereby offers new insight into the fragmentation channel during the control process. Characteristic motions of the involved wave packets are proposed, in order to explain the optimized dynamic dissociation pathways.

Minimal Pharmacophoric Elements and Fragment Hopping, an Approach Directed at Molecular Diversity and Isozyme Selectivity. Design of Selective Neuronal Nitric Oxide Synthase Inhibitors

PubMed Central

Ji, Haitao; Stanton, Benjamin Z.; Igarashi, Jotaro; Li, Huiying; Martásek, Pavel; Roman, Linda J.; Poulos, Thomas L.; Silverman, Richard B.

2010-01-01

Fragment hopping, a new fragment-based approach for de novo inhibitor design focusing on ligand diversity and isozyme selectivity, is described. The core of this approach is the derivation of the minimal pharmacophoric element for each pharmacophore. Sites for both ligand binding and isozyme selectivity are considered in deriving the minimal pharmacophoric elements. Five general-purpose libraries are established: the basic fragment library, the bioisostere library, the rules for metabolic stability, the toxicophore library, and the side chain library. These libraries are employed to generate focused fragment libraries to match the minimal pharmacophoric elements for each pharmacophore and then to link the fragment to the desired molecule. This method was successfully applied to neuronal nitric oxide synthase (nNOS), which is implicated in stroke and neurodegenerative diseases. Starting with the nitroarginine-containing dipeptide inhibitors we developed previously, a small organic molecule with a totally different chemical structure was designed, which showed nanomolar nNOS inhibitory potency and more than 1000-fold nNOS selectivity. The crystallographic analysis confirms that the small organic molecule with a constrained conformation can exactly mimic the mode of action of the dipeptide nNOS inhibitors. Therefore, a new peptidomimetic strategy, referred to as fragment hopping, which creates small organic molecules that mimic the biological function of peptides by a pharmacophore-driven strategy for fragment-based de novo design, has been established as a new type of fragment-based inhibitor design. As an open system, the newly established approach efficiently incorporates the concept of early “ADME/Tox” considerations and provides a basic platform for medicinal chemistry-driven efforts. PMID:18321097

Mechanistic Study on Electronic Excitation Dissociation of the Cellobiose-Na+ Complex

NASA Astrophysics Data System (ADS)

Huang, Yiqun; Pu, Yi; Yu, Xiang; Costello, Catherine E.; Lin, Cheng

2016-02-01

The recent development of electron activated dissociation (ExD) techniques has opened the door for high-throughput, detailed glycan structural elucidation. Among them, ExD methods employing higher-energy electrons offer several advantages over low-energy electron capture dissociation (ECD), owing to their applicability towards chromophore-labeled glycans and singly charged ions, and ability to provide more extensive structural information. However, a lack of understanding of these processes has hindered rational optimization of the experimental conditions for more efficient fragmentation as well as the development of informatics tools for interpretation of the complex glycan ExD spectra. Here, cellobiose-Na+ was used as the model system to investigate the fragmentation behavior of metal-adducted glycans under irradiation of electrons with energy exceeding their ionization potential, and served as the basis on which a novel electronic excitation dissociation (EED) mechanism was proposed. It was found that ionization of the glycan produces a mixture of radical cations and ring-opened distonic ions. These distonic ions then capture a low-energy electron to produce diradicals with trivial singlet-triplet splitting, and subsequently undergo radical-induced dissociation to produce a variety of fragment ions, the abundances of which are influenced by the stability of the distonic ions from which they originate.

Statistical analysis of fragmentation patterns of electron ionization mass spectra of enolized-trimethylsilylated anabolic androgenic steroids

NASA Astrophysics Data System (ADS)

Fragkaki, A. G.; Angelis, Y. S.; Tsantili-Kakoulidou, A.; Koupparis, M.; Georgakopoulos, C.

2009-08-01

Anabolic androgenic steroids (AAS) are included in the List of prohibited substances of the World Anti-Doping Agency (WADA) as substances abused to enhance athletic performance. Gas chromatography coupled to mass spectrometry (GC-MS) plays an important role in doping control analyses identifying AAS as their enolized-trimethylsilyl (TMS)-derivatives using the electron ionization (EI) mode. This paper explores the suitability of complementary GC-MS mass spectra and statistical analysis (principal component analysis, PCA and partial least squares-discriminant analysis, PLS-DA) to differentiate AAS as a function of their structural and conformational features expressed by their fragment ions. The results obtained showed that the application of PCA yielded a classification among the AAS molecules which became more apparent after applying PLS-DA to the dataset. The application of PLS-DA yielded a clear separation among the AAS molecules which were, thus, classified as: 1-ene-3-keto, 3-hydroxyl with saturated A-ring, 1-ene-3-hydroxyl, 4-ene-3-keto, 1,4-diene-3-keto and 3-keto with saturated A-ring anabolic steroids. The study of this paper also presents structurally diagnostic fragment ions and dissociation routes providing evidence for the presence of unknown AAS or chemically modified molecules known as designer steroids.

Half collision resonance phenomena in molecules

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

Maximo Garcia-Sucre; Raseev, G.; Ross, S.C.

1991-01-01

The Escuela Latinoamericana de Fisica (ELAF) is a series of meeting s that for 28 years has played an important role in research-level teaching of physics in Latin America. This book contains the proceedings of ELAF 90 which was held at the Instituto Venezolano de Investigaciones Cientificas (IVIC) in Caracas, Venezuela from July 23 to August 3, 1990, as part of the commemoration of the 30th anniversary of IVIC. In contrast to previous ELAF's that were of general scope, ELAF 90 centered on a particular subject matter: Half Collisional Resonance Phenomena in Molecules, Experimental and Theoretical Approaches. The term Halfmore » Collision'' refers to the fragmentation of a molecular system following is excitation by light. The lack of an incident fragmentation of a molecular system following is excitation by light. The lack of an incident particle (other than the photon) in the fragmentation process is what leads to the term. The purpose of this volume is to present current results in the experimental and theoretical study of half collisions and also to include pedagogical papers at an introductory or intermediate level. The contributions are grouped into several sections; light sources; ionization; dissociation-experimental; dissociation-theory; competition between ionization and dissociation; and particle-molecule collisions.« less

Observation of fast and slow interatomic Coulombic decay in argon dimers induced by electron-impact ionization

NASA Astrophysics Data System (ADS)

Ren, Xueguang; Miteva, Tsveta; Kolorenč, Přemysl; Gokhberg, Kirill; Kuleff, Alexander I.; Cederbaum, Lorenz S.; Dorn, Alexander

2017-09-01

We investigate the interatomic Coulombic decay (ICD) in argon dimers induced by electron-impact ionization (E0=90 eV ) using a multiparticle coincidence experiment in which the momentum vectors and, consequently, the kinetic energies for electrons and fragment ions are determined. The signature of the ICD process is obtained from a correlation map between ejected electron energy and kinetic energy release (KER) for Ar++Ar+ fragment ions where low-energy ICD electrons can be identified. Furthermore, two types of ICD processes, termed fast and slow interatomic decay, are separated by the ICD initial-state energies and projectile energy losses. The dependence of the energies of emitted low-energy ICD electrons on the initial-state energy is studied. ICD electron energy spectra and KER spectra are obtained separately for fast and slow decay processes where the KER spectra for the slow decay channel are strongly influenced by nuclear motion. The KER and ICD electron energy spectra are well reproduced by ab initio calculations.

Communication: Protonation process of formic acid from the ionization and fragmentation of dimers induced by synchrotron radiation in the valence region

NASA Astrophysics Data System (ADS)

Arruda, Manuela S.; Medina, Aline; Sousa, Josenilton N.; Mendes, Luiz A. V.; Marinho, Ricardo R. T.; Prudente, Frederico V.

2016-04-01

The ionization and fragmentation of monomers of organic molecules have been extensively studied in the gas phase using mass spectroscopy. In the spectra of these molecules it is possible to identify the presence of protonated cations, which have a mass-to-charge ratio one unit larger than the parent ion. In this work, we investigate this protonation process as a result of dimers photofragmentation. Experimental photoionization and photofragmentation results of doubly deuterated formic acid (DCOOD) in the gas phase by photons in the vacuum ultraviolet region are presented. The experiment was performed by using a time-of-flight mass spectrometer installed at the Brazilian Synchrotron Light Laboratory and spectra for different pressure values in the experimental chamber were obtained. The coupled cluster approach with single and double substitutions was employed to assist the experimental analysis. Results indicate that protonated formic acid ions are originated from dimer dissociation, and the threshold photoionization of (DCOOD)ṡD+ is also determined.

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera.

PubMed

Amini, Kasra; Boll, Rebecca; Lauer, Alexandra; Burt, Michael; Lee, Jason W L; Christensen, Lauge; Brauβe, Felix; Mullins, Terence; Savelyev, Evgeny; Ablikim, Utuq; Berrah, Nora; Bomme, Cédric; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Johnsson, Per; Kierspel, Thomas; Krecinic, Faruk; Küpper, Jochen; Müller, Maria; Müller, Erland; Redlin, Harald; Rouzée, Arnaud; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Wiese, Joss; Vallance, Claire; Rudenko, Artem; Stapelfeldt, Henrik; Brouard, Mark; Rolles, Daniel

2017-07-07

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C 6 H 3 F 2 I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Quantum Phenomena in High Energy Density Plasmas

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

Murnane, Margaret; Kapteyn, Henry

The possibility of implementing efficient (phase matched) HHG upconversion of deep- UV lasers in multiply-ionized plasmas, with potentially unprecedented conversion efficiency is a fascinating prospect. HHG results from the extreme nonlinear response of matter to intense laser light:high harmonics are radiated as a result of a quantum coherent electron recollision process that occurs during laser field ionization of an atom. Under current support from this grant in work published in Science in 2015, we discovered a new regime of bright HHG in highly-ionized plasmas driven by intense UV lasers, that generates bright harmonics to photon energies >280eV

Fission fragment driven neutron source

DOEpatents

Miller, Lowell G.; Young, Robert C.; Brugger, Robert M.

1976-01-01

Fissionable uranium formed into a foil is bombarded with thermal neutrons in the presence of deuterium-tritium gas. The resulting fission fragments impart energy to accelerate deuterium and tritium particles which in turn provide approximately 14 MeV neutrons by the reactions t(d,n).sup.4 He and d(t,n).sup.4 He.

An unusual case of cerebral penetrating injury by a driven bone fragment secondary to blunt head trauma.

PubMed

Lee, Jae Il; Ko, Jun Kyeung; Cha, Seung Heon; Han, In Ho

2011-12-01

Temple trauma that appears initially localized to the skin might possess intracranial complications. Early diagnosis and management of such complications are important, to avoid neurologic sequelae. Non-penetrating head injuries with intracranial hemorrhage caused by a driven bone fragment are extremely rare. A 53-year-old male was referred to our hospital because of intracerebral hemorrhage. He was a mechanic and one day before admission to a local clinic, tip of metallic rod hit his right temple while cutting the rod. Initial brain computed tomography (CT) and magnetic resonance imaging demonstrated scanty subdural hematoma at right temporal lobe and left falx and intracerebral hematoma at both frontal lobes. Facial CT with 3-D reconstruction images showed a small bony defect at the right sphenoid bone's greater wing and a small bone fragment at the left frontal lobe, crossing the falx. We present the unusual case of a temple trauma patient in whom a sphenoid bone fragment migrated from its origin upward, to the contralateral frontal lobe, producing hematoma along its trajectory.

Low-Pressure, Field-Ionizing Mass Spectrometer

NASA Technical Reports Server (NTRS)

Hartley, Frank; Smith, Steven

2009-01-01

A small mass spectrometer utilizing a miniature field ionization source is now undergoing development. It is designed for use in a variety of applications in which there are requirements for a lightweight, low-power-consumption instrument that can analyze the masses of a wide variety of molecules and ions. The device can operate without need for a high-vacuum, carrier-gas feed radioactive ionizing source, or thermal ionizer. This mass spectrometer can operate either in the natural vacuum of outer space or on Earth at any ambient pressure below 50 torr (below about 6.7 kPa) - a partial vacuum that can easily be reached by use of a small sampling pump. This mass spectrometer also has a large dynamic range - from singly charged small gas ions to deoxyribonucleic acid (DNA) fragments larger than 104 atomic mass units - with sensitivity adequate for detecting some molecules and ions at relative abundances of less than one part per billion. This instrument (see figure) includes a field ionizer integrated with a rotating-field mass spectrometer (RFMS). The field ionizer effects ionization of a type characterized as "soft" in the art because it does not fragment molecules or initiate avalanche arcing. What makes the "soft" ionization mode possible is that the distance between the ionizing electrodes is less than mean free path for ions at the maximum anticipated operating pressure, so that the ionizer always operates on the non-breakdown side of the applicable Paschen curve (a standard plot of breakdown potential on the ordinate and pressure electrode separation on the abscissa). The field ionizer in this instrument is fabricated by micromachining a submicron-thick membrane out of an electrically nonconductive substrate, coating the membrane on both sides to form electrodes, then micromachining small holes through the electrodes and membrane. Because of the submicron electrode separation, even a potential of only 1 V applied between the electrodes gives rise to an electric field with a strength of in excess of a megavolt per meter strong enough to ionize any gas molecules passing through the holes. An accelerator grid and an electrostatic deflector focus the ions from the field ionizer into the rotating-field cell of the RFMS. The potentials applied to the electrodes of the cell to generate the rotating electric field typically range from 1 to 13 V. The ions travel in well-defined helices within this cell, after which they are collected in a Faraday cup. The mass of most of the molecules reaching the Faraday cup decreases with increasing frequency of rotation of the electric field in the cell. Therefore, the frequency of rotation of the electric field is made to vary in order to scan through a desired range of ion masses: For example, lightweight gas molecules are scanned at frequencies in the megahertz range, while DNA and other large organic molecules are scanned at kilohertz frequencies.

Space Environment (Natural and Induced)

NASA Technical Reports Server (NTRS)

Kim, Myung-Hee Y.; George, Kerry A.; Cucinotta, Francis A.

2007-01-01

Considerable effort and improvement have been made in the study of ionizing radiation exposure occurring in various regions of space. Satellites and spacecrafts equipped with innovative instruments are continually refining particle data and providing more accurate information on the ionizing radiation environment. The major problem in accurate spectral definition of ionizing radiation appears to be the detailed energy spectra, especially at high energies, which is important parameter for accurate radiation risk assessment. Magnitude of risks posed by exposure to radiation in future space missions is subject to the accuracies of predictive forecast of event size of SPE, GCR environment, geomagnetic fields, and atmospheric radiation environment. Although heavy ion fragmentations and interactions are adequately resolved through laboratory study and model development, improvements in fragmentation cross sections for the light nuclei produced from HZE nuclei and their laboratory validation are still required to achieve the principal goal of planetary GCR simulation at a critical exposure site. More accurate prediction procedure for ionizing radiation environment can be made with a better understanding of the solar and space physics, fulfillment of required measurements for nuclear/atomic processes, and their validation and verification with spaceflights and heavy ion accelerators experiments. It is certainly true that the continued advancements in solar and space physics combining with physical measurements will strengthen the confidence of future manned exploration of solar system. Advancements in radiobiology will surely give the meaningful radiation hazard assessments for short and long term effects, by which appropriate and effective mitigation measures can be placed to ensure that humans safely live and work in the space, anywhere, anytime.

Injection and trapping of tunnel-ionized electrons into laser-produced wakes.

PubMed

Pak, A; Marsh, K A; Martins, S F; Lu, W; Mori, W B; Joshi, C

2010-01-15

A method, which utilizes the large difference in ionization potentials between successive ionization states of trace atoms, for injecting electrons into a laser-driven wakefield is presented. Here a mixture of helium and trace amounts of nitrogen gas was used. Electrons from the K shell of nitrogen were tunnel ionized near the peak of the laser pulse and were injected into and trapped by the wake created by electrons from majority helium atoms and the L shell of nitrogen. The spectrum of the accelerated electrons, the threshold intensity at which trapping occurs, the forward transmitted laser spectrum, and the beam divergence are all consistent with this injection process. The experimental measurements are supported by theory and 3D OSIRIS simulations.

PIC simulations of post-pulse field reversal and secondary ionization in nanosecond argon discharges

NASA Astrophysics Data System (ADS)

Kim, H. Y.; Gołkowski, M.; Gołkowski, C.; Stoltz, P.; Cohen, M. B.; Walker, M.

2018-05-01

Post-pulse electric field reversal and secondary ionization are investigated with a full kinetic treatment in argon discharges between planar electrodes on nanosecond time scales. The secondary ionization, which occurs at the falling edge of the voltage pulse, is induced by charge separation in the bulk plasma region. This process is driven by a reverse in the electric field from the cathode sheath to the formerly driven anode. Under the influence of the reverse electric field, electrons in the bulk plasma and sheath regions are accelerated toward the cathode. The electron movement manifests itself as a strong electron current generating high electron energies with significant electron dissipated power. Accelerated electrons collide with Ar molecules and an increased ionization rate is achieved even though the driving voltage is no longer applied. With this secondary ionization, in a single pulse (SP), the maximum electron density achieved is 1.5 times higher and takes a shorter time to reach using 1 kV 2 ns pulse as compared to a 1 kV direct current voltage at 1 Torr. A bipolar dual pulse excitation can increase maximum density another 50%–70% above a SP excitation and in half the time of RF sinusoidal excitation of the same period. The first field reversal is most prominent but subsequent field reversals also occur and correspond to electron temperature increases. Targeted pulse designs can be used to condition plasma density as required for fast discharge applications.

Hydrodynamic Models of Line-Driven Accretion Disk Winds III: Local Ionization Equilibrium

NASA Technical Reports Server (NTRS)

Pereyra, Nicolas Antonio; Kallman, Timothy R.; White, Nicholas E. (Technical Monitor)

2002-01-01

We present time-dependent numerical hydrodynamic models of line-driven accretion disk winds in cataclysmic variable systems and calculate wind mass-loss rates and terminal velocities. The models are 2.5-dimensional, include an energy balance condition with radiative heating and cooling processes, and includes local ionization equilibrium introducing time dependence and spatial dependence on the line radiation force parameters. The radiation field is assumed to originate in an optically thick accretion disk. Wind ion populations are calculated under the assumption that local ionization equilibrium is determined by photoionization and radiative recombination, similar to a photoionized nebula. We find a steady wind flowing from the accretion disk. Radiative heating tends to maintain the temperature in the higher density wind regions near the disk surface, rather than cooling adiabatically. For a disk luminosity L (sub disk) = solar luminosity, white dwarf mass M(sub wd) = 0.6 solar mass, and white dwarf radii R(sub wd) = 0.01 solar radius, we obtain a wind mass-loss rate of M(sub wind) = 4 x 10(exp -12) solar mass yr(exp -1) and a terminal velocity of approximately 3000 km per second. These results confirm the general velocity and density structures found in our earlier constant ionization equilibrium adiabatic CV wind models. Further we establish here 2.5D numerical models that can be extended to QSO/AGN winds where the local ionization equilibrium will play a crucial role in the overall dynamics.

Fragmentation studies of fulvic acids using collision induced dissociation fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Witt, Matthias; Fuchser, Jens; Koch, Boris P

2009-04-01

The complex natural organic matter standard Suwannee river fulvic acid (SRFA) was analyzed by negative ion mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS) using on-resonance collision induced dissociation (CID) of single ultrahigh resolved mass peaks in the ICR cell. Molecular formula assignment of precursor masses resulted in exactly one molecular formula for each of the peaks. Analyses of the corresponding fragment spectra and comparison to different standard substances revealed specific neutral losses and fragmentation patterns which result in structures consisting of a high degree of carboxyl- and fewer hydroxyl groups. The comparison of fragmented mass peaks within different pseudohomologous series (CH(2)-series, and CH(4) vs O exchange) suggested structurally based differences between these series. CID FTICR MS allowed isolating single mass peaks in a very complex natural organic matter spectrum. Subsequently, fragmentation gave structural insights into this material. Our results suggest that the structural diversity in complex humic substances is not as high as expected.

Molecular photoionization processes of astrophysical and aeronomical interest

NASA Technical Reports Server (NTRS)

Langhoff, P. W.

1985-01-01

An account is given of aspects of photoionization processes in molecules, with particular reference to recent theoretical and experimental studies of partial cross sections for production of specific final electronic states and of parent and fragment ions. Such cross sections help provide a basis for specifying the state of excitation of the ionized medium, are useful for estimating the kinetic energy distributions of photoejected electrons and fragment ions, provide parent-and fragment-ion yields, and clarify the possible origins of neutral fragments in highly excited rovibronic states. A descriptive account is given of photoionization phenomena, including tabulation of valence- and inner-shell potentials for some molecules of astrophysical and aeronomical interest. Cross sectional expressions are given. Various approximations currently employed in computational studies are described briefly, threshold laws and high-energy limits are indicated, and distinction is drawn between resonant and direct photoionization phenomena. Recent experimental and theoretical studies of partial photoionization cross sections in selected compounds of astrophysical and aeronomical relevance are described and discussed.

Fission-fragment total kinetic energy and mass yields for neutron-induced fission of 235U and 238U with En =200 keV - 30 MeV

NASA Astrophysics Data System (ADS)

Duke, D. L.; Tovesson, F.; Brys, T.; Geppert-Kleinrath, V.; Hambsch, F.-J.; Laptev, A.; Meharchand, R.; Manning, B.; Mayorov, D.; Meierbachtol, K.; Mosby, S.; Perdue, B.; Richman, D.; Shields, D.; Vidali, M.

2017-09-01

The average Total Kinetic Energy (TKE) release and fission-fragment yields in neutron-induced fission of 235U and 238U was measured using a Frisch-gridded ionization chamber. These observables are important nuclear data quantites that are relevant to applications and for informing the next generation of fission models. The measurements were performed a the Los Alamos Neutron Science Center and cover En = 200 keV - 30 MeV. The double-energy (2E) method was used to determine the fission-fragment yields and two methods of correcting for prompt-neutron emission were explored. The results of this study are correlated mass and TKE data.

Trace detection of organic compounds in complex sample matrixes by single photon ionization ion trap mass spectrometry: real-time detection of security-relevant compounds and online analysis of the coffee-roasting process.

PubMed

Schramm, Elisabeth; Kürten, Andreas; Hölzer, Jasper; Mitschke, Stefan; Mühlberger, Fabian; Sklorz, Martin; Wieser, Jochen; Ulrich, Andreas; Pütz, Michael; Schulte-Ladbeck, Rasmus; Schultze, Rainer; Curtius, Joachim; Borrmann, Stephan; Zimmermann, Ralf

2009-06-01

An in-house-built ion trap mass spectrometer combined with a soft ionization source has been set up and tested. As ionization source, an electron beam pumped vacuum UV (VUV) excimer lamp (EBEL) was used for single-photon ionization. It was shown that soft ionization allows the reduction of fragmentation of the target analytes and the suppression of most matrix components. Therefore, the combination of photon ionization with the tandem mass spectrometry (MS/MS) capability of an ion trap yields a powerful tool for molecular ion peak detection and identification of organic trace compounds in complex matrixes. This setup was successfully tested for two different applications. The first one is the detection of security-relevant substances like explosives, narcotics, and chemical warfare agents. One test substance from each of these groups was chosen and detected successfully with single photon ionization ion trap mass spectrometry (SPI-ITMS) MS/MS measurements. Additionally, first tests were performed, demonstrating that this method is not influenced by matrix compounds. The second field of application is the detection of process gases. Here, exhaust gas from coffee roasting was analyzed in real time, and some of its compounds were identified using MS/MS studies.

On the SIMS Ionization Probability of Organic Molecules.

PubMed

Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

2017-06-01

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract .

Indirect double photoionization of water

NASA Astrophysics Data System (ADS)

Resccigno, T. N.; Sann, H.; Orel, A. E.; Dörner, R.

2011-05-01

The vertical double ionization thresholds of small molecules generally lie above the dissociation limits corresponding to formation of two singly charged fragments. This gives the possibility of populating singly charged molecular ions by photoionization in the Franck-Condon region at energies below the lowest dication state, but above the dissociation limit into two singly charged fragment ions. This process can produce a superexcited neutral fragment that autoionizes at large internuclear separation. We study this process in water, where absorption of a photon produces an inner-shell excited state of H2O+ that fragments to H++OH*. The angular distribution of secondary electrons produced by OH* when it autoionizes produces a characteristic asymmetric pattern that reveals the distance, and therefore the time, at which the decay takes place. LBNL, Berkeley, CA, J. W. Goethe Universität, Frankfurt, Germany. Work performed under auspices of US DOE and supported by OBES, Div. of Chemical Sciences.

Microhydration Prevents Fragmentation of Uracil and Thymine by Low-Energy Electrons.

PubMed

Kočišek, J; Pysanenko, A; Fárník, M; Fedor, J

2016-09-01

When ionizing radiation passes biological matter, a large number of secondary electrons with very low energies (<3 eV) is produced. It is known that such electrons cause an efficient fragmentation of isolated nucleobases via dissociative electron attachment. We present an experimental study of the electron attachment to microhydrated nucleobases. Our novel approach allows significant control over the hydration of molecules studied in the molecular beam. We directly show for the first time that the presence of a few water molecules suppresses the dissociative channel and leads exclusively to formation of intact molecular and hydrated anions. The suppression of fragmentation is ascribed to caging-like effects and fast energy transfer to the solvent. This is in contrast with theoretical prediction that microhydration strongly enhances the fragmentation of nucleobases. The current observation impacts mechanisms of reductive DNA strand breaks proposed to date on the basis of gas-phase experiments.

Ultrafast laser-induced modifications of energy bands of non-metal crystals

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2009-10-01

Ultrafast laser-induced variations of electron energy bands of transparent solids significantly influence ionization and conduction-band electron absorption driving the initial stage of laser-induced damage (LID). The mechanisms of the variations are attributed to changing electron functions from bonding to anti-bonding configuration via laser-induced ionization; laser-driven electron oscillations in quasi-momentum space; and direct distortion of the inter-atomic potential by electric field of laser radiation. The ionization results in the band-structure modification via accumulation of broken chemical bonds between atoms and provides significant contribution to the overall modification only when enough excited electrons are accumulated in the conduction band. The oscillations are associated with modification of electron energy by pondermotive potential of the oscillations. The direct action of radiation's electric field leads to specific high-frequency Franz-Keldysh effect (FKE) spreading the allowed electron states into the bands of forbidden energy. Those processes determine the effective band gap that is a laser-driven energy gap between the modified electron energy bands. Among those mechanisms, the latter two provide reversible band-structure modification that takes place from the beginning of the ionization and are, therefore, of special interest due to their strong influence on the initial stage of the ionization. The pondermotive potential results either in monotonous increase or oscillatory variations of the effective band gap that has been taken into account in some ionization models. The classical FKE provides decrease of the band gap. We analyzing the competition between those two opposite trends of the effective-band-gap variations and discuss applications of those effects for considerations of the laser-induced damage and its threshold in transparent solids.

UV DRIVEN EVAPORATION OF CLOSE-IN PLANETS: ENERGY-LIMITED, RECOMBINATION-LIMITED, AND PHOTON-LIMITED FLOWS

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

Owen, James E.; Alvarez, Marcelo A., E-mail: jowen@ias.edu

2016-01-01

We have investigated the evaporation of close-in exoplanets irradiated by ionizing photons. We find that the properties of the flow are controlled by the ratio of the recombination time to the flow timescale. When the recombination timescale is short compared to the flow timescale, the flow is in approximate local ionization equilibrium with a thin ionization front where the photon mean free path is short compared to the flow scale. In this “recombination-limited” flow the mass-loss scales roughly with the square root of the incident flux. When the recombination time is long compared to the flow timescale the ionization frontmore » becomes thick and encompasses the entire flow with the mass-loss rate scaling linearly with flux. If the planet's potential is deep, then the flow is approximately “energy-limited”; however, if the planet's potential is shallow, then we identify a new limiting mass-loss regime, which we term “photon-limited.” In this scenario, the mass-loss rate is purely limited by the incoming flux of ionizing photons. We have developed a new numerical approach that takes into account the frequency dependence of the incoming ionizing spectrum and performed a large suite of 1D simulations to characterize UV driven mass-loss around low-mass planets. We find that the flow is “recombination-limited” at high fluxes but becomes “energy-limited” at low fluxes; however, the transition is broad occurring over several orders of magnitude in flux. Finally, we point out that the transitions between the different flow types do not occur at a single flux value but depend on the planet's properties, with higher-mass planets becoming “energy-limited” at lower fluxes.« less

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

Micheva, Genoveva; Oey, M. S.; Jaskot, Anne E.

We present the remarkable discovery that the dwarf irregular galaxy NGC 2366 is an excellent analog of the Green Pea (GP) galaxies, which are characterized by extremely high ionization parameters. The similarities are driven predominantly by the giant H ii region Markarian 71 (Mrk 71). We compare the system with GPs in terms of morphology, excitation properties, specific star-formation rate, kinematics, absorption of low-ionization species, reddening, and chemical abundance, and find consistencies throughout. Since extreme GPs are associated with both candidate and confirmed Lyman continuum (LyC) emitters, Mrk 71/NGC 2366 is thus also a good candidate for LyC escape. Themore » spatially resolved data for this object show a superbubble blowout generated by mechanical feedback from one of its two super star clusters (SSCs), Knot B, while the extreme ionization properties are driven by the ≲1 Myr-old, enshrouded SSC Knot A, which has ∼10 times higher ionizing luminosity. Very massive stars (>100 M {sub ⊙}) may be present in this remarkable object. Ionization-parameter mapping indicates that the blowout region is optically thin in the LyC, and the general properties also suggest LyC escape in the line of sight. Mrk 71/NGC 2366 does differ from GPs in that it is one to two orders of magnitude less luminous. The presence of this faint GP analog and candidate LyC emitter (LCE) so close to us suggests that LCEs may be numerous and commonplace, and therefore could significantly contribute to the cosmic ionizing budget. Mrk 71/NGC 2366 offers an unprecedentedly detailed look at the viscera of a candidate LCE, and could clarify the mechanisms of LyC escape.« less

Magnetically Driven Accretion Disk Winds and Ultra-fast Outflows in PG 1211+143

NASA Astrophysics Data System (ADS)

Fukumura, Keigo; Tombesi, Francesco; Kazanas, Demosthenes; Shrader, Chris; Behar, Ehud; Contopoulos, Ioannis

2015-05-01

We present a study of X-ray ionization of MHD accretion-disk winds in an effort to constrain the physics underlying the highly ionized ultra-fast outflows (UFOs) inferred by X-ray absorbers often detected in various sub classes of Seyfert active galactic nuclei (AGNs). Our primary focus is to show that magnetically driven outflows are indeed physically plausible candidates for the observed outflows accounting for the AGN absorption properties of the present X-ray spectroscopic observations. Employing a stratified MHD wind launched across the entire AGN accretion disk, we calculate its X-ray ionization and the ensuing X-ray absorption-line spectra. Assuming an appropriate ionizing AGN spectrum, we apply our MHD winds to model the absorption features in an XMM-Newton/EPIC spectrum of the narrow-line Seyfert, PG 1211+143. We find, through identifying the detected features with Fe Kα transitions, that the absorber has a characteristic ionization parameter of log (ξc[erg cm s-1]) ≃ 5-6 and a column density on the order of NH ≃ 1023 cm-2 outflowing at a characteristic velocity of vc/c ≃ 0.1-0.2 (where c is the speed of light). The best-fit model favors its radial location at rc ≃ 200 Ro (Ro is the black hole’s innermost stable circular orbit), with an inner wind truncation radius at Rt ≃ 30 Ro. The overall K-shell feature in the data is suggested to be dominated by Fe xxv with very little contribution from Fe xxvi and weakly ionized iron, which is in good agreement with a series of earlier analyses of the UFOs in various AGNs, including PG 1211+143.

Temporal patterns of damage and decay kinetics of DNA retrieved from plant herbarium specimens.

PubMed

Weiß, Clemens L; Schuenemann, Verena J; Devos, Jane; Shirsekar, Gautam; Reiter, Ella; Gould, Billie A; Stinchcombe, John R; Krause, Johannes; Burbano, Hernán A

2016-06-01

Herbaria archive a record of changes of worldwide plant biodiversity harbouring millions of specimens that contain DNA suitable for genome sequencing. To profit from this resource, it is fundamental to understand in detail the process of DNA degradation in herbarium specimens. We investigated patterns of DNA fragmentation and nucleotide misincorporation by analysing 86 herbarium samples spanning the last 300 years using Illumina shotgun sequencing. We found an exponential decay relationship between DNA fragmentation and time, and estimated a per nucleotide fragmentation rate of 1.66 × 10(-4) per year, which is six times faster than the rate estimated for ancient bones. Additionally, we found that strand breaks occur specially before purines, and that depurination-driven DNA breakage occurs constantly through time and can to a great extent explain decreasing fragment length over time. Similar to what has been found analysing ancient DNA from bones, we found a strong correlation between the deamination-driven accumulation of cytosine to thymine substitutions and time, which reinforces the importance of substitution patterns to authenticate the ancient/historical nature of DNA fragments. Accurate estimations of DNA degradation through time will allow informed decisions about laboratory and computational procedures to take advantage of the vast collection of worldwide herbarium specimens.

Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis

PubMed Central

D’Souza, Malcolm J.; Mahon, Brian P.; Kevill, Dennis N.

2010-01-01

Correlation of the solvent effects through application of the extended Grunwald-Winstein equation to the solvolysis of isopropyl chlorothioformate results in a sensitivity value of 0.38 towards changes in solvent nucleophilicity (l) and a sensitivity value of 0.72 towards changes in solvent ionizing power (m). This tangible l value coupled with the negative entropies of activation observed indicates a favorable predisposition towards a modest rear-side nucleophilic solvation of a developing carbocation. Only in 100% ethanol was the bimolecular pathway dominant. These observations are very different from those obtained for the solvolysis of isopropyl chloroformate, where dual reaction channels were proposed, with the addition-elimination reaction favored in the more nucleophilic solvents and a unimolecular fragmentation-ionization mechanism favored in the highly ionizing solvents. PMID:20717524

Corona discharge ionization of paracetamol molecule: peak assignment.

PubMed

Bahrami, H; Farrokhpour, H

2015-01-25

Ionization of paracetamol was investigated using ion mobility spectrometry equipped with a corona discharge ionization source. The measurements were performed in the positive ion mode and three peaks were observed in the ion mobility spectrum. Experimental evidence and theoretical calculations were used to correlate the peaks to related ionic species of paracetamol. Two peaks were attributed to protonated isomers of paracetamol and the other peak was attributed to paracetamol fragment ions formed by dissociation of the N-C bond after protonation of the nitrogen atom. It was observed that three sites of paracetamol compete for protonation and their relative intensities, depending on the sample concentration. The ratio of ion products could be predicted from the internal proton affinity of the protonation sites at each concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

Total Electron-Impact Ionization Cross-Sections of CFx and NFx (x = 1 - 3)

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Tarnovsky, Vladimir; Becker, Kurt H.; Kwak, Dochan (Technical Monitor)

2001-01-01

The discrepancy between experimental and theoretical total electron-impact ionization cross sections for a group of fluorides, CFx, and NFx, (x = 1 - 3), is attributed to the inadequacies in previous theoretical models. Cross-sections calculated using a recently developed siBED (simulation Binary-Encounter-Dipole) model that takes into account the shielding of the long-range dipole potential between the scattering electron and target are in agreement with experimentation. The present study also carefully reanalyzed the previously reported experimental data to account for the possibility of incomplete collection of fragment ions and the presence of ion-pair formation channels. For NF3, our experimental and theoretical cross-sections compare well with the total ionization cross-sections recently reported by Haaland et al. in the region below dication formation.

High resolution mass spectrometry method and system for analysis of whole proteins and other large molecules

DOEpatents

Reilly, Peter T. A. [Knoxville, TN; Harris, William A [Naperville, IL

2010-03-02

A matrix assisted laser desorption/ionization (MALDI) method and related system for analyzing high molecular weight analytes includes the steps of providing at least one matrix-containing particle inside an ion trap, wherein at least one high molecular weight analyte molecule is provided within the matrix-containing particle, and MALDI on the high molecular weight particle while within the ion trap. A laser power used for ionization is sufficient to completely vaporize the particle and form at least one high molecular weight analyte ion, but is low enough to avoid fragmenting the high molecular weight analyte ion. The high molecular weight analyte ion is extracted out from the ion trap, and is then analyzed using a detector. The detector is preferably a pyrolyzing and ionizing detector.

Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

PubMed

Kiss, András; Hopfgartner, Gérard

2016-07-15

Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Two-color ionization injection using a plasma beatwave accelerator

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

Schroeder, C. B.; Benedetti, C.; Esarey, E.

Two-color laser ionization injection is a method to generate ultra-low emittance (sub-100 nm transverse normalized emittance) beams in a laser-driven plasma accelerator. A plasma beatwave accelerator is proposed to drive the plasma wave for ionization injection, where the beating of the lasers effectively produces a train of long-wavelength pulses. The plasma beatwave accelerator excites a large amplitude plasma wave with low peak laser electric fields, leaving atomically-bound electrons with low ionization potential. A short-wavelength, low-amplitude ionization injection laser pulse (with a small ponderomotive force and large peak electric field) is used to ionize the remaining bound electrons at a wakemore » phase suitable for trapping, generating an ultra-low emittance electron beam that is accelerated in the plasma wave. Using a plasma beatwave accelerator for wakefield excitation, compared to short-pulse wakefield excitation, allows for a lower amplitude injection laser pulse and, hence, a lower emittance beam may be generated.« less

Two-color ionization injection using a plasma beatwave accelerator

DOE PAGES

Schroeder, C. B.; Benedetti, C.; Esarey, E.; ...

2018-01-10

Two-color laser ionization injection is a method to generate ultra-low emittance (sub-100 nm transverse normalized emittance) beams in a laser-driven plasma accelerator. A plasma beatwave accelerator is proposed to drive the plasma wave for ionization injection, where the beating of the lasers effectively produces a train of long-wavelength pulses. The plasma beatwave accelerator excites a large amplitude plasma wave with low peak laser electric fields, leaving atomically-bound electrons with low ionization potential. A short-wavelength, low-amplitude ionization injection laser pulse (with a small ponderomotive force and large peak electric field) is used to ionize the remaining bound electrons at a wakemore » phase suitable for trapping, generating an ultra-low emittance electron beam that is accelerated in the plasma wave. Using a plasma beatwave accelerator for wakefield excitation, compared to short-pulse wakefield excitation, allows for a lower amplitude injection laser pulse and, hence, a lower emittance beam may be generated.« less

Detection, characterization and identification of crucifer phytoalexins using high-performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry.

PubMed

Pedras, M Soledade C; Adio, Adewale M; Suchy, Mojmir; Okinyo, Denis P O; Zheng, Qing-An; Jha, Mukund; Sarwar, Mohammed G

2006-11-10

We have analyzed 23 crucifer phytoalexins (e.g. brassinin, dioxibrassinin, cyclobrassinin, brassicanals A and C) by HPLC with diode array detection and electrospray ionization mass spectrometry (HPLC-DAD-ESI-MS) using both negative and positive ion modes. Positive ion mode ESI-MS appeared more sensitive than negative ion mode ESI-MS in detecting this group of compounds. A new HPLC separation method, new LC-MS and LC-MS(2) data and proposed fragmentation pathways, LC retention times, and UV spectra for selected compounds are reported.

Observation of ionization fronts in low density foam targets

NASA Astrophysics Data System (ADS)

Hoarty, D.; Willi, O.; Barringer, L.; Vickers, C.; Watt, R.; Nazarov, W.

1999-05-01

Ionization fronts have been observed in low density chlorinated foam targets and low density foams confined in gold tubes using time resolved K-shell absorption spectroscopy. The front was driven by an intense pulse of soft x-rays produced by high power laser irradiation. The density and temperature profiles inferred from the radiographs provided detailed measurement of the conditions. The experimental data were compared to radiation hydrodynamics simulations and reasonable agreement was obtained.

Electronic Combat in Space: Examining the Legality of Fielding a Space-Based Disruptive Electromagnetic Jamming System

DTIC Science & Technology

2007-06-15

particles ( asteroids and meteoroids), energetic charged particles (ions, protons, electrons, etc.), and electromagnetic and ionizing radiation (x-rays...These protocols include a ban on Non-Detectable Fragments; restrictions on the use of Mines , Booby Traps, and Other Devices; prohibitions on certain...

Mass-Selective Laser Photoionization.

ERIC Educational Resources Information Center

Smalley, R. E.

1982-01-01

Discusses the nature and applications of mass-selective laser photoionization. The ionization can be done with a single intense laser pulse lasting a few billionths of a second with no molecular fragmentation. Applications focus on: (1) benzene clusters, excimers, and exciplexes; (2) metal clusters; and (3) triplet formation and decay. (Author/JN)

Measurement of gluconeogenesis using glucose fragments and mass spectrometry after ingestion of deuterium oxide.

USDA-ARS?s Scientific Manuscript database

We report a new method to measure the fraction of glucose derived from gluconeogenesis using gas chromatography-mass spectrometry and positive chemical ionization. After ingestion of deuterium oxide by subjects, glucose derived from gluconeogenesis is labeled with deuterium. Our calculations of gluc...

Dissecting the Butterfly: Dual Outflows in the Dual AGN NGC 6240

NASA Astrophysics Data System (ADS)

Mueller Sanchez, Francisco; Comerford, Julie; Nevin, Rebecca; Davies, Richard; Treister, Ezequiel; Privon, George

2018-01-01

Current theories of galaxy evolution invoke some kind of feedback (from the stars or the supermassive black hole) to explain the properties of galaxies. However, numerical simulations and observations have not been able to evaluate the real impact of feedback in galaxies. This is largely because most studies have focused on studying stellar feedback or AGN feedback alone, instead of considering the combined effect of both. In fact, this is an unexplored territory for observations due to the difficulty of separating the contribution from the two sources.In this contribution I present the discovery of a dual outflow of different species of gas in the prototypical merging galaxy NGC 6240 using HST imaging, long-slit and integral-eld spectroscopy: an AGN-driven outflow of highly-ionized gas to the northeast and a starburst-driven outflow of ionized hydrogen to the northwest. The AGN outflow extends up to 4 kpc along a position angle of 56 degrees, has a conical shape with an opening angle of 52 degrees and a maximum line-of-sight velocity of 350 km/s. The WFC3 images also reveal a bubble of Halpha emission in the northwest, which has no counterpart in [O III], consistent with a scenario in which the starburst is ionizing and driving outflowing winds which inflate the bubble at an expansion velocity of 380 km/s. Assuming a spherical geometry for the starburst-driven bubble and a conical geometry for the AGN-driven outflow, we estimate mass outflow rates of 26 Msun/yr and 62 Msun/yr, respectively. We conclude that the AGN contribution to the evolution of the merger remnant and the formation of outflowing winds is signicant in the central 5 kpc of NGC 6240.

Fragmentation mechanisms for methane induced by 55 eV, 75 eV, and 100 eV electron impact

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

Wei, B.; Zhang, Y.; Wang, X., E-mail: xinchengwang@fudan.edu.cn

2014-03-28

The fragmentation of CH{sub 4}{sup 2+} dications following 55 eV, 75 eV, and 100 eV electron impact double ionization of methane was studied using a cold target recoil-ion momentum spectroscopy. From the measured momentum of each recoil ion, the momentum of the neutral particles has been deduced and the kinetic energy release distribution for the different fragmentation channels has been obtained. The doubly charged molecular ions break up into three or more fragments in one or two-step processes, resulting in different signatures in the data. We observed the fragmentation of CH{sub 4}{sup 2+} dications through different mechanisms according to themore » momentum of the neutral particles. For example, our result shows that there are three reaction channels to form CH{sub 2}{sup +}, H{sup +}, and H, one synchronous concerted reaction channel and two two-step reaction channels. For even more complicated fragmentation processes of CH{sub 4}{sup 2+} dications, the fragmentation mechanism can still be identified in the present measurements. The slopes of the peak in the ion-ion coincidence spectra were also estimated here, as they are also related to the fragmentation mechanism.« less

An evaluation of ionizing radiation emitted by high power microwave generators

NASA Astrophysics Data System (ADS)

Lovell, C. David; Bolch, W. Emmett

1992-02-01

Ionizing radiation emitted by electron-beam driven high power microwave (HPM) generators were measured in the near and far-field using lithium fluoride (LiF) thermoluminescent dosimeters (TLD's). Simplified photon energy spectra were determined by measuring radiation transmission, at electron beam energies of 300 to 650 keV, through various thicknesses of steel and lead attenuators. These data were used to calculate the effective energy of the x-rays produced by interactions between the electrons and the walls or other structures of the HPM generators. Operators were polled to determine locations of burn marks or other visible damage to locate potential ionizing radiation source regions.

Drifting potential humps in ionization zones: The “propeller blades” of high power impulse magnetron sputtering

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

Anders, André; Ni, Pavel; Panjan, Matjaž

2013-09-30

Ion energy distribution functions measured for high power impulse magnetron sputtering show features, such as a broad peak at several 10 eV with an extended tail, as well as asymmetry with respect to E×B, where E and B are the local electric and magnetic field vectors, respectively. Here it is proposed that those features are due to the formation of a potential hump of several 10 V in each of the traveling ionization zones. Potential hump formation is associated with a negative-positive-negative space charge that naturally forms in ionization zones driven by energetic drifting electrons.

Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS.

PubMed

Petroselli, Gabriela; Mandal, Mridul Kanti; Chen, Lee Chuin; Ruiz, Gustavo T; Wolcan, Ezequiel; Hiraoka, Kenzo; Nonami, Hiroshi; Erra-Balsells, Rosa

2012-03-01

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355 nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones. Copyright © 2012 John Wiley & Sons, Ltd.

Ionization-Induced Self-Channeling of an Ultrahigh-Power Subnanosecond Microwave Beam in a Neutral Gas

NASA Astrophysics Data System (ADS)

Shafir, G.; Krasik, Ya. E.; Bliokh, Y. P.; Levko, D.; Cao, Y.; Leopold, J. G.; Gad, R.; Bernshtam, V.; Fisher, A.

2018-03-01

Ionization-induced self-channeling of a ≤500 MW , 9.6 GHz, <1 ns microwave beam injected into air at ˜4.5 ×103 Pa or He at ˜103 Pa is experimentally demonstrated for the first time. The plasma, generated by the impact ionization of the gas driven by the microwave beam, has a radial density distribution reducing towards the beam axis, where the microwave field is highest, because the ionization rate is a decreasing function of the microwave amplitude. This forms a plasma channel which prevents the divergence of the microwave beam. The experimental data obtained using various diagnostic methods are in good agreement with the results of analytical calculations, as well as particle in cell Monte Carlo collisional modeling.

Incorporation of fragmentation into a volume average solidification model

NASA Astrophysics Data System (ADS)

Zheng, Y.; Wu, M.; Kharicha, A.; Ludwig, A.

2018-01-01

In this study, a volume average solidification model was extended to consider fragmentation as a source of equiaxed crystals during mixed columnar-equiaxed solidification. The formulation suggested for fragmentation is based on two hypotheses: the solute-driven remelting is the dominant mechanism; and the transport of solute-enriched melt through an interdendritic flow in the columnar growth direction is favorable for solute-driven remelting and is the necessary condition for fragment transportation. Furthermore, a test case with Sn-10 wt%Pb melt solidifying vertically downward in a 2D domain (50 × 60 mm2) was calculated to demonstrate the model’s features. Solidification started from the top boundary, and a columnar structure developed initially with its tip growing downward. Furthermore, thermo-solutal convection led to fragmentation in the mushy zone near the columnar tip front. The fragments transported out of the columnar region continued to grow and sink, and finally settled down and piled up in the bottom domain. The growing columnar structure from the top and pile-up of equiaxed crystals from the bottom finally led to a mixed columnar-equiaxed structure, in turn leading to a columnar-to-equiaxed transition (CET). A special macrosegregation pattern was also predicted, in which negative segregation occurred in both columnar and equiaxed regions and a relatively strong positive segregation occurred in the middle domain near the CET line. A parameter study was performed to verify the model capability, and the uncertainty of the model assumption and parameter was discussed.

Fragmentation Patterns and Mechanisms of Singly and Doubly Protonated Peptoids Studied by Collision Induced Dissociation

NASA Astrophysics Data System (ADS)

Ren, Jianhua; Tian, Yuan; Hossain, Ekram; Connolly, Michael D.

2016-04-01

Peptoids are peptide-mimicking oligomers consisting of N-alkylated glycine units. The fragmentation patterns for six singly and doubly protonated model peptoids were studied via collision-induced dissociation tandem mass spectrometry. The experiments were carried out on a triple quadrupole mass spectrometer with an electrospray ionization source. Both singly and doubly protonated peptoids were found to fragment mainly at the backbone amide bonds to produce peptoid B-type N-terminal fragment ions and Y-type C-terminal fragment ions. However, the relative abundances of B- versus Y-ions were significantly different. The singly protonated peptoids fragmented by producing highly abundant Y-ions and lesser abundant B-ions. The Y-ion formation mechanism was studied through calculating the energetics of truncated peptoid fragment ions using density functional theory and by controlled experiments. The results indicated that Y-ions were likely formed by transferring a proton from the C-H bond of the N-terminal fragments to the secondary amine of the C-terminal fragments. This proton transfer is energetically favored, and is in accord with the observation of abundant Y-ions. The calculations also indicated that doubly protonated peptoids would fragment at an amide bond close to the N-terminus to yield a high abundance of low-mass B-ions and high-mass Y-ions. The results of this study provide further understanding of the mechanisms of peptoid fragmentation and, therefore, are a valuable guide for de novo sequencing of peptoid libraries synthesized via combinatorial chemistry.

A combined thermal dissociation and electron impact ionization source for radioactive ion beam generation{sup a}

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

Alton, G.D.; Williams, C.

1996-04-01

The probability for simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecular feed materials with conventional, hot-cathode, electron-impact ion sources is low and consequently, the ion beams from these sources often appear as mixtures of several molecular sideband beams. This fragmentation process leads to dilution of the intensity of the species of interest for radioactive ion beam (RIB) applications where beam intensity is at a premium. We have conceived an ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high ionization efficiency characteristics of an electron impact ionization source that will, inmore » principle, overcome this handicap. The source concept will be evaluated as a potential candidate for use for RIB generation at the Holifield Radioactive Ion Beam Facility, now under construction at the Oak Ridge National Laboratory. The design features and principles of operation of the source are described in this article. {copyright} {ital 1996 American Institute of Physics.}« less

A combined thermal dissociation and electron impact ionization source for radioactive ion beam generation (abstract){sup a}

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

Alton, G.D.; Williams, C.

1996-03-01

The probability for simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecular feed materials with conventional, hot-cathode, electron-impact ion sources is low and consequently, the ion beams from these sources often appear as mixtures of several molecular sideband beams. This fragmentation process leads to dilution of the intensity of the species of interest for radioactive ion beam (RIB) applications where beam intensity is at a premium. We have conceived an ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high ionization efficiency characteristics of an electron impact ionization source that will, inmore » principle, overcome this handicap. The source concept will be evaluated as a potential candidate for use for RIB generation at the Holifield Radioactive Ion Beam Facility, now under construction at the Oak Ridge National Laboratory. The design features and principles of operation of the source are described in this article. {copyright} {ital 1996 American Institute of Physics.}« less

Fatty acids composition of Caenorhabditis elegans using accurate mass GCMS-QTOF

PubMed Central

Henry, Parise; Owopetu, Olufunmilayo; Adisa, Demilade; Nguyen, Thao; Anthony, Kevin; Ijoni-Animadu, David; Jamadar, Sakha; Abdel-Rahman, Fawzia; Saleh, Mahmoud A.

2016-01-01

The free living nematode Caenorhabditis elegans is a proven model organism for lipid metabolism research. Total lipids of C. elegans were extracted using chloroform, methanol 2:1(v/v). Fatty acids composition of the extracted total lipids were converted to their corresponding methyl esters (FAMEs) and analyzed by gas chromatography/accurate mass quadrupole time of flight mass spectrometry (GCMS-QTOF) using both electron ionization (EI) and chemical ionization (CI) techniques. 28 fatty acids consisting of 12 to 22 carbon atoms were identified, 65% of them were unsaturated. Fatty acids containing 12 to 17 carbons were mostly saturated with stearic acid (18:0) as the major constituent. Several branched-chain fatty acids were identified. Methyl-14-methylhexadecanoate (iso-17:0) was the major identified branched fatty acid. This is the first report to detect the intact molecular parent ions of the identified fatty acids using chemical ionization compared to electron ionization which produced fragmentations of the fatty acids methyl esters (FAMEs). PMID:27166662

Fast quantitative detection of cocaine in beverages using nanoextractive electrospray ionization tandem mass spectrometry.

PubMed

Hu, Bin; Peng, Xuejiao; Yang, Shuiping; Gu, Haiwei; Chen, Huanwen; Huan, Yanfu; Zhang, Tingting; Qiao, Xiaolin

2010-02-01

Without any sample pretreatment, effervescent beverage fluids were manually sprayed into the primary ion plume created by using a nanoelectrospray ionization source for direct ionization, and the analyte ions of interest were guided into an ion trap mass spectrometer for tandem mass analysis. Functional ingredients (e.g., vitamins, taurine, and caffeine, etc.) and spiked impurity (e.g., cocaine) in various beverages, such as Red Bull energy drink, Coco-cola, and Pepsi samples were rapidly identified within 1.5 s. The limit of detection was found to be 7-15 fg (S/N = 3) for cocaine in different samples using the characteristic fragment (m/z 150) observed in the MS(3) experiments. Typical relative standard deviation and recovery of this method were 6.9%-8.6% and 104%-108% for direct analysis of three actual samples, showing that nanoextractive electrospray ionization tandem mass spectrometry is a useful technique for fast screening cocaine presence in beverages. 2010. Published by Elsevier Inc.

Improving N-Glycan Coverage using HPLC-MS with Electrospray Ionization at Subambient Pressure

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

Marginean, Ioan; Kronewitter, Scott R.; Moore, Ronald J.

Human serum glycan profiling with mass spectrometry (MS) has been employed to study several disease conditions and is demonstrating promise for e.g. clinical biomarker discovery. However, the poor glycan ionization efficiency and the large dynamic range of glycan concentrations in human sera hinder comprehensive profiling. In particular, large glycans are problematic because they are present at low concentrations and prone to fragmentation. Here we show that the sub-ambient pressure ionization with nanoelectrospray (SPIN)-MS can expand the serum glycome profile when compared with the conventional atmospheric pressure electrospray ionization (ESI)-MS with a heated capillary inlet. Notably, the ions generated by themore » SPIN interface were observed at higher charge states for 50% of the annotated glycans. Out of a total of 130 detected glycans, 34 were only detected with the SPIN-MS, resulting in improved coverage of glycan families as well as of glycans with larger numbers of labile monosaccharides.« less

Fission fragment yields and total kinetic energy release in neutron-induced fission of235,238U,and239Pu

NASA Astrophysics Data System (ADS)

Tovesson, F.; Duke, D.; Geppert-Kleinrath, V.; Manning, B.; Mayorov, D.; Mosby, S.; Schmitt, K.

2018-03-01

Different aspects of the nuclear fission process have been studied at Los Alamos Neutron Science Center (LANSCE) using various instruments and experimental techniques. Properties of the fragments emitted in fission have been investigated using Frisch-grid ionization chambers, a Time Projection Chamber (TPC), and the SPIDER instrument which employs the 2v-2E method. These instruments and experimental techniques have been used to determine fission product mass yields, the energy dependent total kinetic energy (TKE) release, and anisotropy in neutron-induced fission of U-235, U-238 and Pu-239.

Angular correlations in the prompt neutron emission in spontaneous fission of 252Cf

NASA Astrophysics Data System (ADS)

Kopatch, Yuri; Chietera, Andreina; Stuttgé, Louise; Gönnenwein, Friedrich; Mutterer, Manfred; Gagarski, Alexei; Guseva, Irina; Dorvaux, Olivier; Hanappe, Francis; Hambsch, Franz-Josef

2017-09-01

An experiment aiming at the detailed investigation of angular correlations in the neutron emission from spontaneous fission of 252Cf has been performed at IPHC Strasbourg using the angle-sensitive double ionization chamber CODIS for measuring fission fragments and a set of 60 DEMON scintillator counters for neutron detection. The main aim of the experiment is to search for an anisotropy of neutron emission in the center-of-mass system of the fragments. The present status of the data analysis and the full Monte-Carlo simulation of the experiment are reported in the present paper.

Gas-Phase Coordination Complexes of UVIO{2/2+}, NpVIO{2/2+}, and PuVIO{2/2+} with Dimethylformamide

NASA Astrophysics Data System (ADS)

Rutkowski, Philip X.; Rios, Daniel; Gibson, John K.; van Stipdonk, Michael J.

2011-11-01

Electrospray ionization of actinyl perchlorate solutions in H2O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [AnVIO2(DMF)3(H2O)]2+ and [AnVIO2(DMF)4]2+, where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI).

[Identification of related substances in nicergoline by HPLC-MS].

PubMed

Zeng, Xue-fang; Liu, Jie; Song, Min; Hang, Tai-jun

2015-08-01

To study the related substances in nicergoline, electrospray positive ionization high resolution TOF/MS was used for the determination of the accurate mass and elemental composition of the related substances. Triple quadrupoles tandem MS/MS was employed for the determination of the fragmentations of the parent ions. 16 related substances were detected and identified to be eight synthetic by-products and eight degradation products, by using impurity references matching, product mass spectra fragmentations elucidation, and verified further according to synthetic processes and stress testing results. The results obtained are valuable for nicergoline manufacturing process control and quality assurance.

Photoionization of High-altitude Gas in a Supernova-driven Turbulent Interstellar Medium

NASA Astrophysics Data System (ADS)

Wood, Kenneth; Hill, Alex S.; Joung, M. Ryan; Mac Low, Mordecai-Mark; Benjamin, Robert A.; Haffner, L. Matthew; Reynolds, R. J.; Madsen, G. J.

2010-10-01

We investigate models for the photoionization of the widespread diffuse ionized gas (DIG) in galaxies. In particular, we address the long standing question of the penetration of Lyman continuum photons from sources close to the galactic midplane to large heights in the galactic halo. We find that recent hydrodynamical simulations of a supernova-driven interstellar medium (ISM) have low-density paths and voids that allow for ionizing photons from midplane OB stars to reach and ionize gas many kiloparsecs above the midplane. We find that ionizing fluxes throughout our simulation grids are larger than predicted by one-dimensional slab models, thus allowing for photoionization by O stars of low altitude neutral clouds in the Galaxy that are also detected in Hα. In previous studies of such clouds, the photoionization scenario had been rejected and the Hα had been attributed to enhanced cosmic ray ionization or scattered light from midplane H II regions. We do find that the emission measure distributions in our simulations are wider than those derived from Hα observations in the Milky Way. In addition, the horizontally averaged height dependence of the gas density in the hydrodynamical models is lower than inferred in the Galaxy. These discrepancies are likely due to the absence of magnetic fields in the hydrodynamic simulations and we discuss how magnetohydrodynamic effects may reconcile models and observations. Nevertheless, we anticipate that the inclusion of magnetic fields in the dynamical simulations will not alter our primary finding that midplane OB stars are capable of producing high-altitude DIG in a realistic three-dimensional ISM.

Ultrafast absorption of intense x rays by nitrogen molecules

NASA Astrophysics Data System (ADS)

Buth, Christian; Liu, Ji-Cai; Chen, Mau Hsiung; Cryan, James P.; Fang, Li; Glownia, James M.; Hoener, Matthias; Coffee, Ryan N.; Berrah, Nora

2012-06-01

We devise a theoretical description for the response of nitrogen molecules (N2) to ultrashort and intense x rays from the free electron laser Linac Coherent Light Source (LCLS). We set out from a rate-equation description for the x-ray absorption by a nitrogen atom. The equations are formulated using all one-x-ray-photon absorption cross sections and the Auger and radiative decay widths of multiply-ionized nitrogen atoms. Cross sections are obtained with a one-electron theory and decay widths are determined from ab initio computations using the Dirac-Hartree-Slater (DHS) method. We also calculate all binding and transition energies of nitrogen atoms in all charge states with the DHS method as the difference of two self-consistent field (SCF) calculations (ΔSCF method). To describe the interaction with N2, a detailed investigation of intense x-ray-induced ionization and molecular fragmentation are carried out. As a figure of merit, we calculate ion yields and the average charge state measured in recent experiments at the LCLS. We use a series of phenomenological models of increasing sophistication to unravel the mechanisms of the interaction of x rays with N2: a single atom, a symmetric-sharing model, and a fragmentation-matrix model are developed. The role of the formation and decay of single and double core holes, the metastable states of N_2^{2+}, and molecular fragmentation are explained.

Hydrazinonicotinic acid derivatization for selective ionization and improved glycan structure characterization by MALDI-MS.

PubMed

Jiao, Jing; Yang, Lijun; Zhang, Ying; Lu, Haojie

2015-08-21

The analysis of glycan is important for understanding cell biology and disease processes because the glycans play a key role in many important biological behaviors, such as cell division, cellular localization, tumor immunology and inflammation. Nevertheless, it is still hard work to analyze glycans by MALDI-MS, which generally stems from the inherent low abundance and the low ionization efficiency of glycans. Moreover, the difficulty in generating informative fragmentations further hinders glycans structure characterization. In this work, hydrazinonicotinic acid (HYNIC) was used as a novel derivatized reagent for improved and selective detection of glycans. Through tagging the reducing terminus of glycans with the diazanyl group of HYNIC, significant enhancement of the ionization efficiency of glycans was achieved. After derivatization, the signal to noise ratio (S/N) of the maltoheptaose was improved by more than one order of magnitude in positive mode. HYNIC derivatization also allowed the sensitive detection of sialylated glycan in negative mode, with a 15 fold enhancement of S/N. Interestingly, it is noteworthy that the HYNIC reagent not only effectively labeled the reducing end of glycans in the presence of tryptic peptides, but also suppressed the ionization of peptides, enabling the direct detection of glycans from glycoprotein without separation. Therefore, analysis of glycans became easier due to the omission of a pre-separation step. Importantly, by using different acid reagents as the catalyst, derivatized product signals corresponding to [M + Na](+) or [M + H](+) were obtained respectively, which yield complementary fragmentation patterns for the structure elucidation of glycans. Finally, more than 40 N-glycans were successfully detected in 10 μL human serum using this method.

Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

PubMed

Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

2016-09-21

The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Morphological and transcriptional response of an anhydrobiotic insect to ionizing radiation and desiccation: steps forward in understanding molecular background of extreme radioresistance in higher eukaryotes

NASA Astrophysics Data System (ADS)

Gusev, Oleg; Novikova, Nataliya; Sychev, Vladimir; Okuda, Takashi; Kikawada, Takahiro; Sakashita, Tetsuya; Mukae, Kyosuke

2012-07-01

Life in extreme or drastically changing environments in many cases leads to evolutionary evolvement of mechanisms of cross-resistance to different abiotic stresses, often never actually faced by the organism in its natural habitat. Larvae of the sleeping chironomidPolypedilum vanderplanki (Diptera) are able to resist complete desiccation and in the dry form survive under excess of various abiotic stresses, including exposure to space environment. One of the most intriguing features of the anhydrobiotic larvae is resistance to extremely high doses of different types of ionizing radiation. To understand the cross-tolerance mechanism, we have analyzed the structural changes in the nuclear DNA using transmission electron microscopy and DNA comet assays in relation to anhydrobiosis and radiation. We find that dehydration causes alterations in chromatin structure and a severe fragmentation of nuclear DNA in the cells of the larvae despite successful anhydrobiosis. The DNA fragmentation level and the recovery of DNA integrity in the rehydrated after anhydrobiosis larvae were similar to those of hydrated larvae irradiated with 70 Gy of high-linear energy transfer (LET) ions (4He+). In comparison, low-LET radiation (gamma rays) of the same dose causes less initial damage to the larvae, and recovery of DNA repair is complete within 24 h. Genome-wide analysis of mRNA expression in the larvae revealed that a large group of genes (including antioxidants, anhydrobiosis-specific biomolecules and protein-reparation enzymes) showed a similar patterns of activity in response to both desiccation and ionizing radiation. We conclude that t one of the factors explaining the relationship between the resistance to ionizing radiation and the ability to undergo anhydrobiosis in the sleeping chironomid would be an adaptation to desiccation-inflicted proteins and nuclear DNA damage.

Femtosecond-laser-induced nonadiabatic alignment in photoexcited pyrimidine

NASA Astrophysics Data System (ADS)

Li, Shuai; Ling, Fengzi; Wang, Yanmei; Long, Jinyou; Deng, Xulan; Jin, Bing; Zhang, Bing

2017-09-01

The rotational wave-packet dynamics in electronically excited pyrimidine induced by a femtosecond laser pulse at 321.5 nm has been studied by time-resolved mass spectroscopy and photoelectron velocity-map imaging. The rotational revival features at 81.3 ps, which are the direct manifestation of field-free nonadiabatic alignment, are clearly observed in both the time-dependent ion yields and photoelectron angular distributions. In particular, the out-of-phase recurrences in the parent-ion and fragment-ions transients indicate the different directions of the ionization transition-dipole moments for the generation of the parent ion and fragment ions. By tuning the polarization of the probe light parallel or perpendicular to that of the pump light, we demonstrate the potential application of nonadiabatic alignment to manipulate the branching ratio of photoionization products.

Ionizing gas breakdown waves in strong electric fields.

NASA Technical Reports Server (NTRS)

Klingbeil, R.; Tidman, D. A.; Fernsler, R. F.

1972-01-01

A previous analysis by Albright and Tidman (1972) of the structure of an ionizing potential wave driven through a dense gas by a strong electric field is extended to include atomic structure details of the background atoms and radiative effects, especially, photoionization. It is found that photoionization plays an important role in avalanche propagation. Velocities, electron densities, and temperatures are presented as a function of electric field for both negative and positive breakdown waves in nitrogen.

Observation of Transonic Ionization Fronts in Low-Density Foam Targets

NASA Astrophysics Data System (ADS)

Hoarty, D.; Barringer, L.; Vickers, C.; Willi, O.; Nazarov, W.

1999-04-01

Transonic ionization fronts have been observed in low-density chlorinated foam targets using time-resolved K-shell absorption spectroscopy. The front was driven by an intense pulse of soft x rays produced by high-power laser irradiation of a thin foil. The density and temperature profiles inferred from the radiographs provided detailed measurement of the conditions at a number of times. The experimental data were compared to radiation hydrodynamics simulations and reasonable agreement was obtained.

Fast ionized X-ray absorbers in AGNs

NASA Astrophysics Data System (ADS)

Fukumura, K.; Tombesi, F.; Kazanas, D.; Shrader, C.; Behar, E.; Contopoulos, I.

2016-05-01

We investigate the physics of the X-ray ionized absorbers often identified as warm absorbers (WAs) and ultra-fast outflows (UFOs) in Seyfert AGNs from spectroscopic studies in the context of magnetically-driven accretion-disk wind scenario. Launched and accelerated by the action of a global magnetic field anchored to an underlying accretion disk around a black hole, outflowing plasma is irradiated and ionized by an AGN radiation field characterized by its spectral energy density (SED). By numerically solving the Grad-Shafranov equation in the magnetohydrodynamic (MHD) framework, the physical property of the magnetized disk-wind is determined by a wind parameter set, which is then incorporated into radiative transfer calculations with xstar photoionization code under heating-cooling equilibrium state to compute the absorber's properties such as column density N_H, line-of-sight (LoS) velocity v, ionization parameter ξ, among others. Assuming that the wind density scales as n ∝ r-1, we calculate theoretical absorption measure distribution (AMD) for various ions seen in AGNs as well as line spectra especially for the Fe Kα absorption feature by focusing on a bright quasar PG 1211+143 as a case study and show the model's plausibility. In this note we demonstrate that the proposed MHD-driven disk-wind scenario is not only consistent with the observed X-ray data, but also help better constrain the underlying nature of the AGN environment in a close proximity to a central engine.

Marine fisheries declines viewed upside down: human impacts on consumer-driven nutrient recycling.

PubMed

Layman, Craig A; Allgeier, Jacob E; Rosemond, Amy D; Dahlgren, Craig P; Yeager, Lauren A

2011-03-01

We quantified how two human impacts (overfishing and habitat fragmentation) in nearshore marine ecosystems may affect ecosystem function by altering the role of fish as nutrient vectors. We empirically quantified size-specific excretion rates of one of the most abundant fishes (gray snapper, Lutjanus griseus) in The Bahamas and combined these with surveys of fish abundance to estimate population-level excretion rates. The study was conducted across gradients of two human disturbances: overfishing and ecosystem fragmentation (estuaries bisected by roads), to evaluate how each could result in reduced population-level nutrient cycling by consumers. Mean estimated N and P excretion rates for gray snapper populations were on average 456% and 541% higher, respectively, in unfished sites. Ecosystem fragmentation resulted in significant reductions of recycling rates by snapper, with degree of creek fragmentation explaining 86% and 72% of the variance in estimated excretion for dissolved N and P, respectively. Additionally, we used nutrient limitation assays and primary producer nutrient content to provide a simple example of how marine fishery declines may affect primary production. This study provides an initial step toward integrating marine fishery declines and consumer-driven nutrient recycling to more fully understand the implications of human impacts in marine ecosystems.

CO OBSERVATIONS AND INVESTIGATION OF TRIGGERED STAR FORMATION TOWARD THE N10 INFRARED BUBBLE AND SURROUNDINGS

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

Gama, D. R. G.; Lepine, J. R. D.; Mendoza, E.

We studied the environment of the dust bubble N10 in molecular emission. Infrared bubbles, first detected by the GLIMPSE survey at 8.0 μ m, are ideal regions to investigate the effect of the expansion of the H ii region on its surroundings and the eventual triggering of star formation at its borders. In this work, we present a multi-wavelength study of N10. This bubble is especially interesting because infrared studies of the young stellar content suggest a scenario of ongoing star formation, possibly triggered on the edge of the H ii region. We carried out observations of {sup 12}CO(1-0) andmore » {sup 13}CO(1-0) emission at PMO 13.7 m toward N10. We also analyzed the IR and sub-millimeter emission on this region and compare those different tracers to obtain a detailed view of the interaction between the expanding H ii region and the molecular gas. We also estimated the parameters of the denser cold dust condensation and the ionized gas inside the shell. Bright CO emission was detected and two molecular clumps were identified from which we have derived physical parameters. We also estimate the parameters for the densest cold dust condensation and for the ionized gas inside the shell. The comparison between the dynamical age of this region and the fragmentation timescale favors the “Radiation-Driven Implosion” mechanism of star formation. N10 is a case of particular interest with gas structures in a narrow frontier between the H ii region and surrounding molecular material, and with a range of ages of YSOs situated in the region, indicating triggered star formation.« less

Specific Cα-C Bond Cleavage of β-Carbon-Centered Radical Peptides Produced by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Nagoshi, Keishiro; Yamakoshi, Mariko; Sakamoto, Kenya; Takayama, Mitsuo

2018-04-01

Radical-driven dissociation (RDD) of hydrogen-deficient peptide ions [M - H + H]·+ has been examined using matrix-assisted laser dissociation/ionization in-source decay mass spectrometry (MALDI-ISD MS) with the hydrogen-abstracting matrices 4-nitro-1-naphthol (4,1-NNL) and 5-nitrosalicylic acid (5-NSA). The preferential fragment ions observed in the ISD spectra include N-terminal [a] + ions and C-terminal [x]+, [y + 2]+, and [w]+ ions which imply that β-carbon (Cβ)-centered radical peptide ions [M - Hβ + H]·+ are predominantly produced in MALDI conditions. RDD reactions from the peptide ions [M - Hβ + H]·+ successfully explains the fact that both [a]+ and [x]+ ions arising from cleavage at the Cα-C bond of the backbone of Gly-Xxx residues are missing from the ISD spectra. Furthermore, the formation of [a]+ ions originating from the cleavage of Cα-C bond of deuterated Ala(d3)-Xxx residues indicates that the [a]+ ions are produced from the peptide ions [M - Hβ + H]·+ generated by deuteron-abstraction from Ala(d3) residues. It is suggested that from the standpoint of hydrogen abstraction via direct interactions between the nitro group of matrix and hydrogen of peptides, the generation of the peptide radical ions [M - Hβ + H]·+ is more favorable than that of the α-carbon (Cα)-centered radical ions [M - Hα + H]·+ and the amide nitrogen-centered radical ions [M - HN + H]·+, while ab initio calculations indicate that the formation of [M - Hα + H]·+ is energetically most favorable. [Figure not available: see fulltext.

Ionization and thermal equilibrium models for O star winds based on time-independent radiation-driven wind theory

NASA Technical Reports Server (NTRS)

Drew, J. E.

1989-01-01

Ab initio ionization and thermal equilibrium models are calculated for the winds of O stars using the results of steady state radiation-driven wind theory to determine the input parameters. Self-consistent methods are used for the roles of H, He, and the most abundant heavy elements in both the statistical and the thermal equilibrium. The model grid was chosen to encompass all O spectral subtypes and the full range of luminosity classes. Results of earlier modeling of O star winds by Klein and Castor (1978) are reproduced and used to motivate improvements in the treatment of the hydrogen equilibrium. The wind temperature profile is revealed to be sensitive to gross changes in the heavy element abundances, but insensitive to other factors considered such as the mass-loss rate and velocity law. The reduced wind temperatures obtained in observing the luminosity dependence of the Si IV lambda 1397 wind absorption profile are shown to eliminate any prospect of explaining the observed O VI lambda 1036 line profiles in terms of time-independent radiation-driven wind theory.

Thermodynamic studies for adsorption of ionizable pharmaceuticals onto soil.

PubMed

Maszkowska, Joanna; Wagil, Marta; Mioduszewska, Katarzyna; Kumirska, Jolanta; Stepnowski, Piotr; Białk-Bielińska, Anna

2014-09-01

Although pharmaceutical compounds (PCs) are being used more and more widely, and studies have been carried out to assess their presence in the environment, knowledge of their fate and behavior, especially under different environmental conditions, is still limited. The principle objective of the present work, therefore, is to evaluate the adsorption behavior of three ionizable, polar compounds occurring in different forms: cationic (propranolol - PRO), anionic (sulfisoxazole - SSX) and neutral (sulfaguanidine - SGD) onto soil under various temperature conditions. The adsorption thermodynamics of these researched compounds were extensively investigated using parameters such as enthalpy change (ΔH°), Gibbs free energy change (ΔG°) as well as entropy change (ΔS°). These calculations reveal that sorption of PRO is exothermic, spontaneous and enthalpy driven, sorption of SGD is endothermic, spontaneous and entropy driven whereas sorption of SSX is endothermic, spontaneous only above the temperature of 303.15K and entropy driven. Furthermore, we submit that the calculated values yield valuable information regarding the sorption mechanism of PRO, SGD and SSX onto soils. Copyright © 2014 Elsevier Ltd. All rights reserved.

Communication: Electron ionization of DNA bases.

PubMed

Rahman, M A; Krishnakumar, E

2016-04-28

No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.

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.

Advanced carbon-based material C{sub 60} modification using partially ionized cluster and energetic beams

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

Du Yuancheng; Ren Zhongmin; Ning Zhifeng

1997-06-20

Two processes have been undertaken using Partially ionized cluster deposition (PICBD) and energetic ion bombardment beams deposition (IBD) respectively. C{sub 60} films deposited by PICBD at V=0 and 65 V, which result in highly textured close-packed structure in orientation (110) and being more polycrystalline respectively, the resistance of C{sub 60} films to oxygen diffusion contamination will be improved. In the case of PICBD, the ionized C{sub 60} soccer-balls molecules in the evaporation beams will be fragmented in collision with the substrate under the elevated accelerating fields Va. As a new synthetic IBD processing, two low energy (400 and 1000 eV)more » nitrogen ion beams have been used to bombard C{sub 60} films to synthesize the carbon nitride films.« less

Entropy-driven one-step formation of Phi29 pRNA 3WJ from three RNA fragments.

PubMed

Binzel, Daniel W; Khisamutdinov, Emil F; Guo, Peixuan

2014-04-15

The emerging field of RNA nanotechnology necessitates creation of functional RNA nanoparticles but has been limited by particle instability. It has been shown that the three-way junction of bacteriophage phi29 motor pRNA has unusual stability and can self-assemble from three fragments with high efficiency. It is generally believed that RNA and DNA folding is energy landscape-dependent, and the folding of RNA is driven by enthalpy. Here we examine the thermodynamic characteristics of the 3WJ components as 2'-fluoro RNA, DNA, and RNA. It was seen that the three fragments existed either in 3WJ complex or as monomers, with the intermediate of dimers almost undetectable. It seems that the three fragments can lead to the formation of the 3WJ complex efficiently within a rapid time. A low dissociation constant (apparent KD) of 11.4 nM was determined for RNA, inclusion of 2'-F pyrimidines strengthened the KD to 4.5 nM, and substitution of DNA weakened it to 47.7 nM. The ΔG°37, were -36, -28, and -15 kcal/mol for 3WJ2'-F, 3WJRNA, and 3WJDNA, respectively. It is found that the formation of the three-component complex was governed by entropy, instead of enthalpy, as usually found in RNA complexes. Here entropy-driven is referring to a dominating entropic contribution to the increased stability of the 3WJ(2'-F and 3WJ(RNA) compared to the 3WJ(DNA,) instead of referring to the absolute role or total energy governing 3WJ folding. [corrected].

Radiation-Induced Chromosomal Aberrations and Immunotherapy: Micronuclei, Cytosolic DNA, and Interferon-Production Pathway.

PubMed

Durante, Marco; Formenti, Silvia C

2018-01-01

Radiation-induced chromosomal aberrations represent an early marker of late effects, including cell killing and transformation. The measurement of cytogenetic damage in tissues, generally in blood lymphocytes, from patients treated with radiotherapy has been studied for many years to predict individual sensitivity and late morbidity. Acentric fragments are lost during mitosis and create micronuclei (MN), which are well correlated to cell killing. Immunotherapy is rapidly becoming a most promising new strategy for metastatic tumors, and combination with radiotherapy is explored in several pre-clinical studies and clinical trials. Recent evidence has shown that the presence of cytosolic DNA activates immune response via the cyclic GMP-AMP synthase/stimulator of interferon genes pathway, which induces type I interferon transcription. Cytosolic DNA can be found after exposure to ionizing radiation either as MN or as small fragments leaking through nuclear envelope ruptures. The study of the dependence of cytosolic DNA and MN on dose and radiation quality can guide the optimal combination of radiotherapy and immunotherapy. The role of densely ionizing charged particles is under active investigation to define their impact on the activation of the interferon pathway.

Trimethylation enhancement using diazomethane (TrEnDi): rapid on-column quaternization of peptide amino groups via reaction with diazomethane significantly enhances sensitivity in mass spectrometry analyses via a fixed, permanent positive charge.

PubMed

Wasslen, Karl V; Tan, Le Hoa; Manthorpe, Jeffrey M; Smith, Jeffrey C

2014-04-01

Defining cellular processes relies heavily on elucidating the temporal dynamics of proteins. To this end, mass spectrometry (MS) is an extremely valuable tool; different MS-based quantitative proteomics strategies have emerged to map protein dynamics over the course of stimuli. Herein, we disclose our novel MS-based quantitative proteomics strategy with unique analytical characteristics. By passing ethereal diazomethane over peptides on strong cation exchange resin within a microfluidic device, peptides react to contain fixed, permanent positive charges. Modified peptides display improved ionization characteristics and dissociate via tandem mass spectrometry (MS(2)) to form strong a2 fragment ion peaks. Process optimization and determination of reactive functional groups enabled a priori prediction of MS(2) fragmentation patterns for modified peptides. The strategy was tested on digested bovine serum albumin (BSA) and successfully quantified a peptide that was not observable prior to modification. Our method ionizes peptides regardless of proton affinity, thus decreasing ion suppression and permitting predictable multiple reaction monitoring (MRM)-based quantitation with improved sensitivity.

Characterization of carotenoids and carotenoid esters in red pepper pods (Capsicum annuum L.) by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry.

PubMed

Schweiggert, Ute; Kammerer, Dietmar R; Carle, Reinhold; Schieber, Andreas

2005-01-01

Carotenoids and carotenoid esters were extracted from red pepper pods (Capsicum annuum L.) without saponification. Among the 42 compounds detected, 4 non-esterified, 11 mono- and 17 diesters were characterized based on their retention times, UV/Vis spectra and their fragmentation patterns in collision-induced dissociation experiments in atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Positive and negative ion mode measurements were used for the characterization of major and minor carotenoids and their esters. Capsanthin esterified with lauric, palmitic and myristic acids represented the predominant compounds in the red pepper extracts. Additionally, three beta-cryptoxanthin and one zeaxanthin monoester were tentatively identified in red pepper pods for the first time. Furthermore, the specific fragmentation patterns of capsanthin-laurate-myristate and capsanthin-myristate-palmitate were used for the distinction of both regioisomers. The results obtained from LC-DAD-APCI-MSn experiments demonstrated that the carotenoid profile of red pepper pods is considerably more complex than considered hitherto. Copyright (c) 2005 John Wiley & Sons, Ltd.

Effect-directed analysis via hyphenated high-performance thin-layer chromatography for bioanalytical profiling of sunflower leaves.

PubMed

Móricz, Ágnes M; Ott, Péter G; Yüce, Imanuel; Darcsi, András; Béni, Szabolcs; Morlock, Gertrud E

2018-01-19

High-performance thin-layer chromatography (HPTLC) coupled with effect-directed analysis was used for non-targeted screening of sunflower leaf extract for components exhibiting antioxidant, antibacterial and/or cholinesterase enzyme inhibitory effects. The active compounds were characterized by HPTLC-electrospray ionization-high resolution mass spectrometry (ESI-HRMS) and HPTLC-Direct Analysis in Real Time (DART)-MS/MS. The latter ambient ionization technique (less soft than ESI) resulted in oxidation and fragmentation products and characteristic fragment ions. NMR spectroscopy after targeted isolation via preparative normal phase flash chromatography and semi-preparative reversed phase high-performance liquid chromatography supported the identification of two diterpenes to be (-)-kaur-16-en-19-oic acid and 15-α-angeloyloxy-ent-kaur-16-en-19-oic acid. Both compounds found to be multi-potent as they inhibited acetylcholinesterase and butyrylcholinesterase and showed antibacterial effects against Gram-positive Bacillus subtilis and Gram-negative Aliivibrio fischeri bacteria. Kaurenoic acid was also active against the Gram-negative pepper pathogenic Xanthomonas euvesicatoria bacteria. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron Capture Dissociation of Divalent Metal-adducted Sulfated N-Glycans Released from Bovine Thyroid Stimulating Hormone

NASA Astrophysics Data System (ADS)

Zhou, Wen; Håkansson, Kristina

2013-11-01

Sulfated N-glycans released from bovine thyroid stimulating hormone (bTSH) were ionized with the divalent metal cations Ca2+, Mg2+, and Co by electrospray ionization (ESI). These metal-adducted species were subjected to infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD) and the corresponding fragmentation patterns were compared. IRMPD generated extensive glycosidic and cross-ring cleavages, but most product ions suffered from sulfonate loss. Internal fragments were also observed, which complicated the spectra. ECD provided complementary structural information compared with IRMPD, and all observed product ions retained the sulfonate group, allowing sulfonate localization. To our knowledge, this work represents the first application of ECD towards metal-adducted sulfated N-glycans released from a glycoprotein. Due to the ability of IRMPD and ECD to provide complementary structural information, the combination of the two strategies is a promising and valuable tool for glycan structural characterization. The influence of different metal ions was also examined. Calcium adducts appeared to be the most promising species because of high sensitivity and ability to provide extensive structural information.

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector.

PubMed

Long, Jingming; Furch, Federico J; Durá, Judith; Tremsin, Anton S; Vallerga, John; Schulz, Claus Peter; Rouzée, Arnaud; Vrakking, Marc J J

2017-07-07

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 μm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (10 4 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO 2 ), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector

NASA Astrophysics Data System (ADS)

Long, Jingming; Furch, Federico J.; Durá, Judith; Tremsin, Anton S.; Vallerga, John; Schulz, Claus Peter; Rouzée, Arnaud; Vrakking, Marc J. J.

2017-07-01

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 μm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (104 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO2), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

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

Shukla, Anil, E-mail: Anil.Shukla@pnnl.gov; Bogdanov, Bogdan

2015-02-14

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations ofmore » singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.« less

Communication: Two-step explosion processes of highly charged fullerene cations C{sub 60}{sup q+} (q = 20–60)

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

Yamazaki, Kaoru; Nakamura, Takashi; Kanno, Manabu

2014-09-28

To establish the fundamental understanding of the fragmentation dynamics of highly positive charged nano- and bio-materials, we carried out on-the-fly classical trajectory calculations on the fragmentation dynamics of C{sub 60}{sup q+} (q = 20–60). We used the UB3LYP/3-21G level of density functional theory and the self-consistent charge density-functional based tight-binding theory. For q ≥ 20, we found that a two-step explosion mechanism governs the fragmentation dynamics: C{sub 60}{sup q+} first ejects singly and multiply charged fast atomic cations C{sup z+} (z ≥ 1) via Coulomb explosions on a timescale of 10 fs to stabilize the remaining core cluster. Thermal evaporationsmore » of slow atomic and molecular fragments from the core cluster subsequently occur on a timescale of 100 fs to 1 ps. Increasing the charge q makes the fragments smaller. This two-step mechanism governs the fragmentation dynamics in the most likely case that the initial kinetic energy accumulated upon ionization to C{sub 60}{sup q+} by ion impact or X-ray free electron laser is larger than 100 eV.« less

In Situ Plasma Measurements of Fragmented Comet 73P Schwassmann-Wachmann 3

NASA Astrophysics Data System (ADS)

Gilbert, J. A.; Lepri, S. T.; Rubin, M.; Combi, M.; Zurbuchen, T. H.

2015-12-01

The interiors of comets contain some of the most pristine material in the solar system. Comet 73P/Schwassmann-Wachmann 3, discovered in 1930, is a Jupiter-family comet with a 5.34-year period. This comet split into 5 fragments in 1995 and disintegrated into nearly 70 major pieces in 2006. In 2006 May and June, recently ionized cometary particles originating from fragments including and surrounding some of these major objects were collected with the ACE/SWICS and Wind/STICS sensors. Due to a combination of the instrument characteristics and the close proximity of the fragments passing between those spacecraft and the Sun, unique measurements regarding the charge state composition and the elemental abundances of both cometary and heliospheric plasma were made during that time. The cometary material released from some of these fragments can be identified by the concentrations of water-group pickup ions having a mass-per-charge ratio of 16-18 amu e-1, indicating that while these fragments are small, they are still actively sublimating. We present an analysis of cometary composition, spatial distribution, and heliospheric interactions, with a focus on helium, C+/O+, and water-group ions.

IN SITU PLASMA MEASUREMENTS OF FRAGMENTED COMET 73P SCHWASSMANN–WACHMANN 3

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

Gilbert, J. A.; Lepri, S. T.; Combi, M.

2015-12-10

The interiors of comets contain some of the most pristine material in the solar system. Comet 73P/Schwassmann–Wachmann 3, discovered in 1930, is a Jupiter-family comet with a 5.34-year period. This comet split into 5 fragments in 1995 and disintegrated into nearly 70 major pieces in 2006. In 2006 May and June, recently ionized cometary particles originating from fragments including and surrounding some of these major objects were collected with the ACE/SWICS and Wind/STICS sensors. Due to a combination of the instrument characteristics and the close proximity of the fragments passing between those spacecraft and the Sun, unique measurements regarding themore » charge state composition and the elemental abundances of both cometary and heliospheric plasma were made during that time. The cometary material released from some of these fragments can be identified by the concentrations of water-group pickup ions having a mass-per-charge ratio of 16–18 amu e{sup −1}, indicating that while these fragments are small, they are still actively sublimating. We present an analysis of cometary composition, spatial distribution, and heliospheric interactions, with a focus on helium, C{sup +}/O{sup +}, and water-group ions.« less

Development of position-sensitive time-of-flight spectrometer for fission fragment research

DOE PAGES

Arnold, C. W.; Tovesson, F.; Meierbachtol, K.; ...

2014-07-09

A position-sensitive, high-resolution time-of-flight detector for fission fragments has been developed. The SPectrometer for Ion DEtermination in fission Research (SPIDER) is a 2E–2v spectrometer designed to measure the mass of light fission fragments to a single mass unit. The time pick-off detector pairs to be used in SPIDER have been tested with α-particles from 229Th and its decay chain and α-particles and spontaneous fission fragments from 252Cf. Each detector module is comprised of thin electron conversion foil, electrostatic mirror, microchannel plates, and delay-line anodes. Particle trajectories on the order of 700 mm are determined accurately to within 0.7 mm. Flightmore » times were measured with 250 ps resolution FWHM. Computed particle velocities are accurate to within 0.06 mm/ns corresponding to a precision of 0.5%. As a result, an ionization chamber capable of 400 keV energy resolution coupled with the velocity measurements described here will pave the way for modestly efficient measurements of light fission fragments with unit mass resolution.« less

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

Ren, Xueguang, E-mail: xue.g.ren@ptb.de; Pflüger, Thomas; Weyland, Marvin

We study the low-energy (E{sub 0} = 26 eV) electron-impact induced ionization and fragmentation of tetrahydrofuran using a reaction microscope. All three final-state charged particles, i.e., two outgoing electrons and one fragment ion, are detected in triple coincidence such that the momentum vectors and, consequently, the kinetic energies for charged reaction products are determined. The ionic fragments are clearly identified in the experiment with a mass resolution of 1 amu. The fragmentation pathways of tetrahydrofuran are investigated by measuring the ion kinetic energy spectra and the binding energy spectra where an energy resolution of 1.5 eV has been achieved usingmore » the recently developed photoemission electron source. Here, we will discuss the fragmentation reactions for the cations C{sub 4}H{sub 8}O{sup +}, C{sub 4}H{sub 7}O{sup +}, C{sub 2}H{sub 3}O{sup +}, C{sub 3}H{sub 6}{sup +}, C{sub 3}H{sub 5}{sup +}, C{sub 3}H{sub 3}{sup +}, CH{sub 3}O{sup +}, CHO{sup +}, and C{sub 2}H{sub 3}{sup +}.« less

Identifying the proton transfer reaction mechanism via a proton-bound dimeric intermediate for esomeprazoles by a kinetic method combined with density functional theory calculations.

PubMed

Cao, Xiaoji; Zhang, Feifei; Zhu, Kundan; Ye, Xuemin; Shen, Lingxiao; Chen, Jiaoyu; Mo, Weimin

2014-05-15

Esomeprazole analogs are a class of important proton pump inhibitors for the treatment of gastro-esophageal reflux diseases. Understanding the fragmentation reaction mechanism of the protonated esomeprazole analogs will facilitate the characterization of their complex metabolic fate in humans. In this paper, the kinetic method and theoretical calculations were applied to evaluate the fragmentation of protonated esomeprazole analogs. All collision-induced dissociation (CID) mass spectrometry experiments were carried out using electrospray ionization (ESI) ion trap mass spectrometry in positive ion mode. Also the accurate masses of fragments were measured on by ESI quadrupole time-of-flight (QTOF) MS in positive ion mode. Theoretical calculations were carried out by the density functional theory (DFT) method with the 6-31G(d) basis set in the Gaussian 03 program. In the fragmentation of the protonated esomeprazole analogs, C-S bond breakage is observed, which gives rise to protonated 2-(sulfinylmethylene)pyridines and protonated benzimidazoles. DFT calculations demonstrate that the nitrogen atom of the pyridine part is the thermodynamically most favorable protonation site, and the C-S bond cleavage is triggered by the transfer of this ionizing proton from the nitrogen atom of the pyridine part to the carbon atom of the benzimidazole part to which the sulfinyl is attached. Moreover, with the kinetic plot, the intensity ratios of two protonated product ions yield a linear relationship with the differences in proton affinities of the corresponding neutral molecules, which provides strong experimental evidence that the reaction proceeds via proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complex intermediates. The kinetic method combined with theoretical calculations was successfully applied to probe the proton transfer reaction by proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complexes in the fragmentation of protonated esomeprazole analogs by ESI CID MS, which is a strong evidence that the kinetic method can be applied in identifying a proton-bound dimeric intermediate in the fragmentation of protonated ions. Copyright © 2014 John Wiley & Sons, Ltd.

Production of low kinetic energy electrons and energetic ion pairs by Intermolecular Coulombic Decay.

PubMed

Hergenhahn, Uwe

2012-12-01

The paper gives an introduction into Interatomic and Intermolecular Coulombic Decay (ICD). ICD is an autoionization process, which contrary to Auger decay involves neighbouring sites of the initial vacancy as an integral part of the decay transition. As a result of ICD, slow electrons are produced which generally are known to be active in radiation damage. The author summarizes the properties of ICD and reviews a number of important experiments performed in recent years. Intermolecular Coulombic Decay can generally take place in weakly bonded aggregates in the presence of ionizing particles or ionizing radiation. Examples collected here mostly use soft X-rays produced by synchrotron radiation to ionize, and use rare-gas clusters, water clusters or solutes in a liquid jet to observe ICD after irradiation. Intermolecular Coulombic Decay is initiated by single ionization into an excited state. The subsequent relaxation proceeds via an ultra-fast energy transfer to a neighbouring site, where a second ionization occurs. Secondary electrons from ICD have clearly been identified in numerous systems. ICD can take place after primary ionization, as the second step of a decay cascade which also involves Auger decay, or after resonant excitation with an energy which exceeds the ionization potential of the system. ICD is expected to play a role whenever particles or radiation with photon energies above the ionization energies for inner valence electrons are present in weakly bonded matter, e.g., biological tissue. The process produces at the same time a slow electron and two charged atomic or molecular fragments, which will lead to structural changes around the ionized site.

Ionization waves of arbitrary velocity driven by a flying focus

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

Palastro, J. P.; Turnbull, D.; Bahk, S. -W.

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. For this study, we present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionizationmore » wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.« less

Ionization waves of arbitrary velocity driven by a flying focus

DOE PAGES

Palastro, J. P.; Turnbull, D.; Bahk, S. -W.; ...

2018-03-01

A chirped laser pulse focused by a chromatic lens exhibits a dynamic, or flying, focus in which the trajectory of the peak intensity decouples from the group velocity. In a medium, the flying focus can trigger an ionization front that follows this trajectory. By adjusting the chirp, the ionization front can be made to travel at an arbitrary velocity along the optical axis. For this study, we present analytical calculations and simulations describing the propagation of the flying focus pulse, the self-similar form of its intensity profile, and ionization wave formation. The ability to control the speed of the ionizationmore » wave and, in conjunction, mitigate plasma refraction has the potential to advance several laser-based applications, including Raman amplification, photon acceleration, high-order-harmonic generation, and THz generation.« less

Application of electrospray ionization hybrid ion trap/time-of-flight mass spectrometry in the rapid characterization of quinocetone metabolites formed in vitro.

PubMed

Liu, Zhao-Ying; Huang, Ling-Li; Chen, Dong-Mei; Dai, Meng-Hong; Tao, Yan-Fei; Wang, Yu-Lian; Yuan, Zong-Hui

2010-02-01

The application of electrospray ionization hybrid ion trap/time-of-flight mass spectrometry coupled with high-performance liquid chromatography (LC/MS-IT-TOF) in the rapid characterization of in vitro metabolites of quinocetone was developed. Metabolites formed in rat liver microsomes were separated using a VP-ODS column with gradient elution. Multiple scans of metabolites in MS and MS(2) modes and accurate mass measurements were automatically performed simultaneously through data-dependent acquisition in only a 30-min analysis. Most measured mass errors were less than 10 ppm for both protonated molecules and fragment ions using external mass calibration. The elemental compositions of all fragment ions of quinocetone and its metabolites could be rapidly assigned based upon the known compositional elements of protonated molecules. The structure of metabolites were elucidated based on the combination of three techniques: agreement between their proposed structure, the accurate masses, and the elemental composition of ions in their mass spectra; comparison of their changes in accurate molecular masses and fragment ions with those of parent drug or metabolite; and the elemental compositions of lost mass numbers in proposed fragmentation pathways. Twenty-seven phase I metabolites were identified as 11 reduction metabolites, three direct hydroxylation metabolites, and 13 metabolites with a combination of reduction and hydroxylation. All metabolites except the N-oxide reduction metabolite M6 are new metabolites of quinocetone, which were not previously reported. The ability to conduct expected biotransformation profiling via tandem mass spectrometry coupled with accurate mass measurement, all in a single experimental run, is one of the most attractive features of this methodology. The results demonstrate the use of LC/MS-IT-TOF approach appears to be rapid, efficient, and reliable in structural characterization of drug metabolites.

The Transuranium Elements: Early History (Nobel Lecture)

DOE R&D Accomplishments Database

McMillan, E. M.

1951-12-12

In this talk the author tells of the circumstances that led to the discovery of neptunium, the first element beyond uranium, and the partial identification of plutonium, the next one beyond that. The part of the story that lies before 1939 has already been recounted here in the Nobel lectures of Fermi and Hahn. Rather the author starts with the discovery of fission by Hahn and Strassmann. News of this momentous discovery reached Berkeley early in 1939. The staff of the Radiation Laboratory was put into a state of great excitement and several experiments of a nature designed to check and extend the announced results were started, using ionization chambers and pulse amplifiers, cloud chambers, chemical methods, and so forth. The author decided to do an experiment of a very simple kind. When a nucleus of uranium absorbs a neutron and fission takes place, the two resulting fragments fly apart with great violence, sufficient to propel them through air or other matter for some distance. This distance, called the "range", is quantity of some interest, and the author undertook to measure it by observing the depth of penetration of the fission fragments in a stack of thin aluminum foils. The fission fragments came from a thin layer of uranium oxide spread on a sheet of paper, and exposed to neutrons from a beryllium target bombarded by 8 Mev deuterons in the 37-inch cyclotron. The aluminum foils, each with a thickness of about half a milligram per square centimeter, were stacked like the pages of a book in immediate contact with the layer of uranium oxide. After exposure to the neutrons, the sheets of aluminum were separated and examined for radioactivity by means of an ionization chamber. The fission fragments of course are radioactive atoms, and their activity is found where they stop.

Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge.

PubMed

Ayrton, Stephen T; Jones, Rhys; Douce, David S; Morris, Mike R; Cooks, R Graham

2018-01-15

Atmospheric pressure chemical ionization (APCI) in air or in nitrogen with just traces of oxygen is shown to yield regioselective oxidation, dehydrogenation, and fragmentation of alkanes. Ozone is produced from ambient oxygen in situ and is responsible for the observed ion chemistry, which includes partial oxidation to ketones and C-C cleavage to give aldehydes. The mechanism of oxidation is explored and relationships between ionic species produced from individual alkanes are established. Unusually, dehydrogenation occurs by water loss. Competitive incorporation into the hydrocarbon chain of nitrogen versus oxygen as a mode of ionization is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

AWAKE readiness for the study of the seeded self-modulation of a 400 GeV proton bunch

NASA Astrophysics Data System (ADS)

Muggli, P.; Adli, E.; Apsimon, R.; Asmus, F.; Baartman, R.; Bachmann, A.-M.; Barros Marin, M.; Batsch, F.; Bauche, J.; Berglyd Olsen, V. K.; Bernardini, M.; Biskup, B.; Blanco Vinuela, E.; Boccardi, A.; Bogey, T.; Bohl, T.; Bracco, C.; Braunmuller, F.; Burger, S.; Burt, G.; Bustamante, S.; Buttenschön, B.; Butterworth, A.; Caldwell, A.; Cascella, M.; Chevallay, E.; Chung, M.; Damerau, H.; Deacon, L.; Dexter, A.; Dirksen, P.; Doebert, S.; Farmer, J.; Fedosseev, V.; Feniet, T.; Fior, G.; Fiorito, R.; Fonseca, R.; Friebel, F.; Gander, P.; Gessner, S.; Gorgisyan, I.; Gorn, A. A.; Grulke, O.; Gschwendtner, E.; Guerrero, A.; Hansen, J.; Hessler, C.; Hofle, W.; Holloway, J.; Hüther, M.; Ibison, M.; Islam, M. R.; Jensen, L.; Jolly, S.; Kasim, M.; Keeble, F.; Kim, S.-Y.; Kraus, F.; Lasheen, A.; Lefevre, T.; LeGodec, G.; Li, Y.; Liu, S.; Lopes, N.; Lotov, K. V.; Martyanov, M.; Mazzoni, S.; Medina Godoy, D.; Mete, O.; Minakov, V. A.; Mompo, R.; Moody, J.; Moreira, M. T.; Mitchell, J.; Mutin, C.; Norreys, P.; Öz, E.; Ozturk, E.; Pauw, W.; Pardons, A.; Pasquino, C.; Pepitone, K.; Petrenko, A.; Pitmann, S.; Plyushchev, G.; Pukhov, A.; Rieger, K.; Ruhl, H.; Schmidt, J.; Shalimova, I. A.; Shaposhnikova, E.; Sherwood, P.; Silva, L.; Sosedkin, A. P.; Speroni, R.; Spitsyn, R. I.; Szczurek, K.; Thomas, J.; Tuev, P. V.; Turner, M.; Verzilov, V.; Vieira, J.; Vincke, H.; Welsch, C. P.; Williamson, B.; Wing, M.; Xia, G.; Zhang, H.; AWAKE Collaboration

2018-01-01

AWAKE is a proton-driven plasma wakefield acceleration experiment. We show that the experimental setup briefly described here is ready for systematic study of the seeded self-modulation of the 400 GeV proton bunch in the 10 m long rubidium plasma with density adjustable from 1 to 10× {10}14 cm-3. We show that the short laser pulse used for ionization of the rubidium vapor propagates all the way along the column, suggesting full ionization of the vapor. We show that ionization occurs along the proton bunch, at the laser time and that the plasma that follows affects the proton bunch.

Attosecond Electron Correlation Dynamics in Double Ionization of Benzene Probed with Two-Electron Angular Streaking

NASA Astrophysics Data System (ADS)

Winney, Alexander H.; Lee, Suk Kyoung; Lin, Yun Fei; Liao, Qing; Adhikari, Pradip; Basnayake, Gihan; Schlegel, H. Bernhard; Li, Wen

2017-09-01

With a novel three-dimensional electron-electron coincidence imaging technique and two-electron angular streaking method, we show that the emission time delay between two electrons can be measured from tens of attoseconds to more than 1 fs. Surprisingly, in benzene, the double ionization rate decays as the time delay between the first and second electron emission increases during the first 500 as. This is further supported by the decay of the Coulomb repulsion in the direction perpendicular to the laser polarization. This result reveals that laser-induced electron correlation plays a major role in strong field double ionization of benzene driven by a nearly circularly polarized field.

Specificity enhancement by electrospray ionization multistage mass spectrometry--a valuable tool for differentiation and identification of 'V'-type chemical warfare agents.

PubMed

Weissberg, Avi; Tzanani, Nitzan; Dagan, Shai

2013-12-01

The use of chemical warfare agents has become an issue of emerging concern. One of the challenges in analytical monitoring of the extremely toxic 'V'-type chemical weapons [O-alkyl S-(2-dialkylamino)ethyl alkylphosphonothiolates] is to distinguish and identify compounds of similar structure. MS analysis of these compounds reveals mostly fragment/product ions representing the amine-containing residue. Hence, isomers or derivatives with the same amine residue exhibit similar mass spectral patterns in both classical EI/MS and electrospray ionization-MS, leading to unavoidable ambiguity in the identification of the phosphonate moiety. A set of five 'V'-type agents, including O-ethyl S-(2-diisopropylamino)ethyl methylphosphonothiolate (VX), O-isobutyl S-(2-diethylamino)ethyl methylphosphonothiolate (RVX) and O-ethyl S-(2-diethylamino)ethyl methylphosphonothiolate (VM) were studied by liquid chromatography/electrospray ionization/MS, utilizing a QTRAP mass detector. MS/MS enhanced product ion scans and multistage MS(3) experiments were carried out. Based on the results, possible fragmentation pathways were proposed, and a method for the differentiation and identification of structural isomers and derivatives of 'V'-type chemical warfare agents was obtained. MS/MS enhanced product ion scans at various collision energies provided information-rich spectra, although many of the product ions obtained were at low abundance. Employing MS(3) experiments enhanced the selectivity for those low abundance product ions and provided spectra indicative of the different phosphonate groups. Study of the fragmentation pathways, revealing some less expected structures, was carried out and allowed the formulation of mechanistic rules and the determination of sets of ions typical of specific groups, for example, methylphosphonothiolates versus ethylphosphonothiolates. The new group-specific ions elucidated in this work are also useful for screening unknown 'V'-type agents and related compounds, utilizing precursor ion scan experiments. Copyright © 2013 John Wiley & Sons, Ltd.

Application of high-resolution time-of-flight chemical ionization mass spectrometry measurements to estimate volatility distributions of α-pinene and naphthalene oxidation products

DOE PAGES

Chhabra, P. S.; Lambe, A. T.; Canagaratna, M. R.; ...

2015-01-05

Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functionalmore » groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O 3 and OH oxidation products of α-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 × 10 11 to 9.7 × 10 11 molec s cm −3, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O/C and H/C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. Furthermore, while acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.« less

Dispersion equation for electrostatic ion cyclotron instability under the effect of ionization in a dusty plasma

NASA Astrophysics Data System (ADS)

Singh, Sukhmander

2018-05-01

In the present paper we derive the plasma dispersion equation under the effect of ionization rate in a dust plasma to investigate the electrostatic ion cyclotron instability, where dust charge fluctuation is absent. It has one of the lowest threshold drift velocities among all the current-driven instabilities in isothermal plasma. The Electrostatic ion cyclotron instability in a dusty plasma containing electrons, light ions, and massive negatively charged dust grains which can be investigated both experimentally and theoretically.

Heralded ions via ionization coincidence

NASA Astrophysics Data System (ADS)

McCulloch, A. J.; Speirs, R. W.; Wissenberg, S. H.; Tielen, R. P. M.; Sparkes, B. M.; Scholten, R. E.

2018-04-01

We demonstrate a method for the deterministic production of single ions by exploiting the correlation between an electron and associated ion following ionization. Coincident detection and feedback in combination with Coulomb-driven particle selection allows for high-fidelity heralding of ions at a high repetition rate. Extension of the scheme beyond time-correlated feedback to position- and momentum-correlated feedback will provide a general and powerful means to optimize the ion beam brightness for the development of next-generation focused ion beam technologies.

High resolution far-infrared observations of the evolved H II region M16

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

McBreen, B.; Fazio, G.G.; Jaffe, D.T.

1982-03-01

M16 is an evolved, extremely density bounded H II region, which now consists only of a series of ionization fronts at molecular cloud boundaries. The source of ionization is the OB star cluster (NGC 6611) which is about 5 x 10/sup 6/ years old. We used the CFA/UA 102 cm balloon-borne telescope to map this region and detected three far-infrared (far-IR) sources embedded in an extended ridge of emission. Source I is an unresolved far-IR source embedded in a molecular cloud near a sharp ionization front. An H/sub 2/O maser is associated with this source, but no radio continuum emissionmore » has been observed. The other two far-IR sources (II and III) are associated with ionized gas-molecular cloud interfaces, with the far-IR radiation arising from dust at the boundary heated by the OB cluster. Source II is located at the southern prominent neutral intrusion with its associated bright rims and dark ''elephant trunk'' globules that delineate the current progress of the ionization front into the neutral material, and Source III arises at the interface of the northern molecular cloud fragment.« less

Gas-phase structure and fragmentation pathways of singly protonated peptides with N-terminal arginine.

PubMed

Bythell, Benjamin J; Csonka, István P; Suhai, Sándor; Barofsky, Douglas F; Paizs, Béla

2010-11-25

The gas-phase structures and fragmentation pathways of the singly protonated peptide arginylglycylaspartic acid (RGD) are investigated by means of collision-induced-dissociation (CID) and detailed molecular mechanics and density functional theory (DFT) calculations. It is demonstrated that despite the ionizing proton being strongly sequestered at the guanidine group, protonated RGD can easily be fragmented on charge directed fragmentation pathways. This is due to facile mobilization of the C-terminal or aspartic acid COOH protons thereby generating salt-bridge (SB) stabilized structures. These SB intermediates can directly fragment to generate b(2) ions or facilely rearrange to form anhydrides from which both b(2) and b(2)+H(2)O fragments can be formed. The salt-bridge stabilized and anhydride transition structures (TSs) necessary to form b(2) and b(2)+H(2)O are much lower in energy than their traditional charge solvated counterparts. These mechanisms provide compelling evidence of the role of SB and anhydride structures in protonated peptide fragmentation which complements and supports our recent findings for tryptic systems (Bythell, B. J.; Suhai, S.; Somogyi, A.; Paizs, B. J. Am. Chem. Soc. 2009, 131, 14057-14065.). In addition to these findings we also report on the mechanisms for the formation of the b(1) ion, neutral loss (H(2)O, NH(3), guanidine) fragment ions, and the d(3) ion.

Defining Gas-Phase Fragmentation Propensities of Intact Proteins During Native Top-Down Mass Spectrometry

NASA Astrophysics Data System (ADS)

Haverland, Nicole A.; Skinner, Owen S.; Fellers, Ryan T.; Tariq, Areeba A.; Early, Bryan P.; LeDuc, Richard D.; Fornelli, Luca; Compton, Philip D.; Kelleher, Neil L.

2017-06-01

Fragmentation of intact proteins in the gas phase is influenced by amino acid composition, the mass and charge of precursor ions, higher order structure, and the dissociation technique used. The likelihood of fragmentation occurring between a pair of residues is referred to as the fragmentation propensity and is calculated by dividing the total number of assigned fragmentation events by the total number of possible fragmentation events for each residue pair. Here, we describe general fragmentation propensities when performing top-down mass spectrometry (TDMS) using denaturing or native electrospray ionization. A total of 5311 matched fragmentation sites were collected for 131 proteoforms that were analyzed over 165 experiments using native top-down mass spectrometry (nTDMS). These data were used to determine the fragmentation propensities for 399 residue pairs. In comparison to denatured top-down mass spectrometry (dTDMS), the fragmentation pathways occurring either N-terminal to proline or C-terminal to aspartic acid were even more enhanced in nTDMS compared with other residues. More generally, 257/399 (64%) of the fragmentation propensities were significantly altered ( P ≤ 0.05) when using nTDMS compared with dTDMS, and of these, 123 were altered by 2-fold or greater. The most notable enhancements of fragmentation propensities for TDMS in native versus denatured mode occurred (1) C-terminal to aspartic acid, (2) between phenylalanine and tryptophan (F|W), and (3) between tryptophan and alanine (W|A). The fragmentation propensities presented here will be of high value in the development of tailored scoring systems used in nTDMS of both intact proteins and protein complexes. [Figure not available: see fulltext.

BOW SHOCK FRAGMENTATION DRIVEN BY A THERMAL INSTABILITY IN LABORATORY ASTROPHYSICS EXPERIMENTS

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

Suzuki-Vidal, F.; Lebedev, S. V.; Pickworth, L. A.

The role of radiative cooling during the evolution of a bow shock was studied in laboratory-astrophysics experiments that are scalable to bow shocks present in jets from young stellar objects. The laboratory bow shock is formed during the collision of two counterstreaming, supersonic plasma jets produced by an opposing pair of radial foil Z-pinches driven by the current pulse from the MAGPIE pulsed-power generator. The jets have different flow velocities in the laboratory frame, and the experiments are driven over many times the characteristic cooling timescale. The initially smooth bow shock rapidly develops small-scale nonuniformities over temporal and spatial scalesmore » that are consistent with a thermal instability triggered by strong radiative cooling in the shock. The growth of these perturbations eventually results in a global fragmentation of the bow shock front. The formation of a thermal instability is supported by analysis of the plasma cooling function calculated for the experimental conditions with the radiative packages ABAKO/RAPCAL.« less

Acetonitrile covalent adduct chemical ionization mass spectrometry for double bond localization in non-methylene-interrupted polyene fatty acid methyl esters.

PubMed

Lawrence, Peter; Brenna, J Thomas

2006-02-15

Covalent adduct chemical ionization (CACI) using a product of acetonitrile self-reaction, (1-methyleneimino)-1-ethenylium (MIE; CH2=C=N+=CH2), has been investigated as a method for localizing double bonds in a series of 16 non-methylene-interrupted fatty acid methyl esters (NMI-FAME) of polyenes with three and more double bonds. As with polyunsaturated homoallylic (methylene-interrupted) FAME and conjugated dienes, MIE (m/z 54) reacts across double bonds to yield molecular ions 54 mass units above the parent analyte. [M + 54]+ ions of several 20- and 22-carbon FAME that include one double bond in the C2-C3 position separated by two to five methylene units from a three, four, or five C homoallylic system dissociated according to rules for the homoallylic system, with an additional fragment corresponding to cleavage between the lone double bond and the carboxyl group and defining the position of the lone double bond. Triene FAME with both methylene and ethylene interruption yielded characteristic fragments distinguishable from homoallylic trienes. Fragmentation of fully conjugated trienes in the MS-1 spectra yields ratios of [M + 54]+/[M + 54 - 32]+ (loss of methanol) near unity, which distinguishes them from homoallylic FAME having a ratio of 8 or more; collisionally activated dissociation of [M + 54]+ yields a series of ions, including some rearrangement products, indicative of double bond position. Unlike conjugated dienes, fully conjugated triene diagnostic ion signal ratios did not follow any pattern based on double bond geometry. Partially conjugated trienes behave similarly to monoenes and conjugated dienes, yielding [M + 54]+/[M + 54 - 32]+ of 2-3 and, permitting them to be assigned as partially conjugated FAME using the MS-1 spectrum. They yield unique MS/MS spectra with weaker but assignable fragment ions, along with a diagnostic fragment that locates the lone double bond and permits 6,10,12-octatrienoate to be distinguished from 6,8,12-octatrienoate. The presence of a triple bond did not affect fragment formation in a methylene-interrupted yne-ene but did change fragments in a conjugated yne-ene. These data extend the principle of double bond localization by acetonitrile CACI-MS/MS to double bond structure in complex FAME found in nature.

Studies of fission fragment properties at the Los Alamos Neutron Science Center (LANSCE)

NASA Astrophysics Data System (ADS)

Tovesson, Fredrik; Mayorov, Dmitriy; Duke, Dana; Manning, Brett; Geppert-Kleinrath, Verena

2017-09-01

Nuclear data related to the fission process are needed for a wide variety of research areas, including fundamental science, nuclear energy and non-proliferation. While some of the relevant data have been measured to the required accuracies there are still many aspects of fission that need further investigation. One such aspect is how Total Kinetic Energy (TKE), fragment yields, angular distributions and other fission observables depend on excitation energy of the fissioning system. Another question is the correlation between mass, charge and energy of fission fragments. At the Los Alamos Neutron Science Center (LANSCE) we are studying neutron-induced fission at incident energies from thermal up to hundreds of MeV using the Lujan Center and Weapons Neutron Research (WNR) facilities. Advanced instruments such as SPIDER (time-of-flight and kinetic energy spectrometer), the NIFFTE Time Projection Chamber (TPC), and Frisch grid Ionization Chambers (FGIC) are used to investigate the properties of fission fragments, and some important results for the major actinides have been obtained.

Studies of fission fragment properties at the Los Alamos Neutron Science Center (LANSCE)

DOE PAGES

Tovesson, Fredrik; Mayorov, Dmitriy; Duke, Dana; ...

2017-09-13

Nuclear data related to the fission process are needed for a wide variety of research areas, including fundamental science, nuclear energy and non-proliferation. While some of the relevant data have been measured to the required accuracies there are still many aspects of fission that need further investigation. One such aspect is how Total Kinetic Energy (TKE), fragment yields, angular distributions and other fission observables depend on excitation energy of the fissioning system. Another question is the correlation between mass, charge and energy of fission fragments. At the Los Alamos Neutron Science Center (LANSCE) we are studying neutron-induced fission at incidentmore » energies from thermal up to hundreds of MeV using the Lujan Center and Weapons Neutron Research (WNR) facilities. Advanced instruments such as SPIDER (time-of-flight and kinetic energy spectrometer), the NIFFTE Time Projection Chamber (TPC), and Frisch grid Ionization Chambers (FGIC) are used to investigate the properties of fission fragments, and some important results for the major actinides have been obtained.« less

Studies of fission fragment properties at the Los Alamos Neutron Science Center (LANSCE)

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

Tovesson, Fredrik; Mayorov, Dmitriy; Duke, Dana

Nuclear data related to the fission process are needed for a wide variety of research areas, including fundamental science, nuclear energy and non-proliferation. While some of the relevant data have been measured to the required accuracies there are still many aspects of fission that need further investigation. One such aspect is how Total Kinetic Energy (TKE), fragment yields, angular distributions and other fission observables depend on excitation energy of the fissioning system. Another question is the correlation between mass, charge and energy of fission fragments. At the Los Alamos Neutron Science Center (LANSCE) we are studying neutron-induced fission at incidentmore » energies from thermal up to hundreds of MeV using the Lujan Center and Weapons Neutron Research (WNR) facilities. Advanced instruments such as SPIDER (time-of-flight and kinetic energy spectrometer), the NIFFTE Time Projection Chamber (TPC), and Frisch grid Ionization Chambers (FGIC) are used to investigate the properties of fission fragments, and some important results for the major actinides have been obtained.« less

The competition of charge remote and charge directed fragmentation mechanisms in quaternary ammonium salt derivatized peptides--an isotopic exchange study.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-12-01

Derivatization of peptides as quaternary ammonium salts (QAS) is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry (Cydzik et al. J. Pept. Sci. 2011, 17, 445-453). The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms - charge remote (ChR) and charge directed (ChD). The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms. © The Author(s) 2011. This article is published with open access at Springerlink.com

Stoichiometric control of multiple different tectons in coordination-driven self-assembly: preparation of fused metallacyclic polygons.

PubMed

Lee, Junseong; Ghosh, Koushik; Stang, Peter J

2009-09-02

We present a general strategy for the synthesis of stable, multicomponent fused polygon complexes in which coordination-driven self-assembly allows for single supramolecular species to be formed from multicomponent self-assembly and the shape of the obtained polygons can be controlled simply by changing the ratio of individual components. The compounds have been characterized by multinuclear NMR spectroscopy and electrospray ionization mass spectrometry.

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

PubMed Central

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

2016-01-01

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

Antioxidant activity and ultra-performance LC-electrospray ionization-quadrupole time-of-flight mass spectrometry for phenolics-based fingerprinting of Rose species: Rosa damascena, Rosa bourboniana and Rosa brunonii.

PubMed

Kumar, Neeraj; Bhandari, Pamita; Singh, Bikram; Bari, Shamsher S

2009-02-01

Roses are one of the most important groups of ornamental plants and their fruits and flowers are used in a wide variety of food, nutritional products and different traditional medicines. The antioxidant activity of methanolic extracts from fresh flowers of three rose species (Rosa damascena, Rosa bourboniana and Rosa brunonii) was evaluated by 1,1-diphenyl-2-picryl hydrazyl (DPPH) free-radical method. The ability to scavenge DPPH radical was measured by the discoloration of the solution. The methanolic extract from R. brunonii exhibited maximum free-radical-scavenging activity (64.5+/-0.38%) followed by R. bourboniana (51.8+/-0.46%) and R. damascena (43.6+/-0.25%) at 100 microg/ml. Simultaneously, ultra-performance liquid chromatography coupled with electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used to study phenolic composition in the methanolic extracts from the fresh flowers of rose species. The phenolic constituents were further investigated by direct infusion-ESI-QTOF-MS/MS in negative ion mode. Characteristic Electrospray ionization tandem mass spectrometry (ESI-MS/MS) spectra with other diagnostic fragment ions generated by retro Diels-Alder (RDA) fragmentation pathways were recorded for the flavonoids. Distinct similarities were observed in the relative distribution of polyphenolic compounds among the three species. The dominance of quercetin, kaempferol and their glycosides was observed in all the three species.

Coulomb-driven energy boost of heavy ions for laser-plasma acceleration.

PubMed

Braenzel, J; Andreev, A A; Platonov, K; Klingsporn, M; Ehrentraut, L; Sandner, W; Schnürer, M

2015-03-27

An unprecedented increase of kinetic energy of laser accelerated heavy ions is demonstrated. Ultrathin gold foils have been irradiated by an ultrashort laser pulse at a peak intensity of 8×10^{19}  W/  cm^{2}. Highly charged gold ions with kinetic energies up to >200  MeV and a bandwidth limited energy distribution have been reached by using 1.3 J laser energy on target. 1D and 2D particle in cell simulations show how a spatial dependence on the ion's ionization leads to an enhancement of the accelerating electrical field. Our theoretical model considers a spatial distribution of the ionization inside the thin target, leading to a field enhancement for the heavy ions by Coulomb explosion. It is capable of explaining the energy boost of highly charged ions, enabling a higher efficiency for the laser-driven heavy ion acceleration.

Instantaneous characterization of vegetable oils via TAG and FFA profiles by easy ambient sonic-spray ionization mass spectrometry.

PubMed

Simas, Rosineide C; Catharino, Rodrigo R; Cunha, Ildenize B S; Cabral, Elaine C; Barrera-Arellano, Daniel; Eberlin, Marcos N; Alberici, Rosana M

2010-04-01

A fast and reliable method is presented for the analysis of vegetable oils. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to efficiently desorb and ionize the main oil constituents from an inert surface under ambient conditions and to provide comprehensive triacylglyceride (TAG) and free fatty acid (FFA) profiles detected mainly as either [TAG + Na](+) or [FFA-H](-) ions. EASI(+/-)-MS analysis is simple, easily implemented, requires just a tiny droplet of the oil and is performed without any pre-separation or chemical manipulation. It also causes no fragmentation of TAG ions hence diacylglyceride (DAG) and monoacylglyceride (MAG) profiles and contents can also be measured. The EASI(+/-)-MS profiles of TAG and FFA permit authentication and quality control and can be used, for instance, to access levels of adulteration, acidity, oxidation or hydrolysis of vegetable oils in general.

Remote control of the dissociative ionization of H2 based on electron-H2 + entanglement

NASA Astrophysics Data System (ADS)

Wang, Jun-Ping; He, Feng

2018-04-01

The single ionization of H2 in strong laser fields creates the correlated electron-H2 + pair. Based on such a correlation, we conceive a strategy to control the energy spectra of the freed electron or dissociative fragments by simulating the time-dependent Schrödinger equation. Two attosecond pulses in a train produce the replica of electron-H2 + pairs, which are to be steered by a time-delayed phase-stabilized (mid)infrared laser pulse. By controlling the behavior of the freed electron, the dissociation of H2 + can be controlled even though there is no direct laser-H2 + coupling. On the other hand, the photoelectron energy spectra can be manipulated via laser-H2 + coupling. This study demonstrates the entanglement of molecular quantum wave packets, and affords a route to remotely control molecular dissociative ionization.

Communication: Electron ionization of DNA bases

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

Rahman, M. A.; Krishnakumar, E., E-mail: ekkumar@tifr.res.in

2016-04-28

No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve themore » existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.« less

The laser and optical system for the RIBF-PALIS experiment

NASA Astrophysics Data System (ADS)

Sonoda, T.; Iimura, H.; Reponen, M.; Wada, M.; Katayama, I.; Sonnenschein, V.; Takamatsu, T.; Tomita, H.; Kojima, T. M.

2018-01-01

This paper describes the laser and optical system for the Parasitic radioactive isotope (RI) beam production by Laser Ion-Source (PALIS) in the RIKEN fragment separator facility. This system requires an optical path length of 70 m for transporting the laser beam from the laser light source to the place for resonance ionization. To accomplish this, we designed and implemented a simple optical system consisting of several mirrors equipped with compact stepping motor actuators, lenses, beam spot screens and network cameras. The system enables multi-step laser resonance ionization in the gas cell and gas jet via overlap with a diameter of a few millimeters, between the laser photons and atomic beam. Despite such a long transport distance, we achieved a transport efficiency for the UV laser beam of about 50%. We also confirmed that the position stability of the laser beam stays within a permissible range for dedicated resonance ionization experiments.

The IP vs. VDE competition as a key factor determining the stability of the MgBX 5 (X = F, Cl) compounds

NASA Astrophysics Data System (ADS)

Sikorska, Celina; Skurski, Piotr

2010-11-01

The explanation of the MgBX 5 (X = F, Cl) systems existence and stability is provided on the basis of theoretical considerations supported by ab initio calculations. The equilibrium structures and most probable fragmentation processes of 26 (including isomers) MgBX 5 molecules and six OBX 5 compounds (for comparison) were examined and discussed. The competition between the ionization potential (IP) of the MgX subunit and the electron binding energy (VDE) of the BX 4 fragment was found to be the key factor determining the ability to form a stable compound of MgBX 5 type.

Fragmentation of a valine molecule by electron impact

NASA Astrophysics Data System (ADS)

Vukstich, V. S.; Romanova, L. G.; Megela, I. G.; Papp, A. V.; Snegurskii, A. V.

2017-05-01

The formation of ion products of single and dissociative ionization of a valine molecule (C5H11NO2) by high-energy (11.5 MeV) and low-energy (below 150 eV) electrons has been investigated by mass spectrometry. Mass spectra of this molecule and near-threshold functions of yield of its ion fragments, for which the magnitudes of occurrence energies are determined, have been obtained. The analysis of the changes in mass spectra of valine molecules irradiated with doses of 5 and 20 kGy in comparison with those for unirradiated molecules shows that high-energy irradiation changes irreversibly the structure of some of the initial molecules.

Ratios of regioisomers of the molecular species of triacylglycerols in lesquerella (Physaria fendleri) oil estimated by mass spectrometry

USDA-ARS?s Scientific Manuscript database

The ratios of regioisomers of 74 molecular species of triacylglycerols (TAG) in lesquerella oil were estimated using HPLC and the electrospray ionization mass spectrometry of the lithium adducts of TAG in the HPLC fractions of lequerella oil. The ratios of relative abundances of the fragment ions fr...

Search space mapping: getting a picture of coherent laser control.

PubMed

Shane, Janelle C; Lozovoy, Vadim V; Dantus, Marcos

2006-10-12

Search space mapping is a method for quickly visualizing the experimental parameters that can affect the outcome of a coherent control experiment. We demonstrate experimental search space mapping for the selective fragmentation and ionization of para-nitrotoluene and show how this method allows us to gather information about the dominant trends behind our achieved control.

Characterization of wood decay enzymes by MALDI-MS for post-translational modification and gene identification.

Treesearch

Theodorus H. de Koker; Philip J. Kersten

2002-01-01

The recent sequencing of the Phanerochaete chrysosporium genome presents many opportunities, including the possibility of rapidly correlating specific wood decay proteins of the fungus with the corresponding gene sequences. Here we compare mass fragments of trypsin digests, determined by MALDI-MS (Matrix Assisted Laser Desorption Ionization-Mass Spectrometry), with...

Timeframe Dependent Fragment Ions Observed in In-Source Decay Experiments with β-Casein Using MALDI MS.

PubMed

Sekiya, Sadanori; Nagoshi, Keishiro; Iwamoto, Shinichi; Tanaka, Koichi; Takayama, Mitsuo

2015-09-01

The fragment ions observed with time-of-flight (TOF) and quadrupole ion trap (QIT) TOF mass spectrometers (MS) combined with matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) experiments of phosphorylated analytes β-casein and its model peptide were compared from the standpoint of the residence timeframe of analyte and fragment ions in the MALDI ion source and QIT cell. The QIT-TOF MS gave fragment c-, z'-, z-ANL, y-, and b-ions, and further degraded fragments originating from the loss of neutrals such as H(2)O, NH(3), CH(2)O (from serine), C2H4O (from threonine), and H(3)PO(4), whereas the TOF MS merely showed MALDI source-generated fragment c-, z'-, z-ANL, y-, and w-ions. The fragment ions observed in the QIT-TOF MS could be explained by the injection of the source-generated ions into the QIT cell or a cooperative effect of a little internal energy deposition, a long residence timeframe (140 ms) in the QIT cell, and specific amino acid effects on low-energy CID, whereas the source-generated fragments (c-, z'-, z-ANL, y-, and w-ions) could be a result of prompt radical-initiated fragmentation of hydrogen-abundant radical ions [M + H + H](+) and [M + H - H](-) within the 53 ns timeframe, which corresponds to the delayed extraction time. The further degraded fragment b/y-ions produced in the QIT cell were confirmed by positive- and negative-ion low-energy CID experiments performed on the source-generated ions (c-, z'-, and y-ions). The loss of phosphoric acid (98 u) from analyte and fragment ions can be explained by a slow ergodic fragmentation independent of positive and negative charges.

Timeframe Dependent Fragment Ions Observed in In-Source Decay Experiments with β-Casein Using MALDI MS

NASA Astrophysics Data System (ADS)

Sekiya, Sadanori; Nagoshi, Keishiro; Iwamoto, Shinichi; Tanaka, Koichi; Takayama, Mitsuo

2015-09-01

The fragment ions observed with time-of-flight (TOF) and quadrupole ion trap (QIT) TOF mass spectrometers (MS) combined with matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) experiments of phosphorylated analytes β-casein and its model peptide were compared from the standpoint of the residence timeframe of analyte and fragment ions in the MALDI ion source and QIT cell. The QIT-TOF MS gave fragment c-, z'-, z-ANL, y-, and b-ions, and further degraded fragments originating from the loss of neutrals such as H2O, NH3, CH2O (from serine), C2H4O (from threonine), and H3PO4, whereas the TOF MS merely showed MALDI source-generated fragment c-, z'-, z-ANL, y-, and w-ions. The fragment ions observed in the QIT-TOF MS could be explained by the injection of the source-generated ions into the QIT cell or a cooperative effect of a little internal energy deposition, a long residence timeframe (140 ms) in the QIT cell, and specific amino acid effects on low-energy CID, whereas the source-generated fragments (c-, z'-, z-ANL, y-, and w-ions) could be a result of prompt radical-initiated fragmentation of hydrogen-abundant radical ions [M + H + H]+ and [M + H - H]- within the 53 ns timeframe, which corresponds to the delayed extraction time. The further degraded fragment b/y-ions produced in the QIT cell were confirmed by positive- and negative-ion low-energy CID experiments performed on the source-generated ions (c-, z'-, and y-ions). The loss of phosphoric acid (98 u) from analyte and fragment ions can be explained by a slow ergodic fragmentation independent of positive and negative charges.

Fast Ionized X-Ray Absorbers in AGNs

NASA Technical Reports Server (NTRS)

Fukumura, K.; Tombesi, F.; Kazanas, D.; Shrader, C.; Behar, E.; Contopoulos, I.

2016-01-01

We investigate the physics of the X-ray ionized absorbers often identified as warm absorbers (WAs) and ultra-fast outflows (UFOs) in Seyfert AGNs from spectroscopic studies in the context of magnetically-driven accretion-disk wind scenario. Launched and accelerated by the action of a global magnetic field anchored to an underlying accretion disk around a black hole, outflowing plasma is irradiated and ionized by an AGN radiation field characterized by its spectral energy density (SED). By numerically solving the Grad-Shafranov equation in the magnetohydrodynamic (MHD) framework, the physical property of the magnetized disk-wind is determined by a wind parameter set, which is then incorporated into radiative transfer calculations with xstar photoionization code under heating-cooling equilibrium state to compute the absorber's properties such as column density N(sub H), line-of-sight (LoS) velocity v, ionization parameter xi, among others. Assuming that the wind density scales as n varies as r(exp. -1), we calculate theoretical absorption measure distribution (AMD) for various ions seen in AGNs as well as line spectra especially for the Fe K alpha absorption feature by focusing on a bright quasar PG 1211+143 as a case study and show the model's plausibility. In this note we demonstrate that the proposed MHD-driven disk-wind scenario is not only consistent with the observed X-ray data, but also help better constrain the underlying nature of the AGN environment in a close proximity to a central engine.

Measurements of ion velocity separation and ionization in multi-species plasma shocks

NASA Astrophysics Data System (ADS)

Rinderknecht, Hans G.; Park, H.-S.; Ross, J. S.; Amendt, P. A.; Wilks, S. C.; Katz, J.; Hoffman, N. M.; Kagan, G.; Vold, E. L.; Keenan, B. D.; Simakov, A. N.; Chacón, L.

2018-05-01

The ion velocity structure of a strong collisional shock front in a plasma with multiple ion species is directly probed in laser-driven shock-tube experiments. Thomson scattering of a 263.25 nm probe beam is used to diagnose ion composition, temperature, and flow velocity in strong shocks ( M ˜6 ) propagating through low-density ( ρ˜0.1 mg/cc) plasmas composed of mixtures of hydrogen (98%) and neon (2%). Within the preheat region of the shock front, two velocity populations of ions are observed, a characteristic feature of strong plasma shocks. The ionization state of the Ne is observed to change within the shock front, demonstrating an ionization-timescale effect on the shock front structure. The forward-streaming proton feature is shown to be unexpectedly cool compared to predictions from ion Fokker-Planck simulations; the neon ionization gradient is evaluated as a possible cause.

Correlated multielectron dynamics in mid-infrared laser pulse interactions with neon atoms.

PubMed

Tang, Qingbin; Huang, Cheng; Zhou, Yueming; Lu, Peixiang

2013-09-09

The multielectron dynamics in nonsequential triple ionization (NSTI) of neon atoms driven by mid-infrared (MIR) laser pulses is investigated with the three-dimensional classical ensemble model. In consistent with the experimental result, our numerical result shows that in the MIR regime, the triply charged ion longitudinal momentum spectrum exhibits a pronounced double-hump structure at low laser intensity. Back analysis reveals that as the intensity increases, the responsible triple ionization channels transform from direct (e, 3e) channel to the various mixed channels. This transformation of the NSTI channels leads to the results that the shape of ion momentum spectra becomes narrow and the distinct maxima shift towards low momenta with the increase of the laser intensity. By tracing the triply ionized trajectories, the various ionization channels at different laser intensities are clearly identified and these results provide an insight into the complex dynamics of the correlated three electrons in NSTI.

The identification of disulfides in ricin D using proteolytic cleavage followed by negative-ion nano-electrospray ionization mass spectrometry of the peptide fragments.

PubMed

Tran, T T Nha; Brinkworth, Craig S; Bowie, John H

2015-01-30

To use negative-ion nano-electrospray ionization mass spectrometry of peptides from the tryptic digest of ricin D, to provide sequence information; in particular, to identify disulfide position and connectivity. Negative-ion fragmentations of peptides from the tryptic digest of ricin D was studied using a Waters QTOF2 mass spectrometer operating in MS and MS(2) modes. Twenty-three peptides were obtained following high-performance liquid chromatography and studied by negative-ion mass spectrometry covering 73% of the amino-acid residues of ricin D. Five disulfide-containing peptides were identified, three intermolecular and two intramolecular disulfide-containing peptides. The [M-H](-) anions of the intermolecular disulfides undergo facile cleavage of the disulfide units to produce fragment peptides. In negative-ion collision-induced dissociation (CID) these source-formed anions undergo backbone cleavages, which provide sequencing information. The two intramolecular disulfides were converted proteolytically into intermolecular disulfides, which were identified as outlined above. The positions of the five disulfide groups in ricin D may be determined by characteristic negative-ion cleavage of the disulfide groups, while sequence information may be determined using the standard negative-ion backbone cleavages of the resulting cleaved peptides. Negative-ion mass spectrometry can also be used to provide partial sequencing information for other peptides (i.e. those not containing Cys) using the standard negative-ion backbone cleavages of these peptides. Copyright © 2014 John Wiley & Sons, Ltd.

Parasitic production of slow RI-beam from a projectile fragment separator by ion guide Laser Ion Source (PALIS)

NASA Astrophysics Data System (ADS)

Sonoda, Tetsu

2009-10-01

The projectile fragment separator BigRIPS of RIBF at RIKEN provides a wide variety of short-lived radioactive isotope (RI) ions without restrictions on their lifetime or chemical properties. A universal slow RI-beam facility (SLOWRI) to decelerate the beams from BigRIPS using an RF-carpet ion guide has been proposed as a principal facility of RIBF. However, beam time at such a modern accelerator facility is always limited and operational costs are high. We therefore propose an additional scheme as a complementary option to SLOWRI to drastically enhance the usability of such an expensive facility. In BigRIPS, a single primary beam produces thousands of isotopes but only one isotope is used for an experiment while the other >99.99% of isotopes are simply dumped in the slits or elsewhere in the fragment separator. We plan to locate a compact gas cell with 1 bar Ar at the slits. The thermalized ions in the cell will be quickly neutralized and transported to the exit by gas flow and resonantly re-ionized by lasers. Such low energy RI-beams will always be provided without any restriction to the main experiment. It will allow us to run parasitic experiments for precision atomic or decay spectroscopy, mass measurements. Furthermore, the resonance ionization in the cell itself can be used for high-sensitive laser spectroscopy, which will expand our knowledge of the ground state property of unstable nuclei.

Electrochemical Ionization and Analyte Charging in the Array of Micromachined UltraSonic Electrospray (AMUSE) Ion Source

PubMed Central

Forbes, Thomas P.; Degertekin, F. Levent; Fedorov, Andrei G.

2010-01-01

Electrochemistry and ion transport in a planar array of mechanically-driven, droplet-based ion sources are investigated using an approximate time scale analysis and in-depth computational simulations. The ion source is modeled as a controlled-current electrolytic cell, in which the piezoelectric transducer electrode, which mechanically drives the charged droplet generation using ultrasonic atomization, also acts as the oxidizing/corroding anode (positive mode). The interplay between advective and diffusive ion transport of electrochemically generated ions is analyzed as a function of the transducer duty cycle and electrode location. A time scale analysis of the relative importance of advective vs. diffusive ion transport provides valuable insight into optimality, from the ionization prospective, of alternative design and operation modes of the ion source operation. A computational model based on the solution of time-averaged, quasi-steady advection-diffusion equations for electroactive species transport is used to substantiate the conclusions of the time scale analysis. The results show that electrochemical ion generation at the piezoelectric transducer electrodes located at the back-side of the ion source reservoir results in poor ionization efficiency due to insufficient time for the charged analyte to diffuse away from the electrode surface to the ejection location, especially at near 100% duty cycle operation. Reducing the duty cycle of droplet/analyte ejection increases the analyte residence time and, in turn, improves ionization efficiency, but at an expense of the reduced device throughput. For applications where this is undesirable, i.e., multiplexed and disposable device configurations, an alternative electrode location is incorporated. By moving the charging electrode to the nozzle surface, the diffusion length scale is greatly reduced, drastically improving ionization efficiency. The ionization efficiency of all operating conditions considered is expressed as a function of the dimensionless Peclet number, which defines the relative effect of advection as compared to diffusion. This analysis is general enough to elucidate an important role of electrochemistry in ionization efficiency of any arrayed ion sources, be they mechanically-driven or electrosprays, and is vital for determining optimal design and operation conditions. PMID:20607111

[Fragment-based drug discovery: concept and aim].

PubMed

Tanaka, Daisuke

2010-03-01

Fragment-Based Drug Discovery (FBDD) has been recognized as a newly emerging lead discovery methodology that involves biophysical fragment screening and chemistry-driven fragment-to-lead stages. Although fragments, defined as structurally simple and small compounds (typically <300 Da), have not been employed in conventional high-throughput screening (HTS), the recent significant progress in the biophysical screening methods enables fragment screening at a practical level. The intention of FBDD primarily turns our attention to weakly but specifically binding fragments (hit fragments) as the starting point of medicinal chemistry. Hit fragments are then promoted to more potent lead compounds through linking or merging with another hit fragment and/or attaching functional groups. Another positive aspect of FBDD is ligand efficiency. Ligand efficiency is a useful guide in screening hit selection and hit-to-lead phases to achieve lead-likeness. Owing to these features, a number of successful applications of FBDD to "undruggable targets" (where HTS and other lead identification methods failed to identify useful lead compounds) have been reported. As a result, FBDD is now expected to complement more conventional methodologies. This review, as an introduction of the following articles, will summarize the fundamental concepts of FBDD and will discuss its advantages over other conventional drug discovery approaches.

Oxidative Ionization Under Certain Negative-Ion Mass Spectrometric Conditions

NASA Astrophysics Data System (ADS)

Hassan, Isra; Pavlov, Julius; Errabelli, Ramu; Attygalle, Athula B.

2017-02-01

1,4-Hydroquinone and several other phenolic compounds generate (M - 2) -• radical-anions, rather than deprotonated molecules, under certain negative-ion mass spectrometric conditions. In fact, spectra generated under helium-plasma ionization (HePI) conditions from 1,4-hydroquinone and 1,4-benzoquinone (by electron capture) were practically indistinguishable. Because this process involves a net loss of H• and H+, it can be termed oxidative ionization. The superoxide radical-anion (O2 -•), known to be present in many atmospheric-pressure plasma ion sources operated in the negative mode, plays a critical role in the oxidative ionization process. The presence of a small peak at m/z 142 in the spectrum of 1,4-hydroquinone, but not in that of 1,4-benzoquinone, indicated that the initial step in the oxidative ionization process is the formation of an O2 -• adduct. On the other hand, under bona fide electrospray ionization (ESI) conditions, 1,4-hydroquinone generates predominantly an (M - 1) - ion. It is known that at sufficiently high capillary voltages, corona discharges begin to occur even in an ESI source. At lower ESI capillary voltages, deprotonation predominates; as the capillary voltage is raised, the abundance of O2 -• present in the plasma increases, and the source in turn increasingly behaves as a composite ESI/APCI source. While maintaining post-ionization ion activation to a minimum (to prevent fragmentation), and monitoring the relative intensities of the m/z 109 (due to deprotonation) and 108 (oxidative ionization) peaks recorded from 1,4-hydroquinone, a semiquantitative estimation of the APCI contribution to the overall ion-generation process can be obtained.

Site-Specific Photoconjugation of Beta-Lactamase Fragments to Monoclonal Antibodies Enables Sensitive Analyte Detection via Split-Enzyme Complementation.

PubMed

Yu, Feifan; Alesand, Veronica; Nygren, Per-Åke

2018-02-27

Protein fragment complementation assays (PCA) rely on a proximity-driven reconstitution of a split reporter protein activity, typically via interaction between bait and prey units separately fused to the reporter protein halves. The PCA principle can also be formatted for use in immunossays for analyte detection, e.g., via the use of small immunoglobulin binding proteins (IgBp) as fusion partners to split-reporter protein fragments for conversion of pairs of antibodies into split-protein half-probes. However, the non-covalent binding between IgBp and antibodies is not ideal for development of robust assays. Here, the authors describe how split-enzyme reporter halves can be both site-specifically and covalently photoconjugated at antibody Fc-parts for use in homogeneous dual-antibody in vitro immunoassays based on analyte-dependent split-enzyme fragment complementation. The half-probes consist of parts of a beta-lactamase split-protein reporter fused to an immunoglobulin Fc binding domain equipped with a unique cysteine residue at which a photoactivable maleimide benzophenone group (MBP) is attached. Using such antibody conjugates the authors obtain an analyte-driven complementation of the reporter enzyme fragments monitored via conversion of a chromogenic substrate. Results from detection of human interferon-gamma and the extracellular domain of HER2 is shown. The described principles for site-specific conjugation of proteins to antibodies should be broadly applicable. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic modeling of x-ray laser-driven solid Al plasmas via particle-in-cell simulation

NASA Astrophysics Data System (ADS)

Royle, R.; Sentoku, Y.; Mancini, R. C.; Paraschiv, I.; Johzaki, T.

2017-06-01

Solid-density plasmas driven by intense x-ray free-electron laser (XFEL) radiation are seeded by sources of nonthermal photoelectrons and Auger electrons that ionize and heat the target via collisions. Simulation codes that are commonly used to model such plasmas, such as collisional-radiative (CR) codes, typically assume a Maxwellian distribution and thus instantaneous thermalization of the source electrons. In this study, we present a detailed description and initial applications of a collisional particle-in-cell code, picls, that has been extended with a self-consistent radiation transport model and Monte Carlo models for photoionization and K L L Auger ionization, enabling the fully kinetic simulation of XFEL-driven plasmas. The code is used to simulate two experiments previously performed at the Linac Coherent Light Source investigating XFEL-driven solid-density Al plasmas. It is shown that picls-simulated pulse transmissions using the Ecker-Kröll continuum-lowering model agree much better with measurements than do simulations using the Stewart-Pyatt model. Good quantitative agreement is also found between the time-dependent picls results and those of analogous simulations by the CR code scfly, which was used in the analysis of the experiments to accurately reproduce the observed K α emissions and pulse transmissions. Finally, it is shown that the effects of the nonthermal electrons are negligible for the conditions of the particular experiments under investigation.

Universal fragment descriptors for predicting properties of inorganic crystals

NASA Astrophysics Data System (ADS)

Isayev, Olexandr; Oses, Corey; Toher, Cormac; Gossett, Eric; Curtarolo, Stefano; Tropsha, Alexander

2017-06-01

Although historically materials discovery has been driven by a laborious trial-and-error process, knowledge-driven materials design can now be enabled by the rational combination of Machine Learning methods and materials databases. Here, data from the AFLOW repository for ab initio calculations is combined with Quantitative Materials Structure-Property Relationship models to predict important properties: metal/insulator classification, band gap energy, bulk/shear moduli, Debye temperature and heat capacities. The prediction's accuracy compares well with the quality of the training data for virtually any stoichiometric inorganic crystalline material, reciprocating the available thermomechanical experimental data. The universality of the approach is attributed to the construction of the descriptors: Property-Labelled Materials Fragments. The representations require only minimal structural input allowing straightforward implementations of simple heuristic design rules.

Universal fragment descriptors for predicting properties of inorganic crystals.

PubMed

Isayev, Olexandr; Oses, Corey; Toher, Cormac; Gossett, Eric; Curtarolo, Stefano; Tropsha, Alexander

2017-06-05

Although historically materials discovery has been driven by a laborious trial-and-error process, knowledge-driven materials design can now be enabled by the rational combination of Machine Learning methods and materials databases. Here, data from the AFLOW repository for ab initio calculations is combined with Quantitative Materials Structure-Property Relationship models to predict important properties: metal/insulator classification, band gap energy, bulk/shear moduli, Debye temperature and heat capacities. The prediction's accuracy compares well with the quality of the training data for virtually any stoichiometric inorganic crystalline material, reciprocating the available thermomechanical experimental data. The universality of the approach is attributed to the construction of the descriptors: Property-Labelled Materials Fragments. The representations require only minimal structural input allowing straightforward implementations of simple heuristic design rules.

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Efficient and robust photo-ionization loading of beryllium ions

NASA Astrophysics Data System (ADS)

Wolf, Sebastian; Studer, Dominik; Wendt, Klaus; Schmidt-Kaler, Ferdinand

2018-02-01

We demonstrate the efficient generation of Be^+ ions with a 60 ns and 150 nJ laser pulse near 235 nm for two-step photo-ionization, proven by subsequent counting of the number of ions loaded into a linear Paul trap. The bandwidth and power of the laser pulse are chosen in such a way that a first, resonant step fully saturates the entire velocity distribution of beryllium atoms effusing from a thermal oven. The second excitation step is driven by the same light field causing efficient non-resonant ionization. Our ion-loading scheme has a similar efficiency as compared to former pathways using two-photon continuous wave laser excitation, but with an order of magnitude lower than average UV light power.

Surface-assisted laser desorption ionization mass spectrometry techniques for application in forensics.

PubMed

Guinan, Taryn; Kirkbride, Paul; Pigou, Paul E; Ronci, Maurizio; Kobus, Hilton; Voelcker, Nicolas H

2015-01-01

Matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) is an excellent analytical technique for the rapid and sensitive analysis of macromolecules (>700 Da), such as peptides, proteins, nucleic acids, and synthetic polymers. However, the detection of smaller organic molecules with masses below 700 Da using MALDI-MS is challenging due to the appearance of matrix adducts and matrix fragment peaks in the same spectral range. Recently, nanostructured substrates have been developed that facilitate matrix-free laser desorption ionization (LDI), contributing to an emerging analytical paradigm referred to as surface-assisted laser desorption ionization (SALDI) MS. Since SALDI enables the detection of small organic molecules, it is rapidly growing in popularity, including in the field of forensics. At the same time, SALDI also holds significant potential as a high throughput analytical tool in roadside, work place and athlete drug testing. In this review, we discuss recent advances in SALDI techniques such as desorption ionization on porous silicon (DIOS), nano-initiator mass spectrometry (NIMS) and nano assisted laser desorption ionization (NALDI™) and compare their strengths and weaknesses with particular focus on forensic applications. These include the detection of illicit drug molecules and their metabolites in biological matrices and small molecule detection from forensic samples including banknotes and fingerprints. Finally, the review highlights recent advances in mass spectrometry imaging (MSI) using SALDI techniques. © 2014 Wiley Periodicals, Inc.

Computational model of collisional-radiative nonequilibrium plasma in an air-driven type laser propulsion

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

Ogino, Yousuke; Ohnishi, Naofumi

A thrust power of a gas-driven laser-propulsion system is obtained through interaction with a propellant gas heated by a laser energy. Therefore, understanding the nonequilibrium nature of laser-produced plasma is essential for increasing available thrust force and for improving energy conversion efficiency from a laser to a propellant gas. In this work, a time-dependent collisional-radiative model for air plasma has been developed to study the effects of nonequilibrium atomic and molecular processes on population densities for an air-driven type laser propulsion. Many elementary processes are considered in the number density range of 10{sup 12}/cm{sup 3}<=N<=10{sup 19}/cm{sup 3} and the temperaturemore » range of 300 K<=T<=40,000 K. We then compute the unsteady nature of pulsively heated air plasma. When the ionization relaxation time is the same order as the time scale of a heating pulse, the effects of unsteady ionization are important for estimating air plasma states. From parametric computations, we determine the appropriate conditions for the collisional-radiative steady state, local thermodynamic equilibrium, and corona equilibrium models in that density and temperature range.« less

Fragmentation studies of relativistic iron ions using plastic nuclear track detectors.

PubMed

Scampoli, P; Durante, M; Grossi, G; Manti, L; Pugliese, M; Gialanella, G

2005-01-01

We measured fluence and fragmentation of high-energy (1 or 5 A GeV) 56Fe ions accelerated at the Alternating Gradient Synchrotron or at the NASA Space Radiation Laboratory (Brookhaven National Laboratory, NY, USA) using solid-state CR-39 nuclear track detectors. Different targets (polyethylene, PMMA, C, Al, Pb) were used to produce a large spectrum of charged fragments. CR-39 plastics were exposed both in front and behind the shielding block (thickness ranging from 5 to 30 g/cm2) at a normal incidence and low fluence. The radiation dose deposited by surviving Fe ions and charged fragments was measured behind the shield using an ionization chamber. The distribution of the measured track size was exploited to distinguish the primary 56Fe ions tracks from the lighter fragments. Measurements of projectile's fluence in front of the shield were used to determine the dose per incident particle behind the block. Simultaneous measurements of primary 56Fe ion tracks in front and behind the shield were used to evaluate the fraction of surviving iron projectiles and the total charge-changing fragmentation cross-section. These physical measurements will be used to characterize the beam used in parallel biological experiments. c2005 COSPAR. Published by Elsevier Ltd. All rights reserved.

Imaging mass spectrometry reveals direct albumin fragmentation within the diabetic kidney.

PubMed

Grove, Kerri J; Lareau, Nichole M; Voziyan, Paul A; Zeng, Fenghua; Harris, Raymond C; Hudson, Billy G; Caprioli, Richard M

2018-05-17

Albumin degradation in the renal tubules is impaired in diabetic nephropathy such that levels of the resulting albumin fragments increase with the degree of renal injury. However, the mechanism of albumin degradation is unknown. In particular, fragmentation of the endogenous native albumin has not been demonstrated in the kidney and the enzymes that may contribute to fragmentation have not been identified. To explore this we utilized matrix-assisted laser desorption/ionization imaging mass spectrometry for molecular profiling of specific renal regions without disturbing distinct tissue morphology. Changes in protein expression were measured in kidney sections of eNOS -/- db/db mice, a model of diabetic nephropathy, by high spatial resolution imaging allowing molecular localizations at the level of single glomeruli and tubules. Significant increases were found in the relative abundances of several albumin fragments in the kidney of the mice with diabetic nephropathy compared with control nondiabetic mice. The relative abundance of fragments detected correlated positively with the degree of nephropathy. Furthermore, specific albumin fragments accumulating in the lumen of diabetic renal tubules were identified and predicted the enzymatic action of cathepsin D based on cleavage specificity and in vitro digestions. Importantly, this was demonstrated directly in the renal tissue with the endogenous nonlabeled murine albumin. Thus, our results provide molecular insights into the mechanism of albumin degradation in diabetic nephropathy. Copyright © 2018 International Society of Nephrology. Published by Elsevier Inc. All rights reserved.

Fragmentation characteristics of hydroxycinnamic acids in ESI-MSn by density functional theory.

PubMed

Yin, Zhi-Hui; Sun, Chang-Hai; Fang, Hong-Zhuang

2017-07-01

This work aims to analyze the electrospray ionization multistage mass spectrometry (ESI-MS n ) fragmentation characteristics of hydroxycinnamic acids (HCAs) in negative ion mode. The geometric parameters, energies, natural bond orbitals and frontier orbitals of fragments were calculated by density functional theory (DFT) to investigate mass spectral fragmentation mechanisms. The results showed that proton transfer always occurred during fragmentation of HCAs; their quasi-molecular ions ([M - H] - ) existed in more than one form and were mainly with the lowest energy. The fragmentation characteristics included the followings: (1) according to the different substitution position of phenolic hydroxyl group, the ring contraction reaction by CO elimination from benzene was in an increasingly difficult order: m-phenolic hydroxyl > p-phenolic hydroxyl > o-phenolic hydroxyl; and (2) ortho effect always occurred in o-dihydroxycinnamic acids (o-diHCAs), i.e. one phenolic hydroxyl group offered H + , which combined with the other one to lose H 2 O. In addition, there was a nucleophilic reaction during ring contraction in diHCAs that oxygen atom attacked the carbon atom binding with the other phenolic hydroxyl to lose CO 2 . The fragmentation characteristics and mechanism of HCAs could be used for analysis and identification of such compounds quickly and effectively, and as reference for structural analogues by ESI-MS. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

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.

A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH 4): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH 4 and CH 4 +

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

Chang, Yih -Chung; Xiong, Bo; Bross, David H.

Here, we report on the successful implementation of a high-resolution vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection method for the study of unimolecular dissociation of quantum-state- or energy-selected molecular ions. As a test case, we have determined the 0 K appearance energy (AE 0) for the formation of methylium, CH 3 +, from methane, CH 4, as AE 0 (CH 3 +/CH 4) = 14.32271 ± 0.00013 eV. This value has a significantly smaller error limit, but is otherwise consistent with previous laboratory and/or synchrotron-based studies of this dissociative photoionization onset. Furthermore, the sum of the VUV lasermore » PFI-PI spectra obtained for the parent CH 4 + ion and the fragment CH 3 + ions of methane is found to agree with the earlier VUV pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of methane, providing unambiguous validation of the previous interpretation that the sharp VUV-PFI-PE step observed at the AE 0 (CH 3 +/CH 4) threshold ensues because of higher PFI detection efficiency for fragment CH 3 + than for parent CH 4 +. This, in turn, is a consequence of the underlying high- n Rydberg dissociation mechanism for the dissociative photoionization of CH 4, which was proposed in previous synchrotron-based VUV-PFI-PE and VUV-PFI-PEPICO studies of CH 4. The present highly accurate 0 K dissociative ionization threshold for CH 4 can be utilized to derive accurate values for the bond dissociation energies of methane and methane cation. For methane, the straightforward application of sequential thermochemistry via the positive ion cycle leads to some ambiguity because of two competing VUV-PFI-PE literature values for the ionization energy of methyl radical. The ambiguity is successfully resolved by applying the Active Thermochemical Tables (ATcT) approach, resulting in D 0 (H-CH 3) = 432.463 ± 0.027 kJ/mol and D 0(H-CH 3 +) = 164.701 ± 0.038 kJ/mol.« less

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

PubMed

Lehmann, C Stefan; Ram, N Bhargava; Powis, Ivan; Janssen, Maurice H M

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

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

Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M., E-mail: m.h.m.janssen@vu.nl

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flightmore » mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations. Qualitative agreement is observed between the experimental results and the theoretical calculations of the Legendre moments representing the angular distribution for the two enantiomers. The electron-ion coincidence technique using multiphoton ionization opens new directions in table-top analytical mass-spectrometric applications of mixtures of chiral molecules.« less

A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH 4): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH 4 and CH 4 +

DOE PAGES

Chang, Yih -Chung; Xiong, Bo; Bross, David H.; ...

2017-03-27

Here, we report on the successful implementation of a high-resolution vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection method for the study of unimolecular dissociation of quantum-state- or energy-selected molecular ions. As a test case, we have determined the 0 K appearance energy (AE 0) for the formation of methylium, CH 3 +, from methane, CH 4, as AE 0 (CH 3 +/CH 4) = 14.32271 ± 0.00013 eV. This value has a significantly smaller error limit, but is otherwise consistent with previous laboratory and/or synchrotron-based studies of this dissociative photoionization onset. Furthermore, the sum of the VUV lasermore » PFI-PI spectra obtained for the parent CH 4 + ion and the fragment CH 3 + ions of methane is found to agree with the earlier VUV pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of methane, providing unambiguous validation of the previous interpretation that the sharp VUV-PFI-PE step observed at the AE 0 (CH 3 +/CH 4) threshold ensues because of higher PFI detection efficiency for fragment CH 3 + than for parent CH 4 +. This, in turn, is a consequence of the underlying high- n Rydberg dissociation mechanism for the dissociative photoionization of CH 4, which was proposed in previous synchrotron-based VUV-PFI-PE and VUV-PFI-PEPICO studies of CH 4. The present highly accurate 0 K dissociative ionization threshold for CH 4 can be utilized to derive accurate values for the bond dissociation energies of methane and methane cation. For methane, the straightforward application of sequential thermochemistry via the positive ion cycle leads to some ambiguity because of two competing VUV-PFI-PE literature values for the ionization energy of methyl radical. The ambiguity is successfully resolved by applying the Active Thermochemical Tables (ATcT) approach, resulting in D 0 (H-CH 3) = 432.463 ± 0.027 kJ/mol and D 0(H-CH 3 +) = 164.701 ± 0.038 kJ/mol.« less

Desorption Mass Spectrometry for Nonvolatile Compounds Using an Ultrasonic Cutter

NASA Astrophysics Data System (ADS)

Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T.; Hiraoka, Kenzo

2014-07-01

In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

Desorption mass spectrometry for nonvolatile compounds using an ultrasonic cutter.

PubMed

Habib, Ahsan; Ninomiya, Satoshi; Chen, Lee Chuin; Usmanov, Dilshadbek T; Hiraoka, Kenzo

2014-07-01

In this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40 kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1 ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.

Soft Ionization of Saturated Hydrocarbons, Alcohols and Nonpolar Compounds by Negative-Ion Direct Analysis in Real-Time Mass Spectrometry

NASA Astrophysics Data System (ADS)

Cody, Robert B.; Dane, A. John

2013-03-01

Large polarizable n-alkanes (approximately C18 and larger), alcohols, and other nonpolar compounds can be detected as negative ions when sample solutions are injected directly into the sampling orifice of the atmospheric pressure interface of the time-of-flight mass spectrometer with the direct analysis in real time (DART) ion source operating in negative-ion mode. The mass spectra are dominated by peaks corresponding to [M + O2]‾•. No fragmentation is observed, making this a very soft ionization technique for samples that are otherwise difficult to analyze by DART. Detection limits for cholesterol were determined to be in the low nanogram range.

Soft ionization of saturated hydrocarbons, alcohols and nonpolar compounds by negative-ion direct analysis in real-time mass spectrometry.

PubMed

Cody, Robert B; Dane, A John

2013-03-01

Large polarizable n-alkanes (approximately C18 and larger), alcohols, and other nonpolar compounds can be detected as negative ions when sample solutions are injected directly into the sampling orifice of the atmospheric pressure interface of the time-of-flight mass spectrometer with the direct analysis in real time (DART) ion source operating in negative-ion mode. The mass spectra are dominated by peaks corresponding to [M + O2]‾(•). No fragmentation is observed, making this a very soft ionization technique for samples that are otherwise difficult to analyze by DART. Detection limits for cholesterol were determined to be in the low nanogram range.

Reassembly of a bioluminescent protein Renilla luciferase directed through DNA hybridization.

PubMed

Cissell, Kyle A; Rahimi, Yasmeen; Shrestha, Suresh; Deo, Sapna K

2009-01-01

Reassembly of split reporter proteins, also referred to as protein complementation, is utilized in the detection of protein-protein or protein-nucleic acid interactions. In this strategy, a reporter protein is fragmented into two inactive polypeptides to which interacting/binding partners are fused. The interaction between fused partners leads to the formation of a reassembled, active reporter. In this Communication, we have presented a proof-of-concept for the detection of a target nucleic acid sequence based on the reassembly of the bioluminescent reporter Renilla luciferase (Rluc), which is driven by DNA hybridization. Although, reassembly of Rluc though protein interactions has been demonstrated by others, the Rluc reassembly through DNA hybridization has not been shown yet, which is the novelty of this work. It is well established that bioluminescence detection offers significant advantages due to the absence of any background signal. In our study, two rationally designed fragments of Rluc were conjugated to complementary oligonucleotide probes. Hybridization of the two probes with fused Rluc fragments resulted in the reassembly of the fragments, generating active Rluc, measurable by the intensity of light given off upon addition of coelenterazine. Our study also shows that the reassembly of Rluc can be inhibited by an oligonucleotide probe that competes to bind to the hybridized probe-Rluc fragment complex, indicating a potential strategy for the quantitative detection of target nucleic acid. We were able to achieve the reassembly of Rluc fused to oligonucleotide probes using femtomole amounts of the probe-fragment protein conjugate. This concentration is approximately 4 orders of magnitude less than that reported using green fluorescent protein (GFP) as the reporter. A DNA-driven Rluc reassembly study performed in a cellular matrix did not show any interference from the matrix.

Structural characterization of arginine-vasopressin and lysine-vasopressin by Fourier- transform ion cyclotron resonance mass spectrometry and infrared multiphoton dissociation.

PubMed

Bianco, Giuliana; Battista, Fabio; Buchicchio, Alessandro; Amarena, Concetta G; Schmitt-Kopplin, Philippe; Guerrieri, Antonio

2015-01-01

Arginine-vasopressin (AVP) and lysine-vasopressin (LVP) were analyzed by reversed-phase liquid chromatography/mass spectrometry (LC-MS) using Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) electrospray ionization (ESI) in the positive ion mode. LVP and AVP exhibited the protonated adduct [M+H](+) as the predominant ion at m/z 1056.43965 and at m/z 1084.44561, respectively. Infrared multiphoton dissociation (IRMPD), using a CO(2) laser source at a wavelength of 10.6 μm, was applied to protonated vasopressin molecules. The IRMPD mass spectra presented abundant mass fragments essential for a complete structural information. Several fragment ions, shared between two target molecules, are discussed in detail. Some previously unpublished fragments were identified unambiguously utilizing the high resolution and accurate mass information provided by the FT-ICR mass spectrometer. The opening of the disulfide loop and the cleavage of the peptide bonds within the ring were observed even under low-energy fragmentation conditions. Coupling the high-performance FT-ICR mass spectrometer with IRMPD as a contemporary fragmentation technique proved to be very promising for the structural characterization of vasopressin.

Target fragmentation in radiobiology

NASA Technical Reports Server (NTRS)

Wilson, John W.; Cucinotta, Francis A.; Shinn, Judy L.; Townsend, Lawrence W.

1993-01-01

Nuclear reactions in biological systems produce low-energy fragments of the target nuclei seen as local high events of linear energy transfer (LET). A nuclear-reaction formalism is used to evaluate the nuclear-induced fields within biosystems and their effects within several biological models. On the basis of direct ionization interaction, one anticipates high-energy protons to have a quality factor and relative biological effectiveness (RBE) of unity. Target fragmentation contributions raise the effective quality factor of 10 GeV protons to 3.3 in reasonable agreement with RBE values for induced micronuclei in bean sprouts. Application of the Katz model indicates that the relative increase in RBE with decreasing exposure observed in cell survival experiments with 160 MeV protons is related solely to target fragmentation events. Target fragment contributions to lens opacity given an RBE of 1.4 for 2 GeV protons in agreement with the work of Lett and Cox. Predictions are made for the effective RBE for Harderian gland tumors induced by high-energy protons. An exposure model for lifetime cancer risk is derived from NCRP 98 risk tables, and protraction effects are examined for proton and helium ion exposures. The implications of dose rate enhancement effects on space radiation protection are considered.

The ionization parameter of star-forming galaxies evolves with the specific star formation rate

NASA Astrophysics Data System (ADS)

Kaasinen, Melanie; Kewley, Lisa; Bian, Fuyan; Groves, Brent; Kashino, Daichi; Silverman, John; Kartaltepe, Jeyhan

2018-07-01

We investigate the evolution of the ionization parameter of star-forming galaxies using a high-redshift (z˜ 1.5) sample from the FMOS-COSMOS (Fibre Multi-Object Spectrograph-COSMic evOlution Survey) and matched low-redshift samples from the Sloan Digital Sky Survey. By constructing samples of low-redshift galaxies for which the stellar mass (M*), star formation rate (SFR), and specific star formation rate (sSFR) are matched to the high-redshift sample, we remove the effects of an evolution in these properties. We also account for the effect of metallicity by jointly constraining the metallicity and ionization parameter of each sample. We find an evolution in the ionization parameter for main-sequence, star-forming galaxies and show that this evolution is driven by the evolution of sSFR. By analysing the matched samples as well as a larger sample of z< 0.3, star-forming galaxies we show that high ionization parameters are directly linked to high sSFRs and are not simply the by-product of an evolution in metallicity. Our results are physically consistent with the definition of the ionization parameter, a measure of the hydrogen ionizing photon flux relative to the number density of hydrogen atoms.

Interaction of toluene with two-color asymmetric laser fields: Controlling the directional emission of molecular hydrogen fragments

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

Kaziannis, S.; Kotsina, N.; Kosmidis, C.

The interaction of toluene with strong asymmetric two-color laser irradiation of 40 fs duration is studied by means of Time of flight mass spectrometry. Highly energetic H{sub 2}{sup +} and H{sub 3}{sup +} fragment ions are produced through an isomerization process taking place within transient multiply charged parent ions. Comparative study of deuterium labeled toluene isotopes enables the discrimination between molecular hydrogen fragments formed exclusively within the CH{sub 3}- part from those that require hydrogen atom exchange between the former and the phenyl moiety. It is demonstrated that by manipulating the relative phase of the ω/2ω field components the selectivemore » ionization of oriented toluene molecules can be used as a tool to control the directional emission of the H{sub 2}{sup +}, H{sub 3}{sup +} species.« less

Quantitative analysis of modified proteins and their positional isomers by tandem mass spectrometry: human histone H4.

PubMed

Pesavento, James J; Mizzen, Craig A; Kelleher, Neil L

2006-07-01

Here we show that fragment ion abundances from dissociation of ions created from mixtures of multiply modified histone H4 (11 kDa) or of N-terminal synthetic peptides (2 kDa) correspond to their respective intact ion abundances measured by Fourier transform mass spectrometry. Isomeric mixtures of modified forms of the same protein are resolved and quantitated with a precision of

Meta-analysis of the effects of forest fragmentation on interspecific interactions.

PubMed

Magrach, Ainhoa; Laurance, William F; Larrinaga, Asier R; Santamaria, Luis

2014-10-01

Forest fragmentation dramatically alters species persistence and distribution and affects many ecological interactions among species. Recent studies suggest that mutualisms, such as pollination and seed dispersal, are more sensitive to the negative effects of forest fragmentation than antagonisms, such as predation or herbivory. We applied meta-analytical techniques to evaluate this hypothesis and quantified the relative contributions of different components of the fragmentation process (decreases in fragment size, edge effects, increased isolation, and habitat degradation) to the overall effect. The effects of fragmentation on mutualisms were primarily driven by habitat degradation, edge effects, and fragment isolation, and, as predicted, they were consistently more negative on mutualisms than on antagonisms. For the most studied interaction type, seed dispersal, only certain components of fragmentation had significant (edge effects) or marginally significant (fragment size) effects. Seed size modulated the effect of fragmentation: species with large seeds showed stronger negative impacts of fragmentation via reduced dispersal rates. Our results reveal that different components of the habitat fragmentation process have varying impacts on key mutualisms. We also conclude that antagonistic interactions have been understudied in fragmented landscapes, most of the research has concentrated on particular types of mutualistic interactions such as seed dispersal, and that available studies of interspecific interactions have a strong geographical bias (arising mostly from studies carried out in Brazil, Chile, and the United States). © 2014 Society for Conservation Biology.

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

Barc, B.; Ryszka, M.; Spurrell, J.

Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S{sub 2}(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C{sub 3}H{sub 4}N{sub 2}O{sup +} following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a COmore » group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C{sub 3}H{sub 3}NO{sup +}) but represses C{sub 3}H{sub 4}N{sub 2}O{sup +} production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.« less

Analysis of 62 synthetic cannabinoids by gas chromatography-mass spectrometry with photoionization.

PubMed

Akutsu, Mamoru; Sugie, Ken-Ichi; Saito, Koichi

2017-01-01

Gas chromatography-mass spectrometry (GC-MS) in electron ionization (EI) mode is one of the most commonly used techniques for analysis of synthetic cannabinoids, because the GC-EI-MS spectra contain characteristic fragment ions for identification of a compound; however, the information on its molecular ions is frequently lacking. To obtain such molecular ion information, GC-MS in chemical ionization (CI) mode is frequently used. However, GC-CI-MS requires a relatively tedious process using reagent gas such as methane or isobutane. In this study, we show that GC-MS in photoionization (PI) mode provided molecular ions in all spectra of 62 synthetic cannabinoids, and 35 of the 62 compounds showed only the molecular radical cations. Except for the 35 compounds, the PI spectra showed very simple patterns with the molecular peak plus only a few fragment peak(s). An advantage is that the ion source for GC-PI-MS can easily be used for GC-EI-MS as well. Therefore, GC-EI/PI-MS will be a useful tool for the identification of synthetic cannabinoids contained in a dubious product. To the best of our knowledge, this is the first report to use GC-PI-MS for analysis of synthetic cannabinoids.

The Hall Instability of Weakly Ionized, Radially Stratified, Rotating Disks

NASA Astrophysics Data System (ADS)

Liverts, Edward; Mond, Michael; Chernin, Arthur D.

2007-09-01

Cool weakly ionized gaseous rotating disks are considered by many models to be the origin of the evolution of protoplanetary clouds. Instabilities against perturbations in such disks play an important role in the theory of the formation of stars and planets. Thus, a hierarchy of successive fragmentations into smaller and smaller pieces as a part of the Kant-Laplace theory of formation of the planetary system remains valid also for contemporary cosmogony. Traditionally, axisymmetric magnetohydrodynamic (MHD) and, recently, Hall-MHD instabilities have been thoroughly studied as providers of an efficient mechanism for radial transfer of angular momentum and of radial density stratification. In the current work, the Hall instability against nonaxisymmetric perturbations in compressible rotating fluid in external magnetic field is proposed as a viable mechanism for the azimuthal fragmentation of the protoplanetary disk and, thus, perhaps initiates the road to planet formation. The Hall instability is excited due to the combined effect of the radial stratification of the disk and the Hall electric field, and its growth rate is of the order of the rotation period. This family of instabilities is introduced here for the first time in an astrophysical context.

Sensitive and Structure-Informative N-Glycosylation Analysis by MALDI-MS; Ionization, Fragmentation, and Derivatization

PubMed Central

Nishikaze, Takashi

2017-01-01

Mass spectrometry (MS) has become an indispensable tool for analyzing post translational modifications of proteins, including N-glycosylated molecules. Because most glycosylation sites carry a multitude of glycans, referred to as “glycoforms,” the purpose of an N-glycosylation analysis is glycoform profiling and glycosylation site mapping. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has unique characteristics that are suited for the sensitive analysis of N-glycosylated products. However, the analysis is often hampered by the inherent physico-chemical properties of N-glycans. Glycans are highly hydrophilic in nature, and therefore tend to show low ion yields in both positive- and negative-ion modes. The labile nature and complicated branched structures involving various linkage isomers make structural characterization difficult. This review focuses on MALDI-MS-based approaches for enhancing analytical performance in N-glycosylation research. In particular, the following three topics are emphasized: (1) Labeling for enhancing the ion yields of glycans and glycopeptides, (2) Negative-ion fragmentation for less ambiguous elucidation of the branched structure of N-glycans, (3) Derivatization for the stabilization and linkage isomer discrimination of sialic acid residues. PMID:28794918

UPLC-MSE Profiling of Phytoplankton Metabolites: Application to the Identification of Pigments and Structural Analysis of Metabolites in Porphyridium purpureum

PubMed Central

Juin, Camille; Bonnet, Antoine; Nicolau, Elodie; Bérard, Jean-Baptiste; Devillers, Romain; Thiéry, Valérie; Cadoret, Jean-Paul; Picot, Laurent

2015-01-01

A fast and high-resolution UPLC-MSE analysis was used to identify phytoplankton pigments in an ethanol extract of Porphyridium purpureum (Pp) devoid of phycobiliproteins. In a first step, 22 standard pigments were analyzed by UPLC-MSE to build a database including retention time and accurate masses of parent and fragment ions. Using this database, seven pigments or derivatives previously reported in Pp were unequivocally identified: β,β-carotene, chlorophyll a, zeaxanthin, chlorophyllide a, pheophorbide a, pheophytin a, and cryptoxanthin. Minor amounts of Divinyl chlorophyll a, a chemotaxonomic pigment marker for prochlorophytes, were also unequivocally identified using the database. Additional analysis of ionization and fragmentation patterns indicated the presence of ions that could correspond to hydroxylated derivatives of chlorophyll a and pheophytin a, produced during the ethanolic extraction, as well as previously described galactosyldiacylglycerols, the thylakoid coenzyme plastoquinone, and gracilamide B, a molecule previously reported in the red seaweed Gracillaria asiatica. These data point to UPLC-MSE as an efficient technique to identify phytoplankton pigments for which standards are available, and demonstrate its major interest as a complementary method for the structural elucidation of ionizable marine molecules. PMID:25913708

Residual Agar Determination in Bacterial Spores by Electrospray Ionization Mass Spectrometry

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

Wahl, Karen L.; Colburn, Heather A.; Wunschel, David S.

2010-02-15

Presented here is an analytical method to detect residual agar from a bacterial spore sample as an indication of culturing on an agar plate. This method is based on the resolubilization of agar polysaccharide from a bacterial spore sample, enzymatic digestion, followed by electrospray ionization tandem mass spectrometry (ESI-MSn) analysis for detection of a specific agar fragment ion. A range of Bacillus species and strains were selected to demonstrate the effectiveness of this approach. The characteristic agar fragment ion was detected in the spores grown on agar that were washed from 1 to 5 times, irradiated or non-irradiated and notmore » in the spores grown in broth. A sample containing approximately 108 spores is currently needed for confident detection of residual agar from culture on agar plates in the presence of bacterial spores with a limit of detection of approximately 1 ppm agar spiked into a broth-grown spore sample. The results of a proficiency test with 42 blinded samples are presented demonstrating the utility of this method with no false positives and only 3 false negatives for samples that were below the detection level of the method as documented.« less

Fast atom bombardment tandem mass spectrometry of carotenoids

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

van Breeman, R.B.; Schmitz, H.H.; Schwartz, S.J.

Positive ion fast atom bombardment (FAB) tandem mass spectrometry (MS-MS) using a double-focusing mass spectrometer with linked scanning at constant B/E and high-energy collisionally activated dissociation (CAD) was used to differentiate 17 different cartenoids, including {beta}-apo-8{prime}- carotenal, astaxanthin, {alpha}-carotene, {beta}-carotene, {gamma}-carotene, {zeta}-carotene, canthaxanthin, {beta}-cryptoxanthin, isozeaxanthin bis (pelargonate), neoxanthin, neurosporene, nonaprene, lutein, lycopene, phytoene, phytofluene, and zeaxanthin. The carotenoids were either synthetic or isolated from plant tissues. The use of FAB ionization minimized degradation or rearrangement of the carotenoid structures due to the inherent thermal instability generally ascribed to these compounds. Instead of protonated molecules, both polar xanthophylls and nonpolar carotenesmore » formed molecular ions, M{sup {center_dot}+}, during FAB ionization. Following collisionally activated dissociation, fragment ions of selected molecular ion precursors showed structural features indicative of the presence of hydroxyl groups, ring systems, ester groups, and aldehyde groups and the extent of aliphatic polyene conjugation. The fragmentation patterns observed in the mass spectra herein may be used as a reference for the structural determination of carotenoids isolated from plant and animal tissues. 18 refs., 4 figs.« less

A direct view by immunofluorescent comet assay (IFCA) of DNA damage induced by nicking and cutting enzymes, ionizing (137)Cs radiation, UV-A laser microbeam irradiation and the radiomimetic drug bleomycin.

PubMed

Grigaravicius, Paulius; Rapp, Alexander; Greulich, Karl Otto

2009-03-01

In DNA repair research, DNA damage is induced by different agents, depending on the technical facilities of the investigating researchers. A quantitative comparison of different investigations is therefore often difficult. By using a modified variant of the neutral comet assay, where the histone H1 is detected by immunofluorescence [immunofluorescent comet assay (IFCA)], we achieve previously unprecedented resolution in the detection of fragmented chromatin and show that trillions of ultraviolet A photons (of a few eV), billions of bleomycin (BLM) molecules and thousands of gamma quanta (of 662 keV) generate, in first order, similar damage in the chromatin of HeLa cells. A somewhat more detailed inspection shows that the damage caused by 20 Gy ionizing radiation and by a single laser pulse of 10 microJ are comparable, while the damage caused by 12 microg/ml BLM depends highly on the individual cell. Taken together, this work provides a detailed view of DNA fragmentation induced by different treatments and allows comparing them to some extent, especially with respect to the neutral comet assay.

Laser Desorption Postionization Mass Spectrometry of Antibiotic-Treated Bacterial Biofilms using Tunable Vacuum Ultraviolet Radiation

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

Gasper, Gerald L; Takahashi, Lynelle K; Zhou, Jia

2010-08-04

Laser desorption postionization mass spectrometry (LDPI-MS) with 8.0 ? 12.5 eV vacuum ultraviolet synchrotron radiation is used to single photon ionize antibiotics andextracellular neutrals that are laser desorbed both neat and from intact bacterial biofilms. Neat antibiotics are optimally detected using 10.5 eV LDPI-MS, but can be ionized using 8.0 eV radiation, in agreement with prior work using 7.87 eV LDPI-MS. Tunable vacuum ultraviolet radiation also postionizes laser desorbed neutrals of antibiotics and extracellular material from within intact bacterial biofilms. Different extracellular material is observed by LDPI-MS in response to rifampicin or trimethoprim antibiotic treatment. Once again, 10.5 eV LDPI-MSmore » displays the optimum trade-off between improved sensitivity and minimum fragmentation. Higher energy photons at 12.5 eV produce significant parent ion signal, but fragment intensity and other low mass ions are also enhanced. No matrix is added to enhance desorption, which is performed at peak power densities insufficient to directly produce ions, thus allowing observation of true VUV postionization mass spectra of antibiotic treated biofilms.« less

Characterization of alkaloids in Sophora flavescens Ait. by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry.

PubMed

Liu, Guoqiang; Dong, Jing; Wang, Hong; Hashi, Yuki; Chen, Shizhong

2011-04-05

Sophora flavescens Ait., a well-known Chinese herbal medicine, is widely used in clinical practice for the treatment of viral hepatitis, cancer, gastrointestinal hemorrhage, and skin diseases. This paper is the first report on a method based on the combined use of high-performance liquid chromatography, photodiode array detection, and electrospray ionization tandem mass spectrometry for the comprehensive and systematic separation and characterization of bioactive alkaloids in Sophora flavescens Ait. A total of 22 constituents were identified on the basis of the extracted ion chromatograms for different [M+H](+) ions of the alkaloids present in S. flavescens Ait. Among these, 5 constituents were unambiguously identified by comparing the experimental data on their retention times and MS(n) spectra with those of the authentic compounds, and 17 other constituents were tentatively identified on the basis of their MS(n) fragmentation behaviors and/or molecular weight information from literatures. Furthermore, some characteristic fragmentation pathways of the alkaloids in S. flavescens Ait. were detected and examined. This information may be useful for characterizing the bioactive alkaloids present in S. flavescens Ait. and for possible applications in formulations. Copyright © 2010 Elsevier B.V. All rights reserved.

Separation and identification of twelve catechins in tea using liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry.

PubMed

Zeeb, D J; Nelson, B C; Albert, K; Dalluge, J J

2000-10-15

A method has been developed for the direct microscale determination of 12 catechins in green and black tea infusions. The method is based on liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (LC/APCI-MS). Standard catechin mixtures and tea infusions were analyzed by LC/APCI-MS with detection of protonated molecular ions and characteristic fragment ions for each compound. The identities of eight major catechins and caffeine in tea were established based on LC retention times and simultaneously recorded mass spectra. In addition, monitoring of the catechin-specific retro Diels-Alder fragment ion at m/z 139 throughout the chromatogram provided a unique fingerprint for catechin content in the samples that led to the identification of four minor chemically modified catechin derivatives in the infusions. This report is the first to describe the comprehensive determination of all 12 reported catechins in a single analysis. The utility of LC/APCI-MS for providing routine separation and identification of catechins at femtomole to low-picomole levels without extraction or sample pretreatment, and its potential as a standard analytical tool for the determination of polyphenols in natural products and biological fluids, are discussed.

The coordination between mechanical and chemical subsystems initiates locomotion of Physarum plasmodial fragments

NASA Astrophysics Data System (ADS)

Zhang, Shun; Guy, Robert; Del Alamo, Juan Carlos

2017-11-01

Physarum polycephalum is a multinucleated slime mold whose endoplasm flows periodically driven by the contraction of its ectoplasm, a dense shell of F-actin cross-linked by myosin molecular motors and attached to the cell membrane. We find that physarum fragments smaller than 100 microns remain round and stay in place. However, larger fragments break symmetry leading to sustained forward locomotion, in process that is reminiscent of an interfacial instability that seems to settle around two different limit cycles (traveling waves and standing waves). We use both theory and experiments to study how coordination emerges between the different mechanical and chemical subsystems of the fragment to initiate locomotion. The role of many involved factors, such as fragment size, substratum adhesiveness, rheological properties, actin polymerization and traction stresses are investigated, and we find they agree well with our predictive model.

Luciferase assay to study the activity of a cloned promoter DNA fragment.

PubMed

Solberg, Nina; Krauss, Stefan

2013-01-01

Luciferase based assays have become an invaluable tool for the analysis of cloned promoter DNA fragments, both for verifying the ability of a potential promoter fragment to drive the expression of a luciferase reporter gene in various cellular contexts, and for dissecting binding elements in the promoter. Here, we describe the use of the Dual-Luciferase(®) Reporter Assay System created by Promega (Promega Corporation, Wisconsin, USA) to study the cloned 6.7 kilobases (kb) mouse (m) Tcf3 promoter DNA fragment in mouse embryonic derived neural stem cells (NSC). In this system, the expression of the firefly luciferase driven by the cloned mTcf3 promoter DNA fragment (including transcription initiation sites) is correlated with a co-transfected control reporter expressing Renilla luciferase from the herpes simplex virus (HSV) thymidine kinase promoter. Using an internal control reporter allows to normalize the activity of the experimental reporter to the internal control, which minimizes experimental variability.

Modeling nitrogen plasmas produced by intense electron beams

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

Angus, J. R.; Swanekamp, S. B.; Schumer, J. W.

2016-05-15

A new gas–chemistry model is presented to treat the breakdown of a nitrogen gas with pressures on the order of 1 Torr from intense electron beams with current densities on the order of 10 kA/cm{sup 2} and pulse durations on the order of 100 ns. For these parameter regimes, the gas transitions from a weakly ionized molecular state to a strongly ionized atomic state on the time scale of the beam pulse. The model is coupled to a 0D–circuit model using the rigid–beam approximation that can be driven by specifying the time and spatial profiles of the beam pulse. Simulation results are inmore » good agreement with experimental measurements of the line–integrated electron density from experiments done using the Gamble II generator at the Naval Research Laboratory. It is found that the species are mostly in the ground and metastable states during the atomic phase, but that ionization proceeds predominantly through thermal ionization of optically allowed states with excitation energies close to the ionization limit.« less

Observation of ionization enhancement in two-color circularly polarized laser fields

NASA Astrophysics Data System (ADS)

Mancuso, Christopher A.; Dorney, Kevin M.; Hickstein, Daniel D.; Chaloupka, Jan L.; Tong, Xiao-Min; Ellis, Jennifer L.; Kapteyn, Henry C.; Murnane, Margaret M.

2017-08-01

When atoms are irradiated by two-color circularly polarized laser fields the resulting strong-field processes are dramatically different than when the same atoms are irradiated by a single-color ultrafast laser. For example, electrons can be driven in complex two-dimensional trajectories before rescattering or circularly polarized high harmonics can be generated, which was once thought impossible. Here, we show that two-color circularly polarized lasers also enable control over the ionization process itself and make a surprising finding: the ionization rate can be enhanced by up to 700 % simply by switching the relative helicity of the two-color circularly polarized laser field. This enhancement is experimentally observed in helium, argon, and krypton over a wide range of intensity ratios of the two-color field. We use a combination of advanced quantum and fully classical calculations to explain this ionization enhancement as resulting in part due to the increased density of excited states available for resonance-enhanced ionization in counter-rotating fields compared with co-rotating fields. In the future, this effect could be used to probe the excited state manifold of complex molecules.

The use of nanomaterials for mass spectrometry can be uplifting for analyte detection

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

Li, J.; Lipson, R. H.

2014-03-31

Surface-Assisted Laser Desorption Ionization (SALDI) involves desorbing and ionizing analyte molecules from a nanoporous substrate by laser irradiation for detection in a mass spectrometer. In this work experiments were designed to better understand the mechanisms governing desorption and ionization for Desorption Ionization On Silicon (DIOS), a variant of SALDI which uses porous silicon (pSi) as a substrate. Experiments are also reported for other nanoporous semiconducting materials (WO{sub 3}, TiO{sub 2}) which exhibit very similar behaviors; specifically, that both protonated analyte ions and analyte radical cations can be generated with relative intensities that depend on the position of the incident lasermore » focus relative to substrate surface. While thermal desorption appears to be important, preliminary evidence suggests that the ionization mechanism leading to protonated analytes involves in part electrons and holes formed when photoexciting the substrate above its electronic band gap, and the presence of defect states within the band gap. Radical cation formation appears to be driven in part by electron transfer due to the large electron affinity of each substrate used in this work.« less

Detection, characterization and identification of phenolic acids in Danshen using high-performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry.

PubMed

Liu, Ai-Hua; Guo, Hui; Ye, Min; Lin, Yan-Hua; Sun, Jiang-Hao; Xu, Man; Guo, De-An

2007-08-17

By using HPLC-diode array detection-electrospray ion trap tandem mass spectrometry (HPLC-DAD-ESI-MS(n)) in negative ion mode, we have analyzed the fragmentation pathways of 11 phenolic acids which were isolated from Danshen. Then the extract of Danshen was analyzed, and a total of 42 phenolic acids, including sixteen new minor constituents, were identified or tentatively identified for the first time. A new solid-phase extraction (SPE) method, new HPLC separation method, new liquid chromatography (LC)-MS and LC-MS(n) (n=3-5) data and proposed fragmentation pathways, LC retention time for phenolic acids are reported.

Simultaneous 3D coincidence imaging of cationic, anionic, and neutral photo-fragments

NASA Astrophysics Data System (ADS)

Shahi, Abhishek; Albeck, Yishai; Strasser, Daniel

2018-01-01

We present the design and simulations of a 3D coincidence imaging spectrometer for fast beam photofragmentation experiments. Coincidence detection of cationic, neutral, and anionic fragments involves spectrometer aberrations that are successfully corrected by an analytical model combined with exact numerical simulations. The spectrometer performance is experimentally demonstrated by characterization of four different channels of intense 800 nm pulse interaction with F2-: F- + F photodissociation, F + F dissociative photodetachment, F+ + F dissociative ionization, and F+ + F+ coulomb explosion. Improved measurement of F2- photodissociation with a 400 nm photon allows a better determination of the F2- anion dissociation energy, 1.256 ± 0.005 eV.

Electron distribution function in a plasma generated by fission fragments

NASA Technical Reports Server (NTRS)

Hassan, H. A.; Deese, J. E.

1976-01-01

A Boltzmann equation formulation is presented for the determination of the electron distribution function in a plasma generated by fission fragments. The formulation takes into consideration ambipolar diffusion, elastic and inelastic collisions, recombination and ionization, and allows for the fact that the primary electrons are not monoenergetic. Calculations for He in a tube coated with fissionable material shows that, over a wide pressure and neutron flux range, the distribution function is non-Maxwellian, but the electrons are essentially thermal. Moreover, about a third of the energy of the primary electrons is transferred into the inelastic levels of He. This fraction of energy transfer is almost independent of pressure and neutron flux.

Pump-Probe Fragmentation Action Spectroscopy: A Powerful Tool to Unravel Light-Induced Processes in Molecular Photocatalysts.

PubMed

Imanbaew, Dimitri; Lang, Johannes; Gelin, Maxim F; Kaufhold, Simon; Pfeffer, Michael G; Rau, Sven; Riehn, Christoph

2017-05-08

We present a proof of concept that ultrafast dynamics combined with photochemical stability information of molecular photocatalysts can be acquired by electrospray ionization mass spectrometry combined with time-resolved femtosecond laser spectroscopy in an ion trap. This pump-probe "fragmentation action spectroscopy" gives straightforward access to information that usually requires high purity compounds and great experimental efforts. Results of gas-phase studies on the electronic dynamics of two supramolecular photocatalysts compare well to previous findings in solution and give further evidence for a directed electron transfer, a key process for photocatalytic hydrogen generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational Prediction of Electron Ionization Mass Spectra to Assist in GC/MS Compound Identification.

PubMed

Allen, Felicity; Pon, Allison; Greiner, Russ; Wishart, David

2016-08-02

We describe a tool, competitive fragmentation modeling for electron ionization (CFM-EI) that, given a chemical structure (e.g., in SMILES or InChI format), computationally predicts an electron ionization mass spectrum (EI-MS) (i.e., the type of mass spectrum commonly generated by gas chromatography mass spectrometry). The predicted spectra produced by this tool can be used for putative compound identification, complementing measured spectra in reference databases by expanding the range of compounds able to be considered when availability of measured spectra is limited. The tool extends CFM-ESI, a recently developed method for computational prediction of electrospray tandem mass spectra (ESI-MS/MS), but unlike CFM-ESI, CFM-EI can handle odd-electron ions and isotopes and incorporates an artificial neural network. Tests on EI-MS data from the NIST database demonstrate that CFM-EI is able to model fragmentation likelihoods in low-resolution EI-MS data, producing predicted spectra whose dot product scores are significantly better than full enumeration "bar-code" spectra. CFM-EI also outperformed previously reported results for MetFrag, MOLGEN-MS, and Mass Frontier on one compound identification task. It also outperformed MetFrag in a range of other compound identification tasks involving a much larger data set, containing both derivatized and nonderivatized compounds. While replicate EI-MS measurements of chemical standards are still a more accurate point of comparison, CFM-EI's predictions provide a much-needed alternative when no reference standard is available for measurement. CFM-EI is available at https://sourceforge.net/projects/cfm-id/ for download and http://cfmid.wishartlab.com as a web service.

Structural characterization of saturated branched chain fatty acid methyl esters by collisional dissociation of molecular ions generated by electron ionization[S

PubMed Central

Ran-Ressler, Rinat R.; Lawrence, Peter; Brenna, J. Thomas

2012-01-01

Saturated branched chain fatty acids (BCFA) are present as complex mixtures in numerous biological samples. The traditional method for structure elucidation, electron ionization (EI) mass spectrometry, sometimes does not unambiguously enable assignment of branching in isomeric BCFA. Zirrolli and Murphy (Zirrolli , J. A. , and R. A. Murphy. 1993. Low-energy tandem mass spectrometry of the molecular ion derived from fatty acid methyl esters: a novel method for analysis of branched-chain fatty acids. J. Am. Soc. Mass Spectrom. 4: 223–229.) showed that the molecular ions of four BCFA methyl ester (BCFAME) yield highly characteristic fragments upon collisional dissociation using a triple quadrupole instrument. Here, we confirm and extend these results by analysis using a tabletop 3-D ion trap for activated molecular ion EI-MS/MS to 30 BCFAME. iso-BCFAME produces a prominent ion (30-100% of base peak) for [M-43] (M-C3H7), corresponding to the terminal isopropyl moiety in the original iso-BCFAME. Anteiso-FAME yield prominent ions (20-100% of base peak) corresponding to losses on both side of the methyl branch, [M-29] and [M-57], and tend to produce more prominent m/z 115 peaks corresponding to a cyclization product around the ester. Dimethyl and tetramethyl FAME, with branches separated by at least one methylene group, yield fragment on both sides of the sites of methyl branches that are more than 6 C away from the carboxyl carbon. EI-MS/MS yields uniquely specific ions that enable highly confident structural identification and quantification of BCFAME. PMID:22021637

Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations

NASA Astrophysics Data System (ADS)

Grossert, J. Stuart; Herrera, Lisandra Cubero; Ramaley, Louis; Melanson, Jeremy E.

2014-08-01

Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

Chemical imaging of latent fingerprints by mass spectrometry based on laser activated electron tunneling.

PubMed

Tang, Xuemei; Huang, Lulu; Zhang, Wenyang; Zhong, Hongying

2015-03-03

Identification of endogenous and exogenous chemicals contained in latent fingerprints is important for forensic science in order to acquire evidence of criminal identities and contacts with specific chemicals. Mass spectrometry has emerged as a powerful technique for such applications without any derivatization or fluorescent tags. Among these techniques, MALDI (Matrix Assisted Laser Desorption Ionization) provides small beam size but has interferences with MALDI matrix materials, which cause ion suppressions as well as limited spatial resolution resulting from uneven distribution of MALDI matrix crystals with different sizes. LAET (Laser Activated Electron Tunneling) described in this work offers capabilities for chemical imaging through electron-directed soft ionization. A special film of semiconductors has been designed for collection of fingerprints. Nanoparticles of bismuth cobalt zinc oxide were compressed on a conductive metal substrate (Al or Cu sticky tape) under 10 MPa pressure. Resultant uniform thin films provide tight and shining surfaces on which fingers are impressed. Irradiation of ultraviolet laser pulses (355 nm) on the thin film instantly generates photoelectrons that can be captured by adsorbed organic molecules and subsequently cause electron-directed ionization and fragmentation. Imaging of latent fingerprints is achieved by visualization of the spatial distribution of these molecular ions and structural information-rich fragment ions. Atomic electron emission together with finely tuned laser beam size improve spatial resolution. With the LAET technique, imaging analysis not only can identify physical shapes but also reveal endogenous metabolites present in females and males, detect contacts with prohibited substances, and resolve overlapped latent fingerprints.

Characterization of Hypervelocity Metal Fragments for Explosive Initiation

NASA Astrophysics Data System (ADS)

Yeager, John; Bowden, Patrick; Guildenbecher, Daniel; Olles, Joseph

2017-06-01

The off-normal detonation behavior of two plastic-bonded explosive (PBX) formulations was studied using explosively-driven aluminum fragments moving at hypersonic velocity. Witness plate materials, including copper and polycarbonate, were used to characterize the distribution of particles, finding that the aluminum did not fragment homogeneously but rather with larger particles in a ring surrounding finer particles. Digital holography experiments were conducted to measure three-dimensional shape and size of the fastest-moving fragments, which ranged between 100 and 700 microns and traveled between 2 and 3.5 km/s. Crucially, these experiments showed variability in the fragmentation in terms of the number of fragments at the leading edge of the fragment field, indicating that both single and multiple shock impacts could be imparted to the target material. Lower density PBX 9407 (RDX-based) was initiable at up to 4.5 inches, while higher density PBX 9501 (HMX-based) was only initiable at up to 0.25 inches. This type of data is critical for safety experiments and hydrocode simulations to quantify shock-to-detonation transition mechanisms and the associated risk-margins for these materials.

Monitoring the Gas Composition of the NIFFTE Time Projection Chamber

NASA Astrophysics Data System (ADS)

Towell, Travis; Travis Towell Collaboration

2017-09-01

The Neutron Induced Fission Fragment Tracking Experiment (NIFFTE) at Los Alamos National Laboratory(LANL) is using a Time Projection Chamber (TPC) to measure with high precision the cross section ratio of U238 to P239. When the neutron beam hits a target, it may emit fission fragments. As the fission fragments travels through the chamber, it ionizes the gas it passes through. Based on the time it takes for the ions to drift to the pad planes and the hit location of the ions, the path of fission fragments can be determined. Knowing the composition of the gas mixture is vital to accurately reconstruct the data. A Binary Gas Analyzer (BGA) is used to measure the gas composition. To confirm the accuracy of the BGA, varying amounts of nitrogen and carbon dioxide were flowed through a test gas system. Several tests were performed to validate that the BGA for our gas system is working properly. This poster will describe the test gas system setup, tests of the BGA, and elaborate on the main goals of the NIFFTE experiment.

Dissociative photoionization of isoprene: experiments and calculations.

PubMed

Liu, Xianyun; Zhang, Weijun; Wang, Zhenya; Huang, Mingqiang; Yang, Xibin; Tao, Ling; Sun, Yue; Xu, Yuntao; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi

2009-03-01

Vacuum ultraviolet (VUV) dissociative photoionization of isoprene in the energy region 8.5-18 eV was investigated with photoionization mass spectroscopy (PIMS) using synchrotron radiation (SR). The ionization energy (IE) of isoprene as well as the appearance energies (AEs) of its fragment ions C(5)H(7) (+), C(5)H(5) (+), C(4)H(5) (+), C(3)H(6) (+), C(3)H(5) (+), C(3)H(4) (+), C(3)H(3) (+) and C(2)H(3) (+) were determined with photoionization efficiency (PIE) curves. The dissociation energies of some possible dissociation channels to produce those fragment ions were also determined experimentally. The total energies of C(5)H(8) and its main fragments were calculated using the Gaussian 03 program and the Gaussian-2 method. The IE of C(5)H(8), the AEs for its fragment ions, and the dissociation energies to produce them were predicted using the high-accuracy energy model. According to our results, the experimental dissociation energies were in reasonable agreement with the calculated values of the proposed photodissociation channels of C(5)H(8). Copyright (c) 2009 John Wiley & Sons, Ltd.

Electrostatic field of the large fragment of Escherichia coli DNA polymerase I.

PubMed

Warwicker, J; Ollis, D; Richards, F M; Steitz, T A

1985-12-05

The electrostatic field of the large fragment of Escherichia coli DNA polymerase I (Klenow fragment) has been calculated by the finite difference procedure on a 2 A grid. The potential field is substantially negative at physiological pH (reflecting the net negative charge at this pH). The largest regions of positive potential are in the deep crevice of the C-terminal domain, which is the proposed binding site for the DNA substrate. Within the crevice, the electrostatic potential has a partly helical form. If the DNA is positioned to fulfil stereochemical requirements, then the positive potential generally follows the major groove and (to a lesser extent) the negative potential is in the minor groove. Such an arrangement could stabilize DNA configurations related by screw symmetry. The histidine residues of the Klenow fragment give the positive field of the groove a sensitivity to relatively small pH changes around neutrality. We suggest that the histidine residues could change their ionization states in response to DNA binding, and that this effect could contribute to the protein-DNA binding energy.

Potential for the Vishniac instability in ionizing shock waves propagating into cold gases

NASA Astrophysics Data System (ADS)

Robinson, A. P. L.; Pasley, J.

2018-05-01

The Vishniac instability was posited as an instability that could affect supernova remnants in their late stage of evolution when subject to strong radiative cooling, which can drive the effective ratio of specific heats below 1.3. The potential importance of this instability to these astrophysical objects has motivated a number of laser-driven laboratory studies. However, the Vishniac instability is essentially a dynamical instability that should operate independently of whatever physical processes happen to reduce the ratio of specific heats. In this paper, we examine the possibility that ionization and molecular dissociation processes can achieve this, and we show that this is possible for a certain range of shock wave Mach numbers for ionizing/dissociating shock waves propagating into cold atomic and molecular gases.

Identification of cardiac glycosides in fractions from Periploca forrestii by high-performance liquid chromatography/diode-array detection/electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/nuclear magnetic resonance.

PubMed

Li, Yong; Wu, Xianfu; Li, Jianbei; Wang, Yinghong; Yu, Shishan; Lv, Haining; Qu, Jing; Abliz, Zeper; Liu, Jing; Liu, Yuanyan; Du, Dan

2010-02-01

Cardiac glycosides are a class of naturally occurring compounds that are characterized by some interesting biological activities and are widely distributed in the plant kingdom and can also be found in some animals. There is an interest in the chemical characterization of these molecules due to their toxicity and their use in medicines. In the study reported here, a combination of electrospray ionization tandem mass spectrometry with high-performance liquid chromatography equipped with diode-array detector (HPLC-DAD/ESI-MS(n)), and hyphenation to both liquid chromatography and nuclear magnetic resonance spectroscopy (HPLC/NMR) were utilized for the on-line analyses of cardiac glycosides from Periploca forrestii. The fragmentation patterns and (1)H NMR spectra of nine isolated cardiac glycosides were investigated; their fragmentation rules and (1)H NMR spectral characteristics were summarized and applied to the structural identification of similar constituents in fractions from P. forrestii. As a result, a total of nine trace cardiac glycosides were tentatively determined by analyses of accurate molecular masses, representative fragment ions and characteristic (1)H NMR signals provided by HPLC/high-resolution mass spectrometry (HRMS), HPLC-DAD/ESI-MS(n) and HPLC/(1)H NMR experiments, respectively. Of these, eight (2-9) are new compounds and one (1) is reported from P. forrestii for the first time. Results of the present study can benefit the rapid identification and targeted isolation of new cardiac glycosides from crude plant extracts. 2009 Elsevier B.V. All rights reserved.

The influence of data-driven versus conceptually-driven processing on the development of PTSD-like symptoms.

PubMed

Kindt, Merel; van den Hout, Marcel; Arntz, Arnoud; Drost, Jolijn

2008-12-01

Ehlers and Clark [(2000). A cognitive model of posttraumatic stress disorder. Behaviour Research and Therapy, 38, 319-345] propose that a predominance of data-driven processing during the trauma predicts subsequent PTSD. We wondered whether, apart from data-driven encoding, sustained data-driven processing after the trauma is also crucial for the development of PTSD. Both hypotheses were tested in two analogue experiments. Experiment 1 demonstrated that relative to conceptually-driven processing (n=20), data-driven processing after the film (n=14), resulted in more intrusions. Experiment 2 demonstrated that relative to the neutral condition (n=24) and the data-driven encoding condition (n=24), conceptual encoding (n=25) reduced suppression of intrusions and a trend emerged for memory fragmentation. The difference between the two encoding styles was due to the beneficial effect of induced conceptual encoding and not to the detrimental effect of data-driven encoding. The data support the viability of the distinction between data-driven/conceptually-driven processing for the understanding of the development of PTSD.

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

DOE PAGES

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; ...

2016-04-05

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

UNRAVELLING THE COMPLEX STRUCTURE OF AGN-DRIVEN OUTFLOWS. II. PHOTOIONIZATION AND ENERGETICS

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

Karouzos, Marios; Woo, Jong-Hak; Bae, Hyun-Jin, E-mail: woo@astro.snu.ac.kr

2016-12-20

Outflows have been shown to be prevalent in galaxies hosting luminous active galactic nuclei (AGNs); they present a physically plausible way to couple the AGN energy output with the interstellar medium of their hosts. Despite their prevalence, accurate characterization of these outflows has been challenging. In the second of a series of papers, we use Gemini Multi-Object Spectrograph integral field unit (IFU) data of six local ( z  < 0.1) and moderate-luminosity Type 2 AGNs to study the ionization properties and energetics of AGN-driven outflows. We find strong evidence connecting the extreme kinematics of the ionized gas to the AGN photoionization.more » The kinematic component related to the AGN-driven outflow is clearly separated from other kinematic components, such as virial motions or rotation, on the velocity and velocity dispersion diagram. Our spatially resolved kinematic analysis reveals that 30 to 90% of the total mass and kinetic energy of the outflow is contained within the central kpc of the galaxy. The spatially integrated mass and kinetic energy of the gas entrained in the outflow correlate well with the AGN bolometric luminosity and results in energy conversion efficiencies between 0.01% and 1%. Intriguingly, we detect ubiquitous signs of ongoing circumnuclear star formation. Their small size, the centrally contained mass and energy, and the universally detected circumnuclear star formation cast doubts on the potency of these AGN-driven outflows as agents of galaxy-scale negative feedback.« less

Computational modeling of electrically-driven deposition of ionized polydisperse particulate powder mixtures in advanced manufacturing processes

NASA Astrophysics Data System (ADS)

Zohdi, T. I.

2017-07-01

A key part of emerging advanced additive manufacturing methods is the deposition of specialized particulate mixtures of materials on substrates. For example, in many cases these materials are polydisperse powder mixtures whereby one set of particles is chosen with the objective to electrically, thermally or mechanically functionalize the overall mixture material and another set of finer-scale particles serves as an interstitial filler/binder. Often, achieving controllable, precise, deposition is difficult or impossible using mechanical means alone. It is for this reason that electromagnetically-driven methods are being pursued in industry, whereby the particles are ionized and an electromagnetic field is used to guide them into place. The goal of this work is to develop a model and simulation framework to investigate the behavior of a deposition as a function of an applied electric field. The approach develops a modular discrete-element type method for the simulation of the particle dynamics, which provides researchers with a framework to construct computational tools for this growing industry.

Desorption Electrospray Ionization Mass Spectrometry (DESI-MS) Analysis of Organophosphorus Chemical Warfare Agents: Rapid Acquisition of Time-Aligned Parallel (TAP) Fragmentation Data

DTIC Science & Technology

2010-06-01

phase microextraction. Anal. Chem., 69, 1866-72. [39] Sng , M.T. and Ng ,W.F. (1999). In-situ derivatisation of degradation products of chemical warfare...Chromatogr. A., 1141, 151-157. [46] Lee, H.S.N., Sng , M.T., Basheer, C., and Lee, H.K. (2007). Determination of degradation products of chemical

Reactions of solvated electrons initiated by sodium atom ionization at the vacuum-liquid interface.

PubMed

Alexander, William A; Wiens, Justin P; Minton, Timothy K; Nathanson, Gilbert M

2012-03-02

Solvated electrons are powerful reagents in the liquid phase that break chemical bonds and thereby create additional reactive species, including hydrogen atoms. We explored the distinct chemistry that ensues when electrons are liberated near the liquid surface rather than within the bulk. Specifically, we detected the products resulting from exposure of liquid glycerol to a beam of sodium atoms. The Na atoms ionized in the surface region, generating electrons that reacted with deuterated glycerol, C(3)D(5)(OD)(3), to produce D atoms, D(2), D(2)O, and glycerol fragments. Surprisingly, 43 ± 4% of the D atoms traversed the interfacial region and desorbed into vacuum before attacking C-D bonds to produce D(2).

Application of GC/MS Soft Ionization for Isomeric Biological Compound Analysis.

PubMed

Furuhashi, Takeshi; Okuda, Koji

2017-09-03

Isomers are compounds with the same molecular formula. Many different types of isomers are ubiquitous and play important roles in living organisms. Despite their early discovery, the actual analysis of isomers has been tricky and has confounded researchers. Using mass spectrometry (MS) to distinguish or identify isomers is an emergent topic and challenge for analytical chemists. We review some techniques for analyzing isomers with emphasis on MS, e.g., the roles of ion reaction, hydrogen-deuterium exchange, ion mobility mass spectrometry, ion spectroscopy, and energy change in producing isomer-specific fragments. In particular, soft ionization for gas chromatography-mass spectrometry (GC-MS) is a focus in this review. Awareness of the advantages and technical problems of these techniques would inspire innovation in future approaches.

Prompt and delayed Coulomb explosion of doubly ionized hydrogen chloride molecules in intense femtosecond laser fields

NASA Astrophysics Data System (ADS)

Ma, Junyang; Li, Hui; Lin, Kang; Song, Qiying; Ji, Qinying; Zhang, Wenbin; Li, Hanxiao; Sun, Fenghao; Qiang, Junjie; Lu, Peifen; Gong, Xiaochun; Zeng, Heping; Wu, Jian

2018-06-01

We experimentally investigate the dissociative double ionization of hydrogen chloride (HCl) molecules in intense femtosecond laser pulses. In addition to the prompt dissociation channels which occur on femtosecond timescales, long-lived hydrogen chloride dications which Coulomb-explode in flight towards the detector are clearly identified in the photoion-photoion coincidence spectrum. Different pathways leading to these prompt and delayed dissociation channels involving various bound and repulsive states of the HCl dication are discussed based on the observed kinetic energy release and momentum distributions. Our results indicate that the specific features of the HCl dication potential energy curves are responsible for the generation of the delayed fragmentation channels, which are expected to be general processes for the hydrogen halides.

Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

NASA Astrophysics Data System (ADS)

Bannan, T.; Booth, M.; Benyezzar, M.; Bacak, A.; Alfarra, M. R. R.; Topping, D. O.; Percival, C.

2015-12-01

Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

Application of Lithium Attachment Mass Spectrometry for Knudsen Evaporation and Chemical Ionisation Mass Spectrometry (KEMS, CIMS)

NASA Astrophysics Data System (ADS)

Bannan, Thomas; Booth, A. Murray; Alfarra, Rami; Bacak, Asan; Pericval, Carl

2016-04-01

Lithium ion attachment mass spectrometry provides a non-specific, non-fragmenting and sensitive method for detection of volatile species in the gas phase. The design, manufacture, and results from lithium ion attachment ionisation sources for two mass spectrometry systems are presented. Trace gas analysis is investigated using a modified Chemical Ionization Mass Spectrometer (CIMS) and vapour pressure (VP) measurements using a modified Knudsen Effusion Mass Spectrometer (KEMS) are presented. The Li+ modified CIMS provided limits of detection of 4 ppt for acetone, 0.2 ppt for formic acid, 15 ppt for nitric acid and 120 ppt from ammonia. Despite improvements, the problem of burnout remained persistent. The Li+ CIMS would unlikely be suitable for field or aircraft work, but could be appropriate for certain lab applications. The KEMS currently utilizes an electron impact (EI) ionisation source which provides a highly sensitive source, with the drawback of fragmentation of ionized molecules (Booth et al., 2009). Using Li+ KEMS the VP of samples can be measured without fragmentation and can therefore be used to identify VPs of individual components in mixtures. The validity of using Li+ for determining the VP of mixtures was tested by making single component VP measurements, which showed good agreement with EI measurements of Poly ethylene glycol (PEG) 3 and PEG 4, both when individually measured and when mixed. The Li+ KEMS was then used to investigate a system of atmospheric relevance, α-pinene secondary organic aerosol, generated in a reaction chamber (Alfarra et al., 2012). The VPs of the individual components from this generated sample are within the range we expect for compounds capable of partitioning between the particle and gas phase of an aerosol (0.1-10-5 Pa). Li+ source has a calculated sensitivity approximately 75 times less than that of EI, but the lack of fragmentation using the Li+ source is a significant advantage.

5-Nitrosalicylic Acid as a Novel Matrix for In-Source Decay in Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

PubMed Central

Asakawa, Daiki

2013-01-01

The matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) of peptides and glycans was studied using an oxidizing chemical, 5-nitrosalicylic acid (5-NSA) as the matrix. The use of 5-NSA for the MALDI-ISD of peptides and glycans promoted fragmentation pathways involving “hydrogen-deficient” radical precursors. Hydrogen abstraction from peptides resulted in the production of a “hydrogen-deficient” peptide radical that contained a radical site on the amide nitrogen in the peptide backbone with subsequent radical-induced cleavage at the Cα–C bonds. Cleavage at the Cα–C bond leads to the production of an a•/x fragment pair and the radical a• ions then undergo further hydrogen abstraction to form a ions after Cα–C bond cleavage. Since the Pro residue does not contain a nitrogen-centered radical site, Cα–C bond cleavage does not occur at this site. Alternatively, the specific cleavage of CO−N bonds leads to a b•/y fragment pair at Xxx−Pro which occurs via hydrogen abstraction from the Cα−H in the Pro residue. In contrast, “hydrogen-deficient” glycan radicals were generated by hydrogen abstraction from hydroxyl groups in glycans. Both glycosidic and cross-ring cleavages occurred as the result of the degradation of “hydrogen-deficient” glycan radicals. Cross-ring cleavage ions are potentially useful in linkage analysis, one of the most critical steps in the characterization of glycans. Moreover, isobaric glycans could be distinguished by structure specific ISD ions, and the molar ratio of glycan isomers in a mixture can be estimated from their fragment ions abundance ratios. MALDI-ISD with 5-NSA could be a useful method for the sequencing of peptides including the location of post-translational modifications, identification and semi-quantitative analysis of mixtures of glycan isomers. PMID:24860709

How enhanced molecular ions in Cold EI improve compound identification by the NIST library.

PubMed

Alon, Tal; Amirav, Aviv

2015-12-15

Library-based compound identification with electron ionization (EI) mass spectrometry (MS) is a well-established identification method which provides the names and structures of sample compounds up to the isomer level. The library (such as NIST) search algorithm compares different EI mass spectra in the library's database with the measured EI mass spectrum, assigning each of them a similarity score called 'Match' and an overall identification probability. Cold EI, electron ionization of vibrationally cold molecules in supersonic molecular beams, provides mass spectra with all the standard EI fragment ions combined with enhanced Molecular Ions and high-mass fragments. As a result, Cold EI mass spectra differ from those provided by standard EI and tend to yield lower matching scores. However, in most cases, library identification actually improves with Cold EI, as library identification probabilities for the correct library mass spectra increase, despite the lower matching factors. This research examined the way that enhanced molecular ion abundances affect library identification probability and the way that Cold EI mass spectra, which include enhanced molecular ions and high-mass fragment ions, typically improve library identification results. It involved several computer simulations, which incrementally modified the relative abundances of the various ions and analyzed the resulting mass spectra. The simulation results support previous measurements, showing that while enhanced molecular ion and high-mass fragment ions lower the matching factor of the correct library compound, the matching factors of the incorrect library candidates are lowered even more, resulting in a rise in the identification probability for the correct compound. This behavior which was previously observed by analyzing Cold EI mass spectra can be explained by the fact that high-mass ions, and especially the molecular ion, characterize a compound more than low-mass ions and therefore carries more weight in library search identification algorithms. These ions are uniquely abundant in Cold EI, which therefore enables enhanced compound characterization along with improved NIST library based identification. Copyright © 2015 John Wiley & Sons, Ltd.

Mass spectrometry analysis of etch products from CR-39 plastic irradiated by heavy ions

NASA Astrophysics Data System (ADS)

Kodaira, S.; Nanjo, D.; Kawashima, H.; Yasuda, N.; Konishi, T.; Kurano, M.; Kitamura, H.; Uchihori, Y.; Naka, S.; Ota, S.; Ideguchi, Y.; Hasebe, N.; Mori, Y.; Yamauchi, T.

2012-09-01

As a feasibility study, gas chromatography-mass spectrometry (GC-MS) and matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) have been applied to analyze etch products of CR-39 plastic (one of the most frequently used solid states nuclear track detector) for the understanding of track formation and etching mechanisms by heavy ion irradiation. The etch products of irradiated CR-39 dissolved in sodium hydroxide solution (NaOH) contain radiation-induced fragments. For the GC-MS analysis, we found peaks of diethylene glycol (DEG) and a small but a definitive peak of ethylene glycol (EG) in the etch products from CR-39 irradiated by 60 MeV N ion beams. The etch products of unirradiated CR-39 showed a clear peak of DEG, but no other significant peaks were found. DEG is known to be released from the CR-39 molecule as a fragment by alkaline hydrolysis reaction of the polymer. We postulate that EG was formed as a result of the breaking of the ether bond (C-O-C) of the DEG part of the CR-39 polymer by the irradiation. The mass distribution of polyallylalcohol was obtained from the etch products from irradiated and unirradiated CR-39 samples by MALDI-MS analysis. Polyallylalcohol, with the repeating mass interval of m/z = 58 Da (dalton) between m/z = 800 and 3500, was expected to be produced from CR-39 by alkaline hydrolysis. We used IAA as a matrix to assist the ionization of organic analyte in MALDI-MS analysis and found that peaks from IAA covered mass spectrum in the lower m/z region making difficult to identify CR-39 fragment peaks which were also be seen in the same region. The mass spectrometry analysis using GC-MS and MALDI-MS will be powerful tools to investigate the radiation-induced polymeric fragments and helping to understand the track formation mechanism in CR-39 by heavy ions.

Photodissociation of anisole and absolute photoionization cross-section of the phenoxy radical.

PubMed

Xu, Hong; Pratt, S T

2013-11-21

We have studied the photodissociation dynamics of anisole (C6H5OCH3) at 193 nm and determined the absolute photoionization cross-section of the phenoxy radical at 118.2 nm (10.486 eV) relative to the known cross-section of the methyl radical. Even at this energy, there is extensive fragmentation of the phenoxy radical upon photoionization, which is attributed to ionizing transitions that populate low-lying excited electronic states of the cation. For phenoxy radicals with less than ∼1 eV of internal energy, we find a cross-section for the production of the phenoxy cation of 14.8 ± 3.8 Mb. For radicals with higher internal energy, dissociative ionization is the dominant process, and for internal energies of ∼2.7-3.7 eV, we find a total cross-section (photoionization plus dissociative ionization) of 22.3 ± 4.1 Mb. The results are discussed relative to the recently reported photoionization cross-section of phenol.

Importance of projectile-target interactions in the triple differential cross sections for Low energy (e,2e) ionization of aligned H2

NASA Astrophysics Data System (ADS)

Ali, Esam; Madison, Don; Ren, X.; Dorn, A.; Ning, Chuangang

2014-10-01

Experimental and theoretical Triple Differential Cross Sections (TDCS) are presented for electron impact ionization-excitation of the 2 sσg state of H2 in the perpendicular plane. The excited 2 sσg state immediately dissociates and the alignment of the molecule is determined by detecting one of the fragments. Results are presented for three different alignments in the xy-plane (scattering plane is xz)-alignment along y-axis, x-axis, and 45° between the x- and y-axes for incident electron energies of 4, 10, and 25 eV and different scattered electron angles of 20° and 30° in the perpendicular plane. Theoretical M4DW (molecular 4-body distorted wave) results are compared to experimental data, and overall we found reasonably good agreement between experiment and theory. The Results show that (e,2e) cross sections for excitation-ionization depend strongly on the orientation of the H2 molecule.

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

PubMed

Chen, G; Wong, P; Cooks, R G

1997-09-01

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.