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Sample records for mass fragment ions

  1. Differentiating Fragmentation Pathways of Cholesterol by Two-Dimensional Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

    Science.gov (United States)

    van Agthoven, Maria A; Barrow, Mark P; Chiron, Lionel; Coutouly, Marie-Aude; Kilgour, David; Wootton, Christopher A; Wei, Juan; Soulby, Andrew; Delsuc, Marc-André; Rolando, Christian; O'Connor, Peter B

    2015-12-01

    Two-dimensional Fourier transform ion cyclotron resonance mass spectrometry is a data-independent analytical method that records the fragmentation patterns of all the compounds in a sample. This study shows the implementation of atmospheric pressure photoionization with two-dimensional (2D) Fourier transform ion cyclotron resonance mass spectrometry. In the resulting 2D mass spectrum, the fragmentation patterns of the radical and protonated species from cholesterol are differentiated. This study shows the use of fragment ion lines, precursor ion lines, and neutral loss lines in the 2D mass spectrum to determine fragmentation mechanisms of known compounds and to gain information on unknown ion species in the spectrum. In concert with high resolution mass spectrometry, 2D Fourier transform ion cyclotron resonance mass spectrometry can be a useful tool for the structural analysis of small molecules. Graphical Abstract ᅟ.

  2. Proposal for a common nomenclature for fragment ions in mass spectra of lipids

    DEFF Research Database (Denmark)

    Pauling, Josch K; Hermansson, Martin; Hartler, Jürgen

    2017-01-01

    Advances in mass spectrometry-based lipidomics have in recent years prompted efforts to standardize the annotation of the vast number of lipid molecules that can be detected in biological systems. These efforts have focused on cataloguing, naming and drawing chemical structures of intact lipid...... molecules, but have provided no guidelines for annotation of lipid fragment ions detected using tandem and multi-stage mass spectrometry, albeit these fragment ions are mandatory for structural elucidation and high confidence lipid identification, especially in high throughput lipidomics workflows. Here we...... propose a nomenclature for the annotation of lipid fragment ions, describe its implementation and present a freely available web application, termed ALEX123 lipid calculator, that can be used to query a comprehensive database featuring curated lipid fragmentation information for more than 430...

  3. Differential fragmentation patterns of pectin oligogalacturonides observed by nanoelectrospray quadrupole ion-trap mass spectrometry using automated spectra interpretation

    DEFF Research Database (Denmark)

    Mutenda, Kudzai E; Matthiesen, Rune; Roepstorff, Peter

    2007-01-01

    Oligogalacturonides of different degrees of polymerization (DP) and methyl esterification (DE) were structurally analyzed by nanoESI quadrupole ion-trap mass spectrometry. The fragmentation patterns of the oligogalacturonides were compared using the program 'Virtual Expert Mass Spectrometrist...... with free carboxylic acid groups underwent higher water loss compared to fully methyl-esterified oligogalacturonides under the same fragmentation conditions. Cross-ring cleavage, in which fragmentation occurs across the ring system of the galacturonate residue and signified by unique mass losses...... water loss than methyl-esterified ones will be postulated. In addition, the VEMS program was extended to automatically interpret and assign the fragment ions peaks generated in this study....

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

    Science.gov (United States)

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

    2017-07-15

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

  5. A fragmentation study of kaempferol using electrospray quadrupole time-of-flight mass spectrometry at high mass resolution

    Science.gov (United States)

    March, Raymond E.; Miao, Xiu-Sheng

    2004-02-01

    A mass spectrometric method based on the combined use of electrospray ionization, collision-induced dissociation and tandem mass spectrometry at high mass resolution has been applied to an investigation of the structural characterization of protonated and deprotonated kaempferol (3,5,7,4'-tetrahydroxyflavone). Low-energy product ion mass spectra of [M+H]+ ions showed simple fragmentations of the C ring that permitted characterization of the substituents in the A and B rings. In addition, four rearrangement reactions accompanied by losses of C2H2O, CHO[radical sign], CO, and H2O were observed. Low-energy product ion mass spectra of [M-H]- ions showed only four rearrangement reactions accompanied by losses of OH[radical sign], CO, CH2O, and C2H2O. The use of elevated cone voltages permitted observation of product ion mass spectra of selected primary and secondary fragment ions so that each fragment ion reported was observed as a direct product of its immediate precursor ion. Product ion mass spectra examined at high mass resolution allowed unambiguous determination of the elemental composition of fragment ions and resolution of two pairs of isobars. Fragmentation mechanisms and ion structures have been proposed.

  6. Storage ion trap of an 'In-Flight Capture' type for precise mass measurement of radioactive nuclear reaction products and fission fragments

    International Nuclear Information System (INIS)

    Tarantin, N.I.

    2001-01-01

    Data on nuclear masses provide a basis for creating and testing various nuclear models. A tandem system of FLNR comprised of the U-400M cyclotron, the COMBAS magnetic separator and the mass-spectrometric ion trap of an 'in-flight capture' type is considered as a possible complex for producing of the short-lived nuclei in fragmentation reactions by heavy ions and for precise mass measurement of these nuclei. The plan of scientific and technical FLNR research includes a project DRIBs for producing beams of accelerated radioactive nuclear reaction products and photofission fragments. This project proposes also precise mass measurements of the fission fragment with the help of the ion trap. The in-flight entrance of the ions and their capture in the mass-spectrometric ion trap using the monochromatizing degrader, the static electric and magnetic fields and a new invention, a magnetic unidirectional transporting ventil, is considered

  7. Fragmentation and reactivity of energy-selected ferrocenium ions

    International Nuclear Information System (INIS)

    Mestdagh, H.; Dutuit, O.; Heninger, M.; Thissen, R.; Alcaraz, C.

    2002-01-01

    In this study, results concerning the discussion of state-selected ferrocenium ions (c-C 5 H 5 ) 2 Fe + commonly called Cp 2 Fe + , as well as their reactions with methanol and ethanol are presented. Parent ions Cp 2 Fe + were produced by vacuumultraviolett (VUV) photoionization of neutral ferrocene using synchrotron radiation, and selected in internal energy by threshold photoelectron-photoion coincidences. The apparatus is divided into three differentially pumped regions: the source, the reaction and the detection zones. In source, state-selected parent ions are formed and can be selected in mass by a first quadrupole filter. State-selected ions are then injected in the second zone which is a RF octopole ion guide where reaction product ions are mass analyzed by a second quadrupole filter and detected by microchannelplates. In addition, the long flight time in the octopoles (several hundreds of microseconds) allows studying long-lived metastable ions. Total mass spectra were recorded at different photon energies, in addition to the main CpFe + and Fe + fragments, several minor fragments were detected such as C 10 H 10 + which reflects the formation of a C-C bond between the two Cp ligands. Losses of CH 3 , C 2 H 2 and C-4H 4 also indicate that important structure rearrangements take place before cleavage. The appearance energies of each mass-selected fragment ion were measured by recording fragment ion yields as a function of photon energy. Surprisingly, all fragments were found to have the same energy onset, i.e. 13.2 eV photon energy, except for C 3 H 3 Fe + (m/z 95). For Fe + ions, a sharp increase was observed at 17 eV, above the thermochemical onset of Fe + + 2 Cp. The 13.2 eV appearance energy of Fe + is thus assigned to the formation of Fe - + C 10 H 10 . The reactivity of ferrocenium ion with methanol and ethanol was investigated as a function of photon energy. While no reaction occurs at lower photon energies, several reaction products appear at 13.0 e

  8. Multifactorial Understanding of Ion Abundance in Tandem Mass Spectrometry Experiments.

    Science.gov (United States)

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

    2013-01-29

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

  9. De novo analysis of electron impact mass spectra using fragmentation trees

    International Nuclear Information System (INIS)

    Hufsky, Franziska; Rempt, Martin; Rasche, Florian; Pohnert, Georg; Böcker, Sebastian

    2012-01-01

    Highlights: ► We present a method for de novo analysis of accurate mass EI mass spectra of small molecules. ► This method identifies the molecular ion and thus the molecular formula where the molecular ion is present in the spectrum. ► Fragmentation trees are constructed by automated signal extraction and evaluation. ► These trees explain relevant fragmentation reactions. ► This method will be very helpful in the automated analysis of unknown metabolites. - Abstract: The automated fragmentation analysis of high resolution EI mass spectra based on a fragmentation tree algorithm is introduced. Fragmentation trees are constructed from EI spectra by automated signal extraction and evaluation. These trees explain relevant fragmentation reactions and assign molecular formulas to fragments. The method enables the identification of the molecular ion and the molecular formula of a metabolite if the molecular ion is present in the spectrum. These identifications are independent of existing library knowledge and, thus, support assignment and structural elucidation of unknown compounds. The method works even if the molecular ion is of very low abundance or hidden under contaminants with higher masses. We apply the algorithm to a selection of 50 derivatized and underivatized metabolites and demonstrate that in 78% of cases the molecular ion can be correctly assigned. The automatically constructed fragmentation trees correspond very well to published mechanisms and allow the assignment of specific relevant fragments and fragmentation pathways even in the most complex EI-spectra in our dataset. This method will be very helpful in the automated analysis of metabolites that are not included in common libraries and it thus has the potential to support the explorative character of metabolomics studies.

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

    Science.gov (United States)

    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.

  11. Fragment ion and electron emission from C sub 6 sub 0 by fast heavy ion impact

    CERN Document Server

    Mizuno, T; Itoh, A; Tsuchida, H; Nakai, Y

    2003-01-01

    Correlation between electron emission and fragmentation of C sub 6 sub 0 was studied using 847keV Si sup + ions. Mass distribution of fragment ions, number distribution of secondary electrons, and final charge distribution of outgoing projectiles were successfully measured by means of a triple coincidence time-of-flight method. Strong correlation was observed for electron emission and fragmentation.

  12. Fragmentation of toxicologically relevant drugs in positive-ion liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Niessen, W M A

    2011-01-01

    The identification of drugs and related compounds by LC-MS-MS is an important analytical challenge in several application areas, including clinical and forensic toxicology, doping control analysis, and environmental analysis. Although target-compound based analytical strategies are most frequently applied, at some point the information content of the MS-MS spectra becomes relevant. In this article, the positive-ion MS-MS spectra of a wide variety of drugs and related substances are discussed. Starting point was an MS-MS mass spectral library of toxicologically relevant compounds, available on the internet. The positive-ion MS-MS spectra of ∼570 compounds were interpreted by chemical and therapeutic class, thus involving a wide variety of drug compound classes, such benzodiazepines, beta-blockers, angiotensin-converting enzyme inhibitors, phenothiazines, dihydropyridine calcium channel blockers, diuretics, local anesthetics, vasodilators, as well as various subclasses of anti-diabetic, antidepressant, analgesic, and antihistaminic drugs. In addition, the scientific literature was searched for available MS-MS data of these compound classes and the interpretation thereof. The results of this elaborate study are presented in this article. For each individual compound class, the emphasis is on class-specific fragmentation, as discussing fragmentation of all individual compounds would take far too much space. The recognition of class-specific fragmentation may be quite informative in determining the compound class of a specific unknown, which may further help in the identification. In addition, knowledge on (class-specific) fragmentation may further help in the optimization of the selectivity in targeted analytical approaches of compounds of one particular class. Copyright © 2011 Wiley Periodicals, Inc.

  13. Hypoxia, Radiosensitizers and high-LET radiation - Nimorazole fragmentation using mass spectrometry

    DEFF Research Database (Denmark)

    Feketeova, Linda; Bassler, Niels

    (s): Fragmentation experiments have been performed using a Finnigan- LTQ-FT mass spectrometer equipped with an electrospray ionisation source. Collision-induced dissociation (CID) and electron-induced dissociation (EID) have been carried out by mass selecting the desired ions and subjecting them to activation energy...... using mass spectrometry. Understanding the fragmentation of radiosensitizers is crucial in evaluating the radiosensitization potential and developing new and more effective drugs, which may improve TCP in hypoxic tumours when using ion beams such as carbon-12 along with LET-painting techniques. Method...

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

    Science.gov (United States)

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

    2015-05-01

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

  15. Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  16. 'Collisional Activation of Peptide Ions in FT-ICR Mass Spectrometry'

    International Nuclear Information System (INIS)

    Laskin, Julia; Futrell, Jean H.

    2003-01-01

    In the last decade characterization of complex molecules, particularly biomolecules became a focus of both fundamental and applied research in mass spectrometry. Most of these studies utilize tandem mass spectrometry (MS/MS) for obtaining structural information for complex molecules. . Tandem mass spectrometry (MS/MS) typically involves the mass selection of a primary ion, its activation by collision or photon excitation, unimolecular decay into fragment ions characteristic of the ion structure and its internal excitation, and mass analysis of the fragment ions. Although the fundamental principles of tandem mass spectrometry of relatively small molecules are fairly well understood, our understanding of the activation and fragmentation of large molecules is much more primitive. For small ions a single energetic collision is sufficient to dissociate the ion but this is not the case for complex molecules. For large ions two fundamental limits severely constrain fragmentation in tandem mass spectrometry. First the center-of-mass collision energy?the absolute upper limit of energy transfer in a collision process?decreases with increasing mass of the projectile ion for fixed ion kinetic energy and neutral mass. Secondly, the dramatic increase in density of states with increasing internal degrees of freedom of the ion decreases the rate of dissociation by many orders of magnitude at a given internal energy. Consequently most practical MS/MS experiments with complex ions involve multiple collision activation (MCA-CID), multi-photon activation or surface-induced dissociation (SID). This review is focused on what has been learned in recent research studies concerned with fundamental aspects of MCA-CID and SID of model peptides with emphasis on experiments carried out using Fourier transform ion cyclotron resonance mass spectrometers (FT-ICR MS). These studies provide the first quantitative comparison of gas-phase multiple-collision activation and SID of peptide ions

  17. Combining Fragment-Ion and Neutral-Loss Matching during Mass Spectral Library Searching: A New General Purpose Algorithm Applicable to Illicit Drug Identification.

    Science.gov (United States)

    Moorthy, Arun S; Wallace, William E; Kearsley, Anthony J; Tchekhovskoi, Dmitrii V; Stein, Stephen E

    2017-12-19

    A mass spectral library search algorithm that identifies compounds that differ from library compounds by a single "inert" structural component is described. This algorithm, the Hybrid Similarity Search, generates a similarity score based on matching both fragment ions and neutral losses. It employs the parameter DeltaMass, defined as the mass difference between query and library compounds, to shift neutral loss peaks in the library spectrum to match corresponding neutral loss peaks in the query spectrum. When the spectra being compared differ by a single structural feature, these matching neutral loss peaks should contain that structural feature. This method extends the scope of the library to include spectra of "nearest-neighbor" compounds that differ from library compounds by a single chemical moiety. Additionally, determination of the structural origin of the shifted peaks can aid in the determination of the chemical structure and fragmentation mechanism of the query compound. A variety of examples are presented, including the identification of designer drugs and chemical derivatives not present in the library.

  18. Research at the fragment mass analyser at ATLAS

    International Nuclear Information System (INIS)

    Davids, C.N.; Back, B.; Bearden, I.G.

    1993-01-01

    The experimental program at the Fragment Mass Analyzer (FMA) at the ATLAS heavy ion accelerator of the Argonne National Laboratory is described. The brief description and operational properties of the FMA are presented. The highest mass resolution obtained with the FMA is 525/1. Some experimental results are presented. 5 refs., 7 figs

  19. Fragmentation of anthracene induced by collisions with 40 keV Ar8+ ions

    International Nuclear Information System (INIS)

    Brédy, R; Ortéga, C; Ji, M; Bernard, J; Chen, L; Montagne, G; Martin, S

    2013-01-01

    We report on the fragmentation of anthracene molecular ions C 14 H 10 r+ as a function of the parent ion initial charge r (= 1–4). Neutral anthracene molecules in the gas phase were ionized and excited in collisions with Ar 8+ ions at 40 keV and the mass-to-charge spectra of the parent ions C 14 H 10 r+ (1 ⩽ r ⩽ 4) were obtained. Stable molecular ions C 14 H 10 r+ (1 ⩽ r ⩽ 3) are observed. Branching ratios for the competitive evaporation (loss of neutral fragments) and fragmentation (charge separation) processes were measured for C 14 H 10 2+ parent ions. For C 14 H 10 3+ parent ions, the results indicate that fragmentation is the only dominant process and quasi-symmetric fission is observed. (paper)

  20. Fragment profiling of low molecular weight heparins using reversed phase ion pair liquid chromatography-electrospray mass spectrometry.

    Science.gov (United States)

    Xu, Xiaohui; Li, Daoyuan; Chi, Lequan; Du, Xuzhao; Bai, Xue; Chi, Lianli

    2015-04-30

    Low molecular weight heparins (LMWHs) are linear and highly charged carbohydrate polymers prepared by chemical or enzymatic depolymerization of heparin. Compared to unfractionated heparin (UFH), LMWHs are prevalently used as clinical anticoagulant drugs due to their lower side effects and better bioavailability. The work presented herein provides a rapid and powerful fragment mapping method for structural characterization of LMWHs. The chain fragments of two types of LMWHs, enoxaparin and nadroparin, were generated by controlled enzymatic digestion with each of heparinase I (Hep I, Enzyme Commission (EC) # 4.2.2.7), heparinase II (Hep II, no EC # assigned) and heparinase III (Hep III, EC # 4.2.2.8). Reversed phase ion pair high performance liquid chromatography (RPIP-HPLC) coupled with electrospray ion trap time-of-flight mass spectrometry (ESI-IT-TOF-MS) was used to profile the oligosaccharide chains ranging from disaccharides to decasaccharides. A database containing all theoretical structural compositions was established to assist the mass spectra interpretation. The six digests derived by three enzymes from two types of LMWHs exhibited distinguishable fingerprinting patterns. And a total of 94 enoxaparin fragments and 109 nadroparin fragments were detected and identified. Besides the common LMWH oligosaccharides, many components containing characteristic LMWH structures such as saturated L-idopyranosuronic acid, 2,5-anhydro-D-mannitol, 1,6-anhydro-D-aminopyranose, as well as odd number oligosaccharides were also revealed. Quantitative comparison of major components derived from innovator and generic nadroparin products was presented. This approach to profile LMWHs' fragments offers a highly reproducible, high resolution and information-rich tool for evaluating the quality of this category of anticoagulant drugs or comparing structural similarities among samples from various sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Fragmentation of cluster ions produced by electron impact ionization

    International Nuclear Information System (INIS)

    Parajuli, R.

    2001-12-01

    By studying fragmentation of dimer and cluster ions produced by electron impact ionization of a neutral cluster beam, it is possible to elucidate structure, stability and energetics of these species and the dynamics of the corresponding decay reactions. Fragmentation of carbon cluster ions formed from C 6 0 fullerenes, rare gas cluster ions and dimer ions and simple molecular cluster ions (oxygen and nitrogen) and dimer ions have been studied in this thesis using a high resolution two sector field mass spectrometer of reversed geometry and a NIER type electron impact ion source. Spontaneous decay reactions of triply and quadruply charged C 4 0 z + and C 4 1 z + cluster ions which are formed from C 6 0 fullerenes by electron impact ionization have been analyzed. A new but very weak decay reaction for the even-sized carbon clusters ions is observed, namely loss of C 3 . The odd-sized clusters ions preferentially decay by loss of carbon atoms and, to a lesser degree, trimers. A weak signal due to C 2 loss is observed for C 4 1 3 + ion. These decay channels are discussed in terms of the geometric structure of these metastable, relatively cold cluster ions. Measurements on metastable fragmentation of mass selected rare gas cluster ions (Ne, Ar, Kr) which are produced by electron impact ionization of a neutral rare gas cluster beam have been carried out. From the shape of the fragment ion peaks (MIKE scan technique) information about the distribution of kinetic energy that is released in the decay reaction can be deduced. In this study, the peak shape observed for cluster ions with sizes larger than five is Gaussian and thus from the peak width the mean kinetic energy release of the corresponding decay reactions can be calculated. Using finite heat bath theory, the binding energies of the decaying cluster ions are calculated from these data and have been compared to data in the literature where available. In addition to the decay reactions of cluster ions the metastable

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

    Science.gov (United States)

    Morrison, Kelsey A.; Clowers, Brian H.

    2017-06-01

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

  3. Analysis of intensities of positive and negative ion species from silicon dioxide films using time-of-flight secondary ion mass spectrometry and electronegativity of fragments

    International Nuclear Information System (INIS)

    Chiba, Kiyoshi

    2010-01-01

    Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO 2 films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of 28 Si + and 28 Si - ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) x 10 3 K of the sputtered region bombarded with pulsed 22 kV Au 3 + primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of Si n O m fragments, and a slight shift to negative polarity for PECVD SiO 2 compared to thermally oxidized SiO 2 films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO 2 by those for thermally oxidized SiO 2 films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiO m (m = 1, 2) and Si 2 O m (m = 1-4) fragments for PECVD SiO 2 films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO 2 films compared to the thermally oxidized SiO 2 films.

  4. Multicharged Ion-induced simple molecule fragmentation dynamics

    International Nuclear Information System (INIS)

    Tarisien, M.

    2003-10-01

    The aim of this work is to study the dynamics of swift multicharged ion-induced fragmentation of diatomic (CO) and triatomic (CO 2 ) molecules. Performed at the GANIL facility, this study used the Recoil Ion Momentum Spectroscopy technique (RIMS), which consists of a time-of-flight mass spectrometer, coupled with a multi-hit capability position sensitive detector (delay line anode). The high-resolution measurement of the kinetic energy distribution released (KER) during the CO fragmentation points out the limitation of the Coulomb Explosion Model, revealing, for example, the di-cation CO 2 + electronic state contribution in the case of C + /O + fragmentation pathway. Furthermore, the multi-ionization cross section dependence with the orientation of the internuclear axis of CO is compared with a geometrical model calculation. Finally, different behaviours are observed for the dissociation dynamics of a triatomic molecule (CO 2 ). While triple ionization leads mainly to a synchronous concerted fragmentation dynamics, a weak fraction of dissociating molecule follows a sequential dynamics involving CO 2 + metastable states. In the case of double ionization, (CO 2 ) 2+ di-cation dissociation dynamics is asynchronously concerted and has been interpreted using a simple model involving an asymmetrical vibration of the molecule. (author)

  5. An (e, 2e + ion) study of low-energy electron-impact ionization and fragmentation of tetrahydrofuran with high mass and energy resolutions

    Science.gov (United States)

    Ren, Xueguang; Pflüger, Thomas; Weyland, Marvin; Baek, Woon Yoon; Rabus, Hans; Ullrich, Joachim; Dorn, Alexander

    2014-10-01

    We study the low-energy (E0 = 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 using the recently developed photoemission electron source. Here, we will discuss the fragmentation reactions for the cations C4H8O+, C4H7O+, C2H3O+, C3H_6^+, C3H_5^+, C3H_3^+, CH3O+, CHO+, and C2H_3^+.

  6. Emission of intermediate mass fragments in the heavy ion interaction of (14.0 MeV/u) Pb+Au

    International Nuclear Information System (INIS)

    Khan, E.U.; Qureshi, I.E.; Shahzad, M.I.; Khattak, F.N.; Khan, H.A.

    2001-01-01

    We have studied the heavy ion interactions of (14.0 MeV/u) Pb + Au using two threshold detectors, mica and CN-85. A thin layer of Au was deposited on each of the three mica and two CN-85 detector pieces. These target-detector assemblies were exposed to a beam of 14.0 MeV/u Pb ions having the fluence of 1.5x10 6 cm 2 at GSI, Darmstadt, Germany. After removing the target material and etching the samples in appropriate etchants, we scanned 32.29 cm 2 and 24.97 cm 2 area of mica and CN-85, respectively. Based on the observed number of events of various multiplicities, we have determined the total as well as partial experimental reaction cross-sections. It is shown that a significant number of intermediate mass fragments are emitted along with the heavy fragments in the present reaction

  7. Fragment ion distribution in charge-changing collisions of 2-MeV Si ions with C60

    Science.gov (United States)

    Itoh, A.; Tsuchida, H.; Miyabe, K.; Majima, T.; Nakai, Y.

    2001-09-01

    We have measured positive fragment ions produced in collisions of 2 MeV Siq+ (q=0, 1, 2, 4) projectiles with a C60 molecular target. The measurement was performed with a time-of-flight coincidence method between fragment ions and charge-selected outgoing projectiles. For all the charge-changing collisions investigated here, the mass distribution of small fragment ions C+n (n=1-12) can be approximated fairly well by a power-law form of n-λ as a function of the cluster size n. The power λ derived from each mass distribution is found to change strongly according to different charge-changing collisions. As a remarkable experimental finding, the values of λ(loss) in electron loss collisions are almost the same for the same final charge states k irrespective of the initial charge q, exhibiting a nearly perfect linear relationship with k. We also performed calculations of the projectile ionization on the basis of the semiclassical approximation and obtained inelastic energy deposition for individual collision processes. The estimated energy deposition is found to have a simple correlation with the experimentally determined values of λ(loss).

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

    Science.gov (United States)

    Harvey, David J

    2005-01-01

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

  9. Dynamical scenario of intermediary mass fragments formation in heavy ion collisions

    International Nuclear Information System (INIS)

    Ayik, S.; Belkacem, M.; Gregoire, C.; Stryjewski, J.; Suraud, E.

    1989-01-01

    We briefly remind the possible dynamical scenario of fragments formation in heavy-ion collisions at some tens fo MeV/A. We discuss how present day dynamical models can describe fragment formation. We next turn to the Boltzmann-Langevin formalism which provides a well defined theoretical framework for the understanding of the growing of the dynamical instabilities leading to multifragmentation. We present a first numerical solution of the Boltzmann-Langevin equation and we apply the formalism to the onset of multifragmentation of the 40 Ca + 40 Ca system between 20 and 60 MeV/A beam energy [fr

  10. Towards a dynamical description of intermediate mass fragment formation in heavy-ion collisions at some tens of MeV/A

    International Nuclear Information System (INIS)

    Suraud, E.

    1990-01-01

    We briefly remind the possible dynamical scenario of fragments formation in central heavy-ion collisions at some tens of MeV/A. We discuss how present day dynamical models can describe fragment formation. We show that particle methods provide a reasonable solution of Boltzman-like equations. We next turn to the Boltzmann-Langevin formalism which gives a well defined framework for the understanding of Intermediate Mass Fragments formation. We present a first numerical solution of this equation and show the importance of fluctuations in the dynamics of the collision. We finally apply the formalism to the onset of multifragmentation in the 40 Ca + 40 Ca system between 20 and 60 MeV/A beam energy

  11. Isomeric signatures in the fragmentation of pyridazine and pyrimidine induced by fast ion impact

    Energy Technology Data Exchange (ETDEWEB)

    Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Montenegro, Eduardo C. [Instituto de Física, Universidade Federal do Rio de Janeiro, 21941-972 Rio de Janeiro, RJ (Brazil)

    2015-07-28

    We present fast proton impact induced fragmentations of pyrimidine and pyridazine as an experimental resource to investigate isomeric signatures. Major isomeric imprints are identified for few fragment ions and differences of more than an order of magnitude for the cross sections of fragments of the same mass were measured. The observation of the molecular structure of these isomers gives no apparent indication for the reasons for such substantial differences. It is verified that the simple displacement of the position of one nitrogen atom strongly inhibits or favors the production of some ionic fragment species. The dependency of the fragmentation cross sections on the proton impact energy, investigated by means of time of flight mass spectroscopy and of a model calculation based in first order perturbation theory, allows us to disentangle the complex collision dynamics of the ionic fragments. The proton-induced fragmentation discriminates rather directly the association between a molecular orbital ionization and the fragment-ions creation and abundance, as well as how the redistribution of the energy imparted to the molecules takes place, triggering not only single but also double vacancy and leads to specific fragmentation pathways.

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

    Science.gov (United States)

    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.

  13. Occurrence of C-Terminal Residue Exclusion in Peptide Fragmentation by ESI and MALDI Tandem Mass Spectrometry

    Science.gov (United States)

    Dupré, Mathieu; Cantel, Sonia; Martinez, Jean; Enjalbal, Christine

    2012-02-01

    By screening a data set of 392 synthetic peptides MS/MS spectra, we found that a known C-terminal rearrangement was unexpectedly frequently occurring from monoprotonated molecular ions in both ESI and MALDI tandem mass spectrometry upon low and high energy collision activated dissociations with QqTOF and TOF/TOF mass analyzer configuration, respectively. Any residue localized at the C-terminal carboxylic acid end, even a basic one, was lost, provided that a basic amino acid such arginine and to a lesser extent histidine and lysine was present in the sequence leading to a fragment ion, usually depicted as (bn-1 + H2O) ion, corresponding to a shortened non-scrambled peptide chain. Far from being an epiphenomenon, such a residue exclusion from the peptide chain C-terminal extremity gave a fragment ion that was the base peak of the MS/MS spectrum in certain cases. Within the frame of the mobile proton model, the ionizing proton being sequestered onto the basic amino acid side chain, it is known that the charge directed fragmentation mechanism involved the C-terminal carboxylic acid function forming an anhydride intermediate structure. The same mechanism was also demonstrated from cationized peptides. To confirm such assessment, we have prepared some of the peptides that displayed such C-terminal residue exclusion as a C-terminal backbone amide. As expected in this peptide amide series, the production of truncated chains was completely suppressed. Besides, multiply charged molecular ions of all peptides recorded in ESI mass spectrometry did not undergo such fragmentation validating that any mobile ionizing proton will prevent such a competitive C-terminal backbone rearrangement. Among all well-known nondirect sequence fragment ions issued from non specific loss of neutral molecules (mainly H2O and NH3) and multiple backbone amide ruptures (b-type internal ions), the described C-terminal residue exclusion is highly identifiable giving raise to a single fragment ion in

  14. On the formation of fragments in heavy ion collisions

    International Nuclear Information System (INIS)

    Gossiaux, P.B.; Puri, R.K.; Hartnack, Ch.; Aichelin, J.

    1995-01-01

    Formation of fragments in simulations of symmetric heavy ion reactions between E kin = 50 A MeV and 400 A MeV are investigated employing the Q.M.D. model. After a comparison of the results with existing data the earliest time at which the fragments can be identified is investigated. Investigating the production mechanism it was found at all energies that those nucleons which are finally in a fragment have strong initial - final state correlations in coordinate as well as in momentum space. They are important if one would like to draw conclusions from the mass dependence of dynamical quantities like the flow. (K.A.)

  15. Electron-capture negative-ion mass spectrometry: a technique for environmental contaminant identification

    International Nuclear Information System (INIS)

    Stemmler, E.A.

    1986-01-01

    Electron capture negative ion mass spectrometry (ECNIMS) is a method used to generate negative ions in a mass spectrometer by electron-molecule reactions. This technique facilitates the sensitive and selective detection of many toxic contaminants in environmental samples. Applications of this technique have been hindered by the limited understanding of instrumental parameters, by the questionable reproducibility of negative ion mass spectra, and by the inability to interpret negative ion mass spectra. Instrumental parameters which were important to control include the ion source temperature, ion source pressure, sample concentration, and the focus lens potential. The ability to obtain reproducible spectra was demonstrated by measurement of the spectrum of decafluorotriphenylphosphine (DFTPP) over a period of one year. Negative ion fragmentation mechanisms were studied by measuring the spectra of structurally related classes of compounds and isotopically labelled compounds. These results were combined with data obtained by other researchers. Fragmentations characteristic of particular functional groups or molecular structures have been summarized. From this data set, guidelines for the interpretation of electron capture negative ion mass spectra have been developed

  16. Timeframe Dependent Fragment Ions Observed in In-Source Decay Experiments with β-Casein Using MALDI MS.

    Science.gov (United States)

    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.

  17. Timeframe Dependent Fragment Ions Observed in In-Source Decay Experiments with β-Casein Using MALDI MS

    Science.gov (United States)

    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.

  18. Comprehensive and accurate tracking of carbon origin of LC-tandem mass spectrometry collisional fragments for 13C-MFA.

    Science.gov (United States)

    Kappelmann, Jannick; Klein, Bianca; Geilenkirchen, Petra; Noack, Stephan

    2017-03-01

    In recent years the benefit of measuring positionally resolved 13 C-labeling enrichment from tandem mass spectrometry (MS/MS) collisional fragments for improved precision of 13 C-Metabolic Flux Analysis ( 13 C-MFA) has become evident. However, the usage of positional labeling information for 13 C-MFA faces two challenges: (1) The mass spectrometric acquisition of a large number of potentially interfering mass transitions may hamper accuracy and sensitivity. (2) The positional identity of carbon atoms of product ions needs to be known. The present contribution addresses the latter challenge by deducing the maximal positional labeling information contained in LC-ESI-MS/MS spectra of product anions of central metabolism as well as product cations of amino acids. For this purpose, we draw on accurate mass spectrometry, selectively labeled standards, and published fragmentation pathways to structurally annotate all dominant mass peaks of a large collection of metabolites, some of which with a complete fragmentation pathway. Compiling all available information, we arrive at the most detailed map of carbon atom fate of LC-ESI-MS/MS collisional fragments yet, comprising 170 intense and structurally annotated product ions with unique carbon origin from 76 precursor ions of 72 metabolites. Our 13 C-data proof that heuristic fragmentation rules often fail to yield correct fragment structures and we expose common pitfalls in the structural annotation of product ions. We show that the positionally resolved 13 C-label information contained in the product ions that we structurally annotated allows to infer the entire isotopomer distribution of several central metabolism intermediates, which is experimentally demonstrated for malate using quadrupole-time-of-flight MS technology. Finally, the inclusion of the label information from a subset of these fragments improves flux precision in a Corynebacterium glutamicum model of the central carbon metabolism.

  19. Multicharged Ion-induced simple molecule fragmentation dynamics; Dynamique de la fragmentation de molecules simples induite par impact d'ion multicharge

    Energy Technology Data Exchange (ETDEWEB)

    Tarisien, M

    2003-10-01

    The aim of this work is to study the dynamics of swift multicharged ion-induced fragmentation of diatomic (CO) and triatomic (CO{sub 2}) molecules. Performed at the GANIL facility, this study used the Recoil Ion Momentum Spectroscopy technique (RIMS), which consists of a time-of-flight mass spectrometer, coupled with a multi-hit capability position sensitive detector (delay line anode). The high-resolution measurement of the kinetic energy distribution released (KER) during the CO fragmentation points out the limitation of the Coulomb Explosion Model, revealing, for example, the di-cation CO{sub 2}{sup +} electronic state contribution in the case of C{sup +}/O{sup +} fragmentation pathway. Furthermore, the multi-ionization cross section dependence with the orientation of the internuclear axis of CO is compared with a geometrical model calculation. Finally, different behaviours are observed for the dissociation dynamics of a triatomic molecule (CO{sub 2}). While triple ionization leads mainly to a synchronous concerted fragmentation dynamics, a weak fraction of dissociating molecule follows a sequential dynamics involving CO{sub 2}{sup +} metastable states. In the case of double ionization, (CO{sub 2}){sup 2+} di-cation dissociation dynamics is asynchronously concerted and has been interpreted using a simple model involving an asymmetrical vibration of the molecule. (author)

  20. Variation in yield ratios of fragment ions and of ion-pairs from CF2Cl2 following monochromatic soft X-ray absorption

    International Nuclear Information System (INIS)

    Suzuki, I.H.; Saito, N.; Bozek, J.D.

    1995-01-01

    Fragment ions produced from CF 2 Cl 2 have been measured from 44 to 1200eV using a time-of-flight mass spectrometer and monochromatized synchrotron radiation. Positively charged ion pairs from this molecule were observed in the inner-shell excitation regions using a Selected photoion-photoion coincidence technique. Obtained yield ratios of fragment ions indicate that the atomic chlorine ion, Cl + , has the greatest intensity at all photon energies above 60eV and exhibits a steep increase at the Cl L 2,3 -edges. Some fragment ions, in particular CF 2 + , have a clear intensity increase at the transitions of inner-shell electrons to unoccupied molecular orbitals. The ion pair F + - Cl + exhibits the highest yield at most photon energies, and some of the branching ratios for ion-pair production changed significantly near the Cl L 2,3 -edges. (author)

  1. Site-specific fragmentation of polystyrene molecule using size-selected Ar gas cluster ion beam

    International Nuclear Information System (INIS)

    Moritani, Kousuke; Mukai, Gen; Hashinokuchi, Michihiro; Mochiji, Kozo

    2009-01-01

    The secondary ion mass spectrum (SIMS) of a polystyrene thin film was investigated using a size-selected Ar gas cluster ion beam (GCIB). The fragmentation in the SIM spectrum varied by kinetic energy per atom (E atom ); the E atom dependence of the secondary ion intensity of the fragment species of polystyrene can be essentially classified into three types based on the relationship between E atom and the dissociation energy of a specific bonding site in the molecule. These results indicate that adjusting E atom of size-selected GCIB may realize site-specific bond breaking within a molecule. (author)

  2. Fragment formation in GeV-energy proton and light heavy-ion induced reactions

    International Nuclear Information System (INIS)

    Murakami, T.; Haga, M.; Haseno, M.

    2002-01-01

    We have investigated similarities and differences among the fragment formation processes in GeV-energy light-ion and light heavy-ion induced reactions. We have newly measured inclusive and exclusive energy spectra of intermediate mass fragments (3 ≤ Z ≤ 30; IMFs) for 8-GeV 16 O and 20 Ne and 12-GeV 20 Ne induced target multifragmentations (TMFs) in order to compare them with those previously measured for 8- and 12-GeV proton induced TMFs. We fond noticeable difference in their spectrum shapes and magnitudes but all of them clearly indicate the existence of sideward-peaked components, indicating fragment formations are mainly dictated not by a incident energy per nucleon but by a total energy of the projectile. (author)

  3. The fragment ion C13H9O2 m/z 197 in the mass spectra of 2-(2'-R-phenyl)benzoic acids

    International Nuclear Information System (INIS)

    Gills, R.G.; Porter, Q.N.

    1990-01-01

    In the electron impact mass spectrum of 2-( ' -R-phenyl)benzoic acids where R = H, NO 2 , OCH 3 , COOH, or Br, and abundant fragment ion m/z 197 is formed by an ipso substitution in which R is expelled as a radical. The structure of the ion m/z 197 has been shown by collision-activated dissociation to be identical with that of the protonated molecule formed by methane chemical ionization of 6H-dibenzo[b,d]pyran-6-one. 11 refs., 1 fig., ills

  4. Angular correlations and fragmentation in intermediate energy heavy ion collisions

    International Nuclear Information System (INIS)

    Kristiansson, Anders.

    1990-05-01

    Intermediate energy heavy-ion collisions have been studied from 35 A MeV up to 94 A MeV at various accelerators. Angular correlations between light particles and detection of projectile- and target-fragments have been used to investigate the reaction mechanisms in this transition region between low- and high energy. An excess of correlations is observed in the particle-particle elastic scattering plane. This excess increases with particle mass and can be understood in terms of momentum conservation. The fragmentation measurements gives an indication that both energy and momentum transfer to the spectator volumes does occur. (author)

  5. Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

    DEFF Research Database (Denmark)

    Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka

    2017-01-01

    Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identi......Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could...... be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for Me......V Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples...

  6. Conserved peptide fragmentation as a benchmarking tool for mass spectrometers and a discriminating feature for targeted proteomics.

    Science.gov (United States)

    Toprak, Umut H; Gillet, Ludovic C; Maiolica, Alessio; Navarro, Pedro; Leitner, Alexander; Aebersold, Ruedi

    2014-08-01

    Quantifying the similarity of spectra is an important task in various areas of spectroscopy, for example, to identify a compound by comparing sample spectra to those of reference standards. In mass spectrometry based discovery proteomics, spectral comparisons are used to infer the amino acid sequence of peptides. In targeted proteomics by selected reaction monitoring (SRM) or SWATH MS, predetermined sets of fragment ion signals integrated over chromatographic time are used to identify target peptides in complex samples. In both cases, confidence in peptide identification is directly related to the quality of spectral matches. In this study, we used sets of simulated spectra of well-controlled dissimilarity to benchmark different spectral comparison measures and to develop a robust scoring scheme that quantifies the similarity of fragment ion spectra. We applied the normalized spectral contrast angle score to quantify the similarity of spectra to objectively assess fragment ion variability of tandem mass spectrometric datasets, to evaluate portability of peptide fragment ion spectra for targeted mass spectrometry across different types of mass spectrometers and to discriminate target assays from decoys in targeted proteomics. Altogether, this study validates the use of the normalized spectral contrast angle as a sensitive spectral similarity measure for targeted proteomics, and more generally provides a methodology to assess the performance of spectral comparisons and to support the rational selection of the most appropriate similarity measure. The algorithms used in this study are made publicly available as an open source toolset with a graphical user interface. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  7. Symposium on fast atom and ion induced mass spectrometry of nonvolatile organic solids

    International Nuclear Information System (INIS)

    McNeal, C.J.

    1982-01-01

    The mechanisms of molecular and fragment ion production and the various parameters affecting ion yields were discussed by 6 invited speakers from Europe, Canada, and the US at this symposium. The work reported was almost equally divided between that using low-energy (keV) primary ion (or atom) beams, e.g. fast atom bombardment mass spectrometry (FABMS) and secondary ion mass spectrometry (SIMS) and that using high energy (MeV) particles, e.g. heavy ion induced mass spectrometry (HIIDMS) and 252 Cf-plasma desorption mass spectrometry ( 252 Cf-PDMS). Both theoretical foundations and observed experimental results for both techniques are included

  8. Fragment Size Distribution of Blasted Rock Mass

    Science.gov (United States)

    Jug, Jasmin; Strelec, Stjepan; Gazdek, Mario; Kavur, Boris

    2017-12-01

    Rock mass is a heterogeneous material, and the heterogeneity of rock causes sizes distribution of fragmented rocks in blasting. Prediction of blasted rock mass fragmentation has a significant role in the overall economics of opencast mines. Blasting as primary fragmentation can significantly decrease the cost of loading, transport, crushing and milling operations. Blast fragmentation chiefly depends on the specific blast design (geometry of blast holes drilling, the quantity and class of explosive, the blasting form, the timing and partition, etc.) and on the properties of the rock mass (including the uniaxial compressive strength, the rock mass elastic Young modulus, the rock discontinuity characteristics and the rock density). Prediction and processing of blasting results researchers can accomplish by a variety of existing software’s and models, one of them is the Kuz-Ram model, which is possibly the most widely used approach to estimating fragmentation from blasting. This paper shows the estimation of fragmentation using the "SB" program, which was created by the authors. Mentioned program includes the Kuz-Ram model. Models of fragmentation are confirmed and calibrated by comparing the estimated fragmentation with actual post-blast fragmentation from image processing techniques. In this study, the Kuz-Ram fragmentation model has been used for an open-pit limestone quarry in Dalmatia, southern Croatia. The resulting calibrated value of the rock factor enables the quality prognosis of fragmentation in further blasting works, with changed drilling geometry and blast design parameters. It also facilitates simulation in the program to optimize blasting works and get the desired fragmentations of the blasted rock mass.

  9. Rapid profiling of polymeric phenolic acids in Salvia miltiorrhiza by hybrid data-dependent/targeted multistage mass spectrometry acquisition based on expected compounds prediction and fragment ion searching.

    Science.gov (United States)

    Shen, Yao; Feng, Zijin; Yang, Min; Zhou, Zhe; Han, Sumei; Hou, Jinjun; Li, Zhenwei; Wu, Wanying; Guo, De-An

    2018-04-01

    Phenolic acids are the major water-soluble components in Salvia miltiorrhiza (>5%). According to previous studies, many of them contribute to the cardiovascular effects and antioxidant effects of S. miltiorrhiza. Polymeric phenolic acids can be considered as the tanshinol derived metabolites, e.g., dimmers, trimers, and tetramers. A strategy combined with tanshinol-based expected compounds prediction, total ion chromatogram filtering, fragment ion searching, and parent list-based multistage mass spectrometry acquisition by linear trap quadropole-orbitrap Velos mass spectrometry was proposed to rapid profile polymeric phenolic acids in S. miltiorrhiza. More than 480 potential polymeric phenolic acids could be screened out by this strategy. Based on the fragment information obtained by parent list-activated data dependent multistage mass spectrometry acquisition, 190 polymeric phenolic acids were characterized by comparing their mass information with literature data, and 18 of them were firstly detected from S. miltiorrhiza. Seven potential compounds were tentatively characterized as new polymeric phenolic acids from S. miltiorrhiza. This strategy facilitates identification of polymeric phenolic acids in complex matrix with both selectivity and sensitivity, which could be expanded for rapid discovery and identification of compounds from complex matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Mass distribution and multiple fragmentation events in high energy cluster-cluster collisions: evidence for a predicted phase transition

    International Nuclear Information System (INIS)

    Farizon, B.; Farizon, M.; Gaillard, M.J.; Genre, R.; Louc, S.; Martin, J.; Senn, G.; Scheier, P.; Maerk, T.D.

    1996-09-01

    Fragment size distributions including multiple fragmentation events have been measured for high energy H 25 + cluster ions (60 keV/amu) colliding with a neutral C 60 target. In contrast to earlier collision experiments with a helium target the present studies do not show a U-shaped fragment mass distribution, but a single power-law falloff with increasing fragment mass. This behaviour is similar to what is known for the intermediate regime in nuclear collision physics and thus confirms a recently predicted scaling from nuclear to molecular collisions

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

    Science.gov (United States)

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

    2017-04-04

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

  12. Identification and imaging of modern paints using Secondary Ion Mass Spectrometry with MeV ions

    Science.gov (United States)

    Bogdanović Radović, Iva; Siketić, Zdravko; Jembrih-Simbürger, Dubravka; Marković, Nikola; Anghelone, Marta; Stoytschew, Valentin; Jakšić, Milko

    2017-09-01

    Secondary Ion Mass Spectrometry using MeV ion excitation was applied to analyse modern paint materials containing synthetic organic pigments and binders. It was demonstrated that synthetic organic pigments and binder components with molecular masses in the m/z range from 1 to 1200 could be identified in different paint samples with a high efficiency and in a single measurement. Different ways of mounting of mostly insulating paint samples were tested prior to the analysis in order to achieve the highest possible yield of pigment main molecular ions. As Time-of-Flight mass spectrometer for MeV Secondary Ion Mass Spectrometry is attached to the heavy ion microprobe, molecular imaging on cross-sections of small paint fragments was performed using focused ions. Due to the fact that molecules are extracted from the uppermost layer of the sample and to avoid surface contamination, the paint samples were not embedded in the resin as is usually done when imaging of paint samples using different techniques in the field of cultural heritage.

  13. The FRS Ion Catcher : A facility for high-precision experiments with stopped projectile and fission fragments

    NARCIS (Netherlands)

    Plass, W. R.; Dickel, T.; Purushothaman, S.; Dendooven, P.; Geissel, H.; Ebert, J.; Haettner, E.; Jesch, C.; Ranjan, M.; Reiter, M. P.; Weick, H.; Amjad, F.; Ayet, S.; Diwisch, M.; Estrade, A.; Farinon, F.; Greiner, F.; Kalantar-Nayestanaki, N.; Knoebel, R.; Kurcewicz, J.; Lang, J.; Moore, I.; Mukha, I.; Nociforo, C.; Petrick, M.; Pfuetzner, M.; Pietri, S.; Prochazka, A.; Rink, A. -K.; Rinta-Antila, S.; Schaefer, D.; Scheidenberger, C.; Takechi, M.; Tanaka, Y. K.; Winfield, J. S.; Yavor, M. I.

    2013-01-01

    At the FRS Ion Catcher at GSI, projectile and fission fragments are produced at relativistic energies, separated in-flight, range-focused, slowed down and thermalized in a cryogenic stopping cell. A multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) is used to perform direct mass

  14. High precision mass measurements of thermalized relativistic uranium projectile and fission fragments with a multiple-reflection time-of-flight mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Ayet San Andres, Samuel [GSI Helmholtzzentrum fuer Schwerionenforschung, Darmstadt (Germany); Justus Liebig Universitaet, Giessen (Germany); Collaboration: FRS Ion Catcher-Collaboration

    2016-07-01

    At the FRS Ion Catcher at GSI, a relativistic beam of {sup 238}U at 1GeV/u was used to produce fission and projectile fragments on a beryllium target. The ions were separated in-flight at the FRS, thermalized in a cryogenic stopping cell and transferred to a multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS) where high precision mass measurements were performed. The masses of several fission and projectile fragments were measured (including short-lived nuclei with half-lives down to 18 ms) and the possibility of tailoring an isomerically clean beam for other experiments was demonstrated. With the demonstrated performance of the MR-TOF-MS and the expected production rates of exotic nuclei far from stability at the next-generation facilities such as FAIR, novel mass measurements of nuclei close to the neutron drip line will be possible and key information for understanding the r-process will be available. The results from the last experiment and an outlook of possible future mass measurements close to the neutron drip line at FAIR with the MR-TOF-MS are presented.

  15. Structure and further fragmentation of significant [a3 + Na - H]+ ions from sodium-cationized peptides.

    Science.gov (United States)

    Wang, Huixin; Wang, Bing; Wei, Zhonglin; Zhang, Hao; Guo, Xinhua

    2015-01-01

    A good understanding of gas-phase fragmentation chemistry of peptides is important for accurate protein identification. Additional product ions obtained by sodiated peptides can provide useful sequence information supplementary to protonated peptides and improve protein identification. In this work, we first demonstrate that the sodiated a3 ions are abundant in the tandem mass spectra of sodium-cationized peptides although observations of a3 ions have rarely been reported in protonated peptides. Quantum chemical calculations combined with tandem mass spectrometry are used to investigate this phenomenon by using a model tetrapeptide GGAG. Our results reveal that the most stable [a3 + Na - H](+) ion is present as a bidentate linear structure in which the sodium cation coordinates to the two backbone carbonyl oxygen atoms. Due to structural inflexibility, further fragmentation of the [a3 + Na - H](+) ion needs to overcome several relatively high energetic barriers to form [b2 + Na - H](+) ion with a diketopiperazine structure. As a result, low abundance of [b2 + Na - H](+) ion is detected at relatively high collision energy. In addition, our computational data also indicate that the common oxazolone pathway to generate [b2 + Na - H](+) from the [a3 + Na - H](+) ion is unlikely. The present work provides a mechanistic insight into how a sodium ion affects the fragmentation behaviors of peptides. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Fragmentation of acetic acid ions with selected internal energies

    Science.gov (United States)

    Zha, Qingmei; Nishimura, Toshihide; Bertrand, Michel J.; Meisels, G. G.

    1991-08-01

    The unimolecular dissociation of acetic acid ion in the photon energy range 10.5-17.0 eV was studied using threshold photoelectron photoion coincidence mass spectrometry. The detailed breakdown graph was obtained and the fragmentation pathways were elucidated. The breakdown graph calculated using statistical theories was found to be consistent with the experimental data up to a photon energy of about 12.5 eV. The average kinetic energy release observed is higher than that calculated on the basis of quasi-equilibrium theory for the formation of COOH+ while it seems to be statistical for the formation of CH3CO+. The origin of kinetic energy release accompanying the formation of these two ions is discussed. The structure of [COH3]+ ion (m/z 31) is determined to be hydroxymethyl cation, CH2OH+, which could be formed by a two-step rearrangement prior to dissociation.

  17. Anisotropy in highly charged ion induced molecule fragmentation

    International Nuclear Information System (INIS)

    Juhasz, Z.; Sulik, B.; Fremont, F.; Chesnel, J.Y.; Hajaji, A.

    2006-01-01

    Complete text of publication follows. Studying fragmentation processes of biologically relevant molecules due to highly charged ion impact is important to understand radiation damage in biological tissues. Energy spectra of the charged molecule fragments may reveal the different fragmentation patterns meanwhile the angular distributions of the fragments characterize the dependence of fragmentation probability on the initial orientation of the molecule. The research to explore the angular distribution of the molecule fragments has only recently been started[1]. In 2006 we performed measurements at ARIBE facility at GANIL, Caen (France), in order to investigate orientation effects in molecule fragmentation. Fragmentation of H 2 O, C 6 H 6 and CH 4 , which represent different level of symmetry, have been studied by 60 keV N 6+ ion impact. Energy spectra of the charged fragments at different observation angles have been taken. As our example spectra show the different protonic peaks can be attributed to different fragmentation processes. Significant anisotropy can be seen in the different processes. The strongest evidence for the anisotropy can be seen in the spectra of C 6 H 6 , where the spectra appear isotropic in almost the whole observed energy range except one peak, which has a strong angular dependence and is maximal around 90 deg. (author)

  18. Analysis of fission-fragment mass distribution within the quantum-mechanical fragmentation theory

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Pardeep; Kaur, Harjeet [Guru Nanak Dev University, Department of Physics, Amritsar (India)

    2016-11-15

    The fission-fragment mass distribution is analysed for the {sup 208}Pb({sup 18}O, f) reaction within the quantum-mechanical fragmentation theory (QMFT). The reaction potential has been calculated by taking the binding energies, Coulomb potential and proximity potential of all possible decay channels and a stationary Schroedinger equation has been solved numerically to calculate the fission-fragment yield. The overall results for mass distribution are compared with those obtained in experiment. Fine structure dips in yield, corresponding to fragment shell closures at Z = 50 and N=82, which are observed by Bogachev et al., are reproduced successfully in the present calculations. These calculations will help to estimate the formation probabilities of fission fragments and to understand many related phenomena occurring in the fission process. (orig.)

  19. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Charity, R.J.; Sobotka, L.G.

    1993-01-01

    The study of intermediate-energy heavy-ion nuclear reactions is reported. This work has two foci: the properties of nuclear matter under abnormal conditions, in this energy domain, predominately low densities and the study of the relevant reaction mechanisms. Nuclear matter properties, such as phase transitions, are reflected in the dynamics of the reactions. The process leads to an understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. The program has the following objectives: to study energy, mass, and angular momentum deposition by studying incomplete fusion reactions; to gain confidence in the understanding of how highly excited systems decompose by studying all emissions from the highly excited systems; to push these kinds of studies into the intermediate energy domain (where intermediate mass fragment emission is not improbable) with excitation function studies; and to learn about the dynamics of the decays using particle-particle correlations. The last effort focuses on simple systems, where definitive statements are possible. These avenues of research share a common theme, large complex fragment production. It is this feature, more than any other, which distinguishes the intermediate energy domain

  20. Gas-phase fragmentation of peptides to increase the spatial resolution of the Hydrogen Exchange Mass Spectrometry experiment

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    are produced after precursor ion selection and thus do not add complexity to the LC-MS analysis. The key to obtaining optimal spatial resolution in a hydrogen exchange mass spectrometry (HX-MS) experiment is the fragmentation efficiency. This chapter discusses common fragmentation techniques like collision....../D scrambling, thus making them suitable for HX applications. By combining the classic bottom-up HX-MS workflow with gas-phase fragmentation by ETD, detailed information on protein HX can be obtained....

  1. Analysis of multi-fragmentation reactions induced by relativistic heavy ions using the statistical multi-fragmentation model

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, T., E-mail: ogawa.tatsuhiko@jaea.go.jp [Research Group for Radiation Protection, Division of Environment and Radiation Sciences, Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan); Sato, T.; Hashimoto, S. [Research Group for Radiation Protection, Division of Environment and Radiation Sciences, Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Shirakata-Shirane, Tokai, Ibaraki 319-1195 (Japan); Niita, K. [Research Organization for Information Science and Technology, Shirakata-shirane, Tokai, Ibaraki 319-1188 (Japan)

    2013-09-21

    The fragmentation cross-sections of relativistic energy nucleus–nucleus collisions were analyzed using the statistical multi-fragmentation model (SMM) incorporated with the Monte-Carlo radiation transport simulation code particle and heavy ion transport code system (PHITS). Comparison with the literature data showed that PHITS-SMM reproduces fragmentation cross-sections of heavy nuclei at relativistic energies better than the original PHITS by up to two orders of magnitude. It was also found that SMM does not degrade the neutron production cross-sections in heavy ion collisions or the fragmentation cross-sections of light nuclei, for which SMM has not been benchmarked. Therefore, SMM is a robust model that can supplement conventional nucleus–nucleus reaction models, enabling more accurate prediction of fragmentation cross-sections.

  2. Analysis of multi-fragmentation reactions induced by relativistic heavy ions using the statistical multi-fragmentation model

    International Nuclear Information System (INIS)

    Ogawa, T.; Sato, T.; Hashimoto, S.; Niita, K.

    2013-01-01

    The fragmentation cross-sections of relativistic energy nucleus–nucleus collisions were analyzed using the statistical multi-fragmentation model (SMM) incorporated with the Monte-Carlo radiation transport simulation code particle and heavy ion transport code system (PHITS). Comparison with the literature data showed that PHITS-SMM reproduces fragmentation cross-sections of heavy nuclei at relativistic energies better than the original PHITS by up to two orders of magnitude. It was also found that SMM does not degrade the neutron production cross-sections in heavy ion collisions or the fragmentation cross-sections of light nuclei, for which SMM has not been benchmarked. Therefore, SMM is a robust model that can supplement conventional nucleus–nucleus reaction models, enabling more accurate prediction of fragmentation cross-sections

  3. Isomer Information from Ion Mobility Separation of High-Mannose Glycan Fragments.

    Science.gov (United States)

    Harvey, David J; Seabright, Gemma E; Vasiljevic, Snezana; Crispin, Max; Struwe, Weston B

    2018-05-01

    Extracted arrival time distributions of negative ion CID-derived fragments produced prior to traveling-wave ion mobility separation were evaluated for their ability to provide structural information on N-linked glycans. Fragmentation of high-mannose glycans released from several glycoproteins, including those from viral sources, provided over 50 fragments, many of which gave unique collisional cross-sections and provided additional information used to assign structural isomers. For example, cross-ring fragments arising from cleavage of the reducing terminal GlcNAc residue on Man 8 GlcNAc 2 isomers have unique collision cross-sections enabling isomers to be differentiated in mixtures. Specific fragment collision cross-sections enabled identification of glycans, the antennae of which terminated in the antigenic α-galactose residue, and ions defining the composition of the 6-antenna of several of the glycans were also found to have different cross-sections from isomeric ions produced in the same spectra. Potential mechanisms for the formation of the various ions are discussed and the estimated collisional cross-sections are tabulated. Graphical Abstract ᅟ.

  4. Ionization and fragmentation of water clusters by fast highly charged ions

    International Nuclear Information System (INIS)

    Adoui, L; Cassimi, A; Gervais, B; Grandin, J-P; Guillaume, L; Maisonny, R; Legendre, S; Tarisien, M; Lopez-Tarifa, P; Alcami, M; Martin, F; Politis, M-F; Penhoat, M-A Herve du; Vuilleumier, R; Gaigeot, M-P; Tavernelli, I

    2009-01-01

    We study the dissociative ionization of water clusters by impact of 12 MeV/u Ni 25+ ions. Cold target recoil ion momentum spectroscopy (COLTRIMS) is used to obtain information about stability, energetics and charge mobility of the ionized water clusters. An unusual stability of the H 9 O + 4 ion is observed, which could be the signature of the so-called Eigen structure in gas-phase water clusters. From the analysis of coincidences between charged fragments, we conclude that charge mobility is very high and is responsible for the formation of protonated water clusters, (H 2 O) n H + , that dominate the mass spectrum. These results are supported by Car-Parrinello molecular dynamics and time-dependent density functional theory simulations, which also reveal the mechanisms of such mobility.

  5. Mass measurements of {sup 238}U-projectile fragments for the first time with a multiple-reflection time-of-flight mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Ebert, Jens

    2016-07-01

    Mass measurements of short-lived uranium projectile fragments were performed for the first time with a Multiple-Reflexion-Time-of-Flight Mass Spectrometer (MR-TOF-MS). A major part of this doctoral work was a novel development of a data analysis method for the MR-TOF-MS mass measurements of exotic nuclei at the fragment separator FRS at GSI. The developed method was successfully applied to the data obtained from two pilot experiments with the MR-TOF-MS at the FRS in 2012 and 2014. A substantial upgrade of the experimental setup of the MR-TOF-MS was also performed in the frame work of this doctoral thesis after the first run. In the experiments projectile fragments were created with 1000 MeV/u {sup 238}U ions in a Be/Nb target at the entrance of the in-flight separator FRS. The exotic nuclei were spatially separated, energy bunched and slowed down with the ion-optical system of the FRS combined with monoenergetic and homogeneous degraders. At the final focal plane of the FRS the fragments were completely slowed down and thermalized in a cryogenic stopping cell (CSC) filled with 3-5 mg/cm{sup 2} pure helium gas. The exotic nuclei were fast extracted from the CSC to enable mass measurements of very short-lived fragments with the MR-TOF-MS. The achievement of this goal was successfully demonstrated with the mass measurement of {sup 220}Ra ions with a half-life of 17.9 ms and 11 detected events. The mass measurements of the isobars {sup 211}Fr, {sup 211}Po and {sup 211}Rn have clearly demonstrated the scientific potential of the MR-TOF-MS for the investigation of exotic nuclei and the power of the data analysis system. Difficult measurements with overlapping mass distributions with only a few counts in the measured spectra were the challenge for the new data analysis method based on the maximum likelihood method. The drifts during the measurements were corrected with the developed time-resolved calibration method. After the improvements of the setup as a consequence of

  6. Gamma Radiation from Fission Fragments Experimental Apparatus-Mass Spectrum Resolution

    Energy Technology Data Exchange (ETDEWEB)

    Higbie, Jack

    1969-08-15

    The gamma-radiation from fission fragments was studied as a function of the fragment mass. The mass was determined from the fragment energies using solid state detectors. The mass resolution which can be achieved by this method is treated in detail. The average initial fragment mass and the initial mass resolution is calculated as a function of the measured (apparent) mass yield for three different thicknesses of the fissile material deposit. This treatment gives a clear indication of those factors most important for good mass resolution work. A detailed description of the experimental apparatus is given in the appendices.

  7. Influence of mass-asymmetry and ground state spin on fission fragment angular distributions

    International Nuclear Information System (INIS)

    Thomas, R.G.; Biswas, D.C.; Saxena, A.; Pant, L.M.; Nayak, B.K.; Vind, R.P.; Sahu, P.K.; Sinha, Shrabani; Choudhury, R.K.

    2001-01-01

    The strong influence of the target or/and projectile ground state spin on the anomalously large anisotropies of fission fragments produced in the heavy-ion induced fission of actinide targets were reported earlier. Interestingly, all those systems studied were having a mass asymmetry greater than the Businaro-Gallone critical asymmetry and hence the presence of pre-equilibrium fission was unambiguously ruled out. The observed anisotropies were successfully explained using the ECD-K-States model. It is of interest to know the influence of the target/projectile ground state spin on systems having an entrance channel mass asymmetry less than the critical value where pre-equilibrium fission cannot be ignored. With this motivation we performed measurements of fission fragment angular distributions of the 16 O+ 235 U (spin=7/2) system

  8. Validation of Geant4 fragmentation for Heavy Ion Therapy

    Science.gov (United States)

    Bolst, David; Cirrone, Giuseppe A. P.; Cuttone, Giacomo; Folger, Gunter; Incerti, Sebastien; Ivanchenko, Vladimir; Koi, Tatsumi; Mancusi, Davide; Pandola, Luciano; Romano, Francesco; Rosenfeld, Anatoly B.; Guatelli, Susanna

    2017-10-01

    12C ion therapy has had growing interest in recent years for its excellent dose conformity. However at therapeutic energies, which can be as high as 400 MeV/u, carbon ions produce secondary fragments. For an incident 400 MeV/u 12C ion beam, ∼ 70 % of the beam will undergo fragmentation before the Bragg Peak. The dosimetric and radiobiological impact of these fragments must be accurately characterised, as it can result in increasing the risk of secondary cancer for the patient as well as altering the relative biological effectiveness. This work investigates the accuracy of three different nuclear fragmentation models available in the Monte Carlo Toolkit Geant4, the Binary Intranuclear Cascade (BIC), the Quantum Molecular Dynamics (QMD) and the Liege Intranuclear Cascade (INCL++). The models were benchmarked against experimental data for a pristine 400 MeV/u 12C beam incident upon a water phantom, including fragment yield, angular and energy distribution. For fragment yields the three alternative models agreed between ∼ 5 and ∼ 35 % with experimental measurements, the QMD using the "Frag" option gave the best agreement for lighter fragments but had reduced agreement for larger fragments. For angular distributions INCL++ was seen to provide the best agreement among the models for all elements with the exception of Hydrogen, while BIC and QMD was seen to produce broader distributions compared to experiment. BIC and QMD performed similar to one another for kinetic energy distributions while INCL++ suffered from producing lower energy distributions compared to the other models and experiment.

  9. Versatile lipid profiling by liquid chromatography-high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer.

    Science.gov (United States)

    Gallart-Ayala, H; Courant, F; Severe, S; Antignac, J-P; Morio, F; Abadie, J; Le Bizec, B

    2013-09-24

    Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC-HRMS or LC-MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC-HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and "all ion fragmentation" (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Analytical applications of ion/molecule reactions in a triple quadrupole mass spectrometer

    International Nuclear Information System (INIS)

    Kinter, M.T.

    1986-01-01

    The development of triple quadrupole mass spectrometers as a means of performing tandem mass spectrometry has provided a versatile instrument on which the ion/molecule reactions of a mass selected ion can be studied. This dissertation details the application of ion/molecule reactions in a triple quadrupole to two analytical problems. Part I. Ion/Molecule Reactions of Ammonia with Translationally Excited C 2 H 5 O + /Ions. The ability to impart low center-of-mass translational energies, which upon collision are converted into internal energy, allows the observation of reactions that require energy input. In addition, the systematic variation of the ion kinetic energy, often referred to as energy-resolved mass spectrometer, adds another dimension to the mass spectrum and can allow the observation of thresholds for reactions requiring energy input. This investigation develops methods for determining these thresholds. Part 2. The Use of Ion/Molecule Reactions in selected Reaction Monitoring GC/MSD/MS Analyses. An approach to improving the selectivity of an analysis is to improve the selectivity of the detection method. In GC/MS, one method has been to monitor a selected fragmentation reaction, either metastable or collisionally activated, in a selected reaction monitoring (SRM) analysis. This develops the use of ion/molecule reactions for selected reaction monitoring analyses

  11. Cluster ion formation during sputtering processes: a complementary investigation by ToF-SIMS and plasma ion mass spectrometry

    International Nuclear Information System (INIS)

    Welzel, T; Ellmer, K; Mändl, S

    2014-01-01

    Plasma ion mass spectrometry using a plasma process monitor (PPM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been complementarily employed to investigate the sputtering and ion formation processes of Al-doped zinc oxide. By comparing the mass spectra, insights on ion formation and relative cross-sections have been obtained: positive ions as measured during magnetron sputtering by PPM are originating from the plasma while those in SIMS start at the surface leading to large differences in the mass spectra. In contrast, negative ions originating at the surface will be accelerated through the plasma sheath. They arrive at the PPM after traversing the plasma nearly collisionless as seen from the rather similar spectra. Hence, it is possible to combine the high mass resolution of ToF-SIMS to obtain insight for separating cluster ions, e.g. Zn x and ZnO y , and the energy resolution of PPM to find fragmentation patterns for negative ions. While the ion formation processes during both experiments can be assumed to be similar, differences may arise due to the lower volume probed by SIMS. In the latter case, there is a chance of small target inhomogeneities being able to be enhanced and lower surface temperatures leading to less outgassing and, thus, retention of volatile compounds. (paper)

  12. Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon [Chungnam National Univ., Daejeon (Korea, Republic of); Cho, Soo Gyeong; Goh, Eun Mee [Agency for Defense Development, Daejeon (Korea, Republic of); Lee, Sungman; Koh, Sungsuk [Sensor Tech Inc., Seoul (Korea, Republic of)

    2013-12-15

    Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H]{sup -} for TNT and DNT or [M]{sup ·-}. for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO]{sup -}. These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available.

  13. Mass Spectrometric Analysis of Eight Common Chemical Explosives Using Ion Trap Mass Spectrometer

    International Nuclear Information System (INIS)

    Park, Sehwan; Lee, Jihyeon; KIm, Jeongkwon; Cho, Soo Gyeong; Goh, Eun Mee; Lee, Sungman; Koh, Sungsuk

    2013-01-01

    Eight representative explosives (ammonium perchlorate (AP), ammonium nitrate (AN), trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), cyclonite (RDX), cyclotetramethylenetetranitramine (HMX), pentaerythritol tetranitrate (PETN), and hexanitrostilbene (HNS)) were comprehensively analyzed with an ion trap mass spectrometer in negative ion mode using direct infusion electrospray ionization. MS/MS experiments were performed to generate fragment ions from the major parent ion of each explosive. Explosives in salt forms such as AP or AN provided cluster parent ions with their own anions. Explosives with an aromatic ring were observed as either [M.H] - for TNT and DNT or [M] ·- . for HNS, while explosives without an aromatic ring such as RDX, HMX, and PETN were detected as an adduct ion with a formate anion, i. e., [M+HCOO] - . These findings provide a guideline for the rapid and accurate detection of explosives once portable MS instruments become more readily available

  14. Dynamics of Neutral Cluster Growth and Cluster Ion Fragmentation for Toluene/Water, Aniline/Argon, and 4-Fluorostyrene/Argon Clusters: Covariance Mapping of the Mass Spectral Data

    National Research Council Canada - National Science Library

    Foltin, M

    1998-01-01

    .... To explore sensitivity of the parent ion/fragment ion correlation coefficient to cluster fragmentation, correlation coefficients are measured as a function of ionization photon energy as thresholds...

  15. On-line Mass Spectrometric Study of Heavy-Ion Induced Reactions at Energies up to 86 MeV/amu

    CERN Multimedia

    2002-01-01

    The aim of the experiment was to measure isotopic distributions of Li, Na, K, Rb, Cs and Fr as reaction fragments in heavy ion collisions. In order to get an overall view of the new energy range for heavy ions available from the SC, different energies and projectile-target combinations had to be studied. The data taking status is now finished. |1|2C and |1|8O beams were used in bombarding |1|2C, |9|3Nb, |1|8|1Ta and |2|3|8U in order to look at target fragmentation, projectile fragmentation and evaporative residues of spallation processes. The experimental apparatus is composed of three parts: \\item a)~A target-oven-ionizer assembly where selective thermal diffusion and selective surface ionization takes place in order to obtain a chemical separation of the reaction products. \\item b)~The mass spectrometer where the different-mass fragments are selected. \\item c)~An electrostatic ion beam line through which the fragments are transported to a low-background area where the detector (an electron multiplier) is lo...

  16. Mass spectrometric study of the negative and positive secondary ions emitted from ethanol microdroplets by MeV-energy heavy ion impact

    Science.gov (United States)

    Kitajima, Kensei; Majima, Takuya; Nishio, Tatsuya; Oonishi, Yoshiki; Mizutani, Shiori; Kohno, Jun-ya; Saito, Manabu; Tsuchida, Hidetsugu

    2018-06-01

    We have investigated the negative and positive secondary ions emitted from ethanol droplets by 4.0-MeV C3+ impact to reveal the characteristic features of the reaction processes induced by fast heavy ions at the liquid ethanol surface. Analysis of the secondary ions was performed by time-of-flight mass spectrometry for microdroplet targets in a high vacuum environment. Fragment ions, deprotonated cluster ions, and trace amounts of the reaction product ions are observed in the negative secondary ions. The main fragment anions are C2HmO- (m = 1, 3, and 5) and C2H- generated by loss of hydrogen and oxygen atoms. The reaction product anions include deprotonated glycols, larger alcohols, and their dehydrated and dehydrogenated forms generated by secondary reactions between fragments and radicals. Furthermore, C3Hm- (m = 0-2) and C4Hm- (m = 0 and 1) are observed, which could be produced through a plasma state generated in the heavy ion track. Deprotonated ethanol cluster ions, [(EtOH)n - H]-, are observed up to about n = 25. [(EtOH)n - H]- have smaller kinetic energies than the protonated cluster ions (EtOH)nH+. This probably represents the effect of the positive Coulomb potential transiently formed in the ion track. We also discuss the size distributions and structures of the water- and CH2OH-radical-attached ethanol cluster ions.

  17. Large fragment production calculations in relativistic heavy-ion reactions

    International Nuclear Information System (INIS)

    Seixas de Oliveira, L.F.

    1978-12-01

    The abrasion-ablation model is briefly described and then used to calculate cross sections for production of large fragments resulting from target or projectile fragmentation in high-energy heavy-ion collisions. The number of nucleons removed from the colliding nuclei in the abrasion stage and the excitation energy of the remaining fragments (primary products) are calculated with the geometrical picture of two different models: the fireball and the firestreak models. The charge-to-mass dispersion of the primary products is calculated using either a model which assumes no correlations between proton and neutron positions inside the nucleus (hypergeometric distribution) or a model based upon the zero-point oscillations of the giant dipole resonance (NUC-GDR). Standard Weisskopf--Ewing statistical evaporation calculations are used to calculate final product distributions. Results of the pure abrasion-ablation model are compared with a variety of experimental data. The comparisons show the insufficiency of the extra-surface energy term used in the abrasion calculations. A frictional spectator interaction (FSI) is introduced which increases the average excitation energy of the primary products, and improves the results considerably in most cases. Agreements and discrepancies of the results calculated with the different theoretical assumptions and the experimental data are studied. Of particular relevance is the possibility of observing nuclear ground-state correlations.Results of the recently completed experiment of fragmentation of 213 Mev/A 40 Ar projectiles are studied and shown not to be capable of answering that question unambiguously. But predictions for the upcoming 48 Ca fragmentation experiment clearly show the possibility of observing correlation effects. 78 references

  18. Versatile lipid profiling by liquid chromatography–high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer

    International Nuclear Information System (INIS)

    Gallart-Ayala, H.; Courant, F.; Severe, S.; Antignac, J.-P.; Morio, F.; Abadie, J.; Le Bizec, B.

    2013-01-01

    Graphical abstract: -- Highlights: •Lipidomics, high resolution mass spectrometry, polarity switching, serum, canine mammary cancer. -- Abstract: Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC–HRMS or LC–MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC–HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and “all ion fragmentation” (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale

  19. Versatile lipid profiling by liquid chromatography–high resolution mass spectrometry using all ion fragmentation and polarity switching. Preliminary application for serum samples phenotyping related to canine mammary cancer

    Energy Technology Data Exchange (ETDEWEB)

    Gallart-Ayala, H., E-mail: laberca@oniris-nantes.fr [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France); Courant, F.; Severe, S.; Antignac, J.-P. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France); Morio, F.; Abadie, J. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), Cancers Animaux, Modèles pour la Recherche en Oncologie Comparée (AMaROC), Site de la Chantrerie–CS50707, 44307 Nantes cedex 3 (France); Le Bizec, B. [LUNAM, Ecole Nationale Vétérinaire, Agroalimentaire et de l’Alimentation Nantes Atlantique (Oniris), USC 1329 INRA Laboratoire d’Etude des résidus et Contaminants dans les Aliments (LABERCA), Site de la Chantrerie – CS50707, 44307 Nantes cedex 3 (France)

    2013-09-24

    Graphical abstract: -- Highlights: •Lipidomics, high resolution mass spectrometry, polarity switching, serum, canine mammary cancer. -- Abstract: Lipids represent an extended class of substances characterized by such high variety and complexity that makes their unified analyses by liquid chromatography coupled to either high resolution or tandem mass spectrometry (LC–HRMS or LC–MS/MS) a real challenge. In the present study, a new versatile methodology associating ultra high performance liquid chromatography coupled to high resolution tandem mass spectrometry (UHPLC–HRMS/MS) have been developed for a comprehensive analysis of lipids. The use of polarity switching and “all ion fragmentation” (AIF) have been two action levels particularly exploited to finally permit the detection and identification of a multi-class and multi-analyte extended range of lipids in a single run. For identification purposes, both higher energy collision dissociation (HCD) and in-source CID (collision induced dissociation) fragmentation were evaluated in order to obtain information about the precursor and product ions in the same spectra. This approach provides both class-specific and lipid-specific fragments, enhancing lipid identification. Finally, the developed method was applied for differential phenotyping of serum samples collected from pet dogs developing spontaneous malignant mammary tumors and health controls. A biological signature associated with the presence of cancer was then successfully revealed from this lipidome analysis, which required to be further investigated and confirmed at larger scale.

  20. Fission fragment mass distributions via prompt γ-ray spectroscopy

    Indian Academy of Sciences (India)

    The distribution of fragment masses formed in nuclear fission is one of the most strik- ing features .... 80. 100. 120. 140. 160. 10. 3. 10. 4. Fragment Mass. Relative yield. Sn. Cd. Te. Pd ... the secondary fragment at Z = 50 and N = 82 shells, where the yields are depleted. Both ... More systematic experimental data are required.

  1. 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.

    Science.gov (United States)

    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

  2. Fragmentation of molecular ions in slow electron collisions

    International Nuclear Information System (INIS)

    Novotny, Steffen

    2008-01-01

    The fragmentation of positively charged hydrogen molecular ions by the capture of slow electrons, the so called dissociative recombination (DR), has been investigated in storage ring experiments at the TSR, Heidelberg, where an unique twin-electron-beam arrangement was combined with high resolution fragment imaging detection. Provided with well directed cold electrons the fragmentation kinematics were measured down to meV collision energies where pronounced rovibrational Feshbach resonances appear in the DR cross section. For thermally excited HD + the fragmentation angle and the kinetic energy release were studied at variable precisely controlled electron collision energies on a dense energy grid from 10 to 80 meV. The anisotropy described for the first time by Legendre polynomials higher 2 nd order and the extracted rotational state contributions were found to vary on a likewise narrow energy scale as the rotationally averaged DR rate coefficient. Ro-vibrationally resolved DR experiments were performed on H 2 + produced in distinct internal excitations by a novel ion source. Both the low-energy DR rate as well as the fragmentation dynamics at selected resonances were measured individually in the lowest two vibrational and first three excited rotational states. State-specific DR rates and angular dependences are reported. (orig.)

  3. Fragmentation of molecular ions in slow electron collisions

    Energy Technology Data Exchange (ETDEWEB)

    Novotny, Steffen

    2008-06-25

    The fragmentation of positively charged hydrogen molecular ions by the capture of slow electrons, the so called dissociative recombination (DR), has been investigated in storage ring experiments at the TSR, Heidelberg, where an unique twin-electron-beam arrangement was combined with high resolution fragment imaging detection. Provided with well directed cold electrons the fragmentation kinematics were measured down to meV collision energies where pronounced rovibrational Feshbach resonances appear in the DR cross section. For thermally excited HD{sup +} the fragmentation angle and the kinetic energy release were studied at variable precisely controlled electron collision energies on a dense energy grid from 10 to 80 meV. The anisotropy described for the first time by Legendre polynomials higher 2{sup nd} order and the extracted rotational state contributions were found to vary on a likewise narrow energy scale as the rotationally averaged DR rate coefficient. Ro-vibrationally resolved DR experiments were performed on H{sub 2}{sup +} produced in distinct internal excitations by a novel ion source. Both the low-energy DR rate as well as the fragmentation dynamics at selected resonances were measured individually in the lowest two vibrational and first three excited rotational states. State-specific DR rates and angular dependences are reported. (orig.)

  4. Mass spectrometry analysis of etch products from CR-39 plastic irradiated by heavy ions

    Science.gov (United States)

    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.

  5. Structural characterization of phospholipids by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Marto, J A; White, F M; Seldomridge, S; Marshall, A G

    1995-11-01

    Matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry provides for structural analysis of the principal biological phospholipids: glycerophosphatidylcholine, -ethanolamine, -serine, and -inositol. Both positive and negative molecular or quasimolecular ions are generated in high abundance. Isolated molecular ions may be collisionally activated in the source side of a dual trap mass analyzer, yielding fragments serving to identify the polar head group (positive ion mode) and fatty acid side chains (negative ion mode). Azimuthal quadrupolar excitation following collisionally activated dissociation refocuses productions close to the solenoid axis; subsequent transfer of product ions to the analyzer ion trap allows for high-resolution mass analysis. Cyro-cooling of the sample probe with liquid nitrogen greatly reduces matrix adduction encountered in the negative ion mode.

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

    Science.gov (United States)

    König, Simone; Marco, Heather; Gäde, Gerd

    2017-11-01

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

  7. Evidence for Sequence Scrambling and Divergent H/D Exchange Reactions of Doubly-Charged Isobaric b-Type Fragment Ions

    Science.gov (United States)

    Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H.; Somogyi, Arpad; Solouki, Touradj

    2014-02-01

    To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10 2+ that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10 2+ and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10 2+, suggesting that b10 2+ may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10 2+; over 30 % of the observed SORI-CID fragment ions from substance P b10 2+ had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10 2+, whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10 2+.

  8. Evidence for sequence scrambling and divergent H/D exchange reactions of doubly-charged isobaric b-type fragment ions.

    Science.gov (United States)

    Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H; Somogyi, Arpad; Solouki, Touradj

    2014-02-01

    To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10(2+) that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10(2+) and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10(2+), suggesting that b10(2+) may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10(2+); over 30% of the observed SORI-CID fragment ions from substance P b10(2+) had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10(2+), whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10(2+).

  9. Multiple and sequential data acquisition method: an improved method for fragmentation and detection of cross-linked peptides on a hybrid linear trap quadrupole Orbitrap Velos mass spectrometer.

    Science.gov (United States)

    Rudashevskaya, Elena L; Breitwieser, Florian P; Huber, Marie L; Colinge, Jacques; Müller, André C; Bennett, Keiryn L

    2013-02-05

    The identification and validation of cross-linked peptides by mass spectrometry remains a daunting challenge for protein-protein cross-linking approaches when investigating protein interactions. This includes the fragmentation of cross-linked peptides in the mass spectrometer per se and following database searching, the matching of the molecular masses of the fragment ions to the correct cross-linked peptides. The hybrid linear trap quadrupole (LTQ) Orbitrap Velos combines the speed of the tandem mass spectrometry (MS/MS) duty circle with high mass accuracy, and these features were utilized in the current study to substantially improve the confidence in the identification of cross-linked peptides. An MS/MS method termed multiple and sequential data acquisition method (MSDAM) was developed. Preliminary optimization of the MS/MS settings was performed with a synthetic peptide (TP1) cross-linked with bis[sulfosuccinimidyl] suberate (BS(3)). On the basis of these results, MSDAM was created and assessed on the BS(3)-cross-linked bovine serum albumin (BSA) homodimer. MSDAM applies a series of multiple sequential fragmentation events with a range of different normalized collision energies (NCE) to the same precursor ion. The combination of a series of NCE enabled a considerable improvement in the quality of the fragmentation spectra for cross-linked peptides, and ultimately aided in the identification of the sequences of the cross-linked peptides. Concurrently, MSDAM provides confirmatory evidence from the formation of reporter ions fragments, which reduces the false positive rate of incorrectly assigned cross-linked peptides.

  10. New experiments in organic, fast-atom-bomdardment, and secondary-ion mass spectrometry

    International Nuclear Information System (INIS)

    DiDonato, G.C.

    1987-01-01

    The goal of research presented in this dissertation is the creative use of new ionization and instrumental techniques in mass spectrometry. This goal manifests itself in three areas of mass spectrometry. In the first portion, modern, state-of-the-art instrumentation and new experiments were used to re-examine the mass spectra of transition-metal acetates and acetylacetonates. High resolution, chemical ionization, negative chemical ionization, and extended-mass-range mass spectrometry uncovered a wealth of new gas-phase ionic species. Energy-resolved mass spectrometry/mass spectrometry was applied to the characterization of molecular and fragment ion first-row transition-metal acetylacetonates, and comprises the second portion of the thesis. Studies in fast-atom-bombardment mass spectrometry are the subject of the third portion of the dissertation. Since fast-atom bombardment samples a liquid matrix, absolute and relative abundances of sputtered secondary ions are influenced by solution chemistry. The design and construction of an imaging secondary-ion mass spectrometer is the subject of the final portion of the thesis. This instrument provides for direct mass-spectrometric analysis of thin-layer and paper chromatograms and electrophoretograms

  11. Identification of membrane proteins by tandem mass spectrometry of protein ions

    Science.gov (United States)

    Carroll, Joe; Altman, Matthew C.; Fearnley, Ian M.; Walker, John E.

    2007-01-01

    The most common way of identifying proteins in proteomic analyses is to use short segments of sequence (“tags”) determined by mass spectrometric analysis of proteolytic fragments. The approach is effective with globular proteins and with membrane proteins with significant polar segments between membrane-spanning α-helices, but it is ineffective with other hydrophobic proteins where protease cleavage sites are either infrequent or absent. By developing methods to purify hydrophobic proteins in organic solvents and by fragmenting ions of these proteins by collision induced dissociation with argon, we have shown that partial sequences of many membrane proteins can be deduced easily by manual inspection. The spectra from small proteolipids (1–4 transmembrane α-helices) are dominated usually by fragment ions arising from internal amide cleavages, from which internal sequences can be obtained, whereas the spectra from larger membrane proteins (5–18 transmembrane α-helices) often contain fragment ions from N- and/or C-terminal parts yielding sequences in those regions. With these techniques, we have, for example, identified an abundant protein of unknown function from inner membranes of mitochondria that to our knowledge has escaped detection in proteomic studies, and we have produced sequences from 10 of 13 proteins encoded in mitochondrial DNA. They include the ND6 subunit of complex I, the last of its 45 subunits to be analyzed. The procedures have the potential to be developed further, for example by using newly introduced methods for protein ion dissociation to induce fragmentation of internal regions of large membrane proteins, which may remain partially folded in the gas phase. PMID:17720804

  12. Validating PHITS for heavy ion fragmentation reactions

    International Nuclear Information System (INIS)

    Ronningen, Reginald M.

    2015-01-01

    The performance of the Monte Carlo code system PHITS is validated for heavy-ion transport capabilities by performing simulations and comparing results against experimental data from heavy-ion reactions of benchmark quality. These data are from measurements of isotope yields produced in the fragmentation of a 140 MeV/u "4"8Ca beam on a beryllium target and on a tantalum target. The results of this study show that PHITS performs reliably. (authors)

  13. Liquid-vapor phase transition, collective flow and entropy determination from future measurements of intermediate mass fragments

    International Nuclear Information System (INIS)

    Coffin, J.P.

    1991-01-01

    Some global variables reflecting the highly collective character of nuclear matter produced in relativistic heavy-ion collisions are briefly reviewed on the basis of presently available experimental results and of Quantum Statistical Model and Quantum Molecular Dynamic Model predictions relative to intermediate mass fragments. Possible future measurements are suggested. (author) 27 refs., 8 figs

  14. Mass and kinetic-energy distributions of fragments formed in the heavy-ion-induced fission of 208Po

    International Nuclear Information System (INIS)

    Cuninghame, J.G.; Goodall, J.A.B.

    1980-01-01

    Fission fragments following the decay of a 208 Po compound nucleus have been observed by using radiochemical and particle-counting techniques. The (α+ 204 Pb), ( 12 C+ 196 Pt) and ( 16 O+ 192 Os) reactions were studied at two or three bombarding energies, covering overlapping ranges of excitation energies. - Radiochemical separations of As, Br, Y, Nb, Tc, Ag, Sb and I isotopes were made from catcher foils sandwiching isotopic targets, and their isotopic yield distributions determined. The distributions are used to estimate the average number of neutrons associated with each fission event, including neutrons emitted before and after fission. - Prompt coincidence measurements of fragments are used to derive the overall mass and kinetic-energy distributions of primary fragments, taking into account the effects of pre- and post-fission neutron emission. The mass distributions are well fitted by the statistical theory, at a temperature corresponding to an excitation about 10 MeV above that at the saddle point. No evidence is found for an increase of kinetic-energy with increasing angular momentum of the compound nucleus. (author)

  15. reSpect: Software for Identification of High and Low Abundance Ion Species in Chimeric Tandem Mass Spectra

    Science.gov (United States)

    Shteynberg, David; Mendoza, Luis; Hoopmann, Michael R.; Sun, Zhi; Schmidt, Frank; Deutsch, Eric W.; Moritz, Robert L.

    2015-11-01

    Most shotgun proteomics data analysis workflows are based on the assumption that each fragment ion spectrum is explained by a single species of peptide ion isolated by the mass spectrometer; however, in reality mass spectrometers often isolate more than one peptide ion within the window of isolation that contribute to additional peptide fragment peaks in many spectra. We present a new tool called reSpect, implemented in the Trans-Proteomic Pipeline (TPP), which enables an iterative workflow whereby fragment ion peaks explained by a peptide ion identified in one round of sequence searching or spectral library search are attenuated based on the confidence of the identification, and then the altered spectrum is subjected to further rounds of searching. The reSpect tool is not implemented as a search engine, but rather as a post-search engine processing step where only fragment ion intensities are altered. This enables the application of any search engine combination in the iterations that follow. Thus, reSpect is compatible with all other protein sequence database search engines as well as peptide spectral library search engines that are supported by the TPP. We show that while some datasets are highly amenable to chimeric spectrum identification and lead to additional peptide identification boosts of over 30% with as many as four different peptide ions identified per spectrum, datasets with narrow precursor ion selection only benefit from such processing at the level of a few percent. We demonstrate a technique that facilitates the determination of the degree to which a dataset would benefit from chimeric spectrum analysis. The reSpect tool is free and open source, provided within the TPP and available at the TPP website.

  16. The collision of a hypervelocity massive projectile with free-standing graphene: Investigation of secondary ion emission and projectile fragmentation

    Science.gov (United States)

    Geng, Sheng; Verkhoturov, Stanislav V.; Eller, Michael J.; Della-Negra, Serge; Schweikert, Emile A.

    2017-02-01

    We present here the study of the individual hypervelocity massive projectiles (440-540 keV, 33-36 km/s Au4004+ cluster) impact on 1-layer free-standing graphene. The secondary ions were detected and recorded separately from each individual impact in the transmission direction using a time-of-flight mass spectrometer. We observed C1-10± ions emitted from graphene, the projectiles which penetrated the graphene, and the Au1-3± fragment ions in mass spectra. During the projectile-graphene interaction, the projectile loses ˜15% of its initial kinetic energy (˜0.18 keV/atom, 72 keV/projectile). The Au projectiles are neutralized when approaching the graphene and then partially ionized again via electron tunneling from the hot rims of the holes on graphene, obtaining positive and negative charges. The projectile reaches an internal energy of ˜450-500 eV (˜4400-4900 K) after the impact and then undergoes a ˜90-100 step fragmentation with the ejection of Au1 atoms in the experimental time range of ˜0.1 μs.

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

    Science.gov (United States)

    Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

    2010-07-22

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

  18. Fragments emission from light mass composite nuclei within collective clusterization mechanism

    International Nuclear Information System (INIS)

    Singh, BirBikram

    2016-01-01

    Based on the quantum mechanical fragmentation theory (QMFT) the dynamical cluster decay model (DCM) has been developed by Gupta and Collaborators to study the decay of hot and rotating compound systems. Number of compound nuclei (CN) in different mass regions have been studied quite extensively while taking into consideration nuclear structure effects in the same. It is quite relevant to mention here that in the binary decay of CN nuclear structure effects comes into picture, within DCM, via preformation probability P_0 of the complimentary fragments before penetrating the potential barrier between them with certain probability P . It is interesting to note here that the statistical models treat various decay modes of the CN on different footing contrary to the DCM. In very light mass region the decay of number of composite systems "2"0","2"1","2"2Ne*, "2"6"-"2"9Al, "2"8Si, "3"1P, "3"2S, "3"9K and "4"0Ca*, formed in low energy heavy ion reactions, have been investigated for different reaction mechanisms particularly fusion-fission (FF) and deep inelastic orbiting (DIO) from equilibrated and non-equilibrated compound nucleus processes, respectively

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

    Science.gov (United States)

    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.

  20. The application of "double isolation" in Fourier transform ion cyclotron resonance sustained off-resonance irradiation collisionally-induced dissociation tandem mass spectrometry to remove labile isobaric impurities.

    Science.gov (United States)

    Gates, Paul J; Lopes, Norberto P; Pinto, Emani; Colepicolo, Pio; Cardozo, Karina H M

    2011-01-01

    This study reports the application of "double isolation" in sustained off-resonance irradiation collisionally-induced dissociation tandem mass spectrometry (SORI-CID-MS/MS) to remove radio- frequency (RF) fragment ions of very close mass isobaric ions (0.02 m/z apart). Analyses were performed with a fraction of a biological extract isolated from a macroalgae containing the mycosporine-like amino acid asterina-330. Direct isolation of the precursor ion by narrowing the isolation window proved ineffective as it impinged upon the required ion thus substantially reducing its intensity. By increasing the correlated sweep time, ejection efficiency of the isolation was improved, but caused the unwanted side-effect of RF fragmentation of labile ions. Finally, by skipping the ion activation step and performing a second isolation (in the MS(3) module) the RF fragments from the first isolation were removed leaving a very pure isolation of the required precursor ion and allowed a very clean CID fragmentation. We demonstrated that the m/z 272.1351 ion is derived from the loss of NH(3) from m/z 289.1620 isobaric impurity and is not related to asterina-330. This application represents a powerful tool to remove unwanted ions in the MS/MS spectrum that result from fragmentation of isobaric ions.

  1. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1989-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this omission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of energy, mass, and angular momentum transfer in incomplete fusion and non-compound reactions. This thread joins the apparently divergent subjects covered in this report

  2. Jet Fragmentation Function Moments in Heavy Ion Collisions

    CERN Document Server

    Cacciari, Matteo; Salam, Gavin P; Soyez, Gregory

    2013-01-01

    The nature of a jet's fragmentation in heavy-ion collisions has the potential to cast light on the mechanism of jet quenching. However the presence of the huge underlying event complicates the reconstruction of the jet fragmentation function as a function of the momentum fraction z of hadrons in the jet. Here we propose the use of moments of the fragmentation function. These quantities appear to be as sensitive to quenching modifications as the fragmentation function directly in z. We show that they are amenable to background subtraction using the same jet-area based techniques proposed in the past for jet p_t's. Furthermore, complications due to correlations between background-fluctuation contributions to the jet's p_t and to its particle content are easily corrected for.

  3. Organic secondary ion mass spectrometry: sensitivity enhancement by gold deposition.

    Science.gov (United States)

    Delcorte, A; Médard, N; Bertrand, P

    2002-10-01

    Hydrocarbon oligomers, high-molecular-weight polymers, and polymer additives have been covered with 2-60 nmol of gold/cm2 in order to enhance the ionization efficiency for static secondary ion mass spectrometry (s-SIMS) measurements. Au-cationized molecules (up to -3,000 Da) and fragments (up to the trimer) are observed in the positive mass spectra of metallized polystyrene (PS) oligomer films. Beyond 3,000 Da, the entanglement of polymer chains prevents the ejection of intact molecules from a "thick" organic film. This mass limit can be overcome by embedding the polymer chains in a low-molecular-weight matix. The diffusion of organic molecules over the metal surfaces is also demonstrated for short PS oligomers. In the case of high-molecular-weight polymers (polyethylene, polypropylene, PS) and polymer additives (Irganox 1010, Irgafos 168), the metallization procedure induces a dramatic increase of the fingerprint fragment ion yields as well as the formation of new Aucationized species that can be used for chemical diagnostics. In comparison with the deposition of submonolayers of organic molecules on metallic surfaces, metal evaporation onto organic samples provides a comparable sensitivity enhancement. The distinct advantage of the metal evaporation procedure is that it can be used for any kind of organic sample, irrespective of thickness, opening new perspectives for "real world" sample analysis and chemical imaging by s-SIMS.

  4. reSpect: software for identification of high and low abundance ion species in chimeric tandem mass spectra.

    Science.gov (United States)

    Shteynberg, David; Mendoza, Luis; Hoopmann, Michael R; Sun, Zhi; Schmidt, Frank; Deutsch, Eric W; Moritz, Robert L

    2015-11-01

    Most shotgun proteomics data analysis workflows are based on the assumption that each fragment ion spectrum is explained by a single species of peptide ion isolated by the mass spectrometer; however, in reality mass spectrometers often isolate more than one peptide ion within the window of isolation that contribute to additional peptide fragment peaks in many spectra. We present a new tool called reSpect, implemented in the Trans-Proteomic Pipeline (TPP), which enables an iterative workflow whereby fragment ion peaks explained by a peptide ion identified in one round of sequence searching or spectral library search are attenuated based on the confidence of the identification, and then the altered spectrum is subjected to further rounds of searching. The reSpect tool is not implemented as a search engine, but rather as a post-search engine processing step where only fragment ion intensities are altered. This enables the application of any search engine combination in the iterations that follow. Thus, reSpect is compatible with all other protein sequence database search engines as well as peptide spectral library search engines that are supported by the TPP. We show that while some datasets are highly amenable to chimeric spectrum identification and lead to additional peptide identification boosts of over 30% with as many as four different peptide ions identified per spectrum, datasets with narrow precursor ion selection only benefit from such processing at the level of a few percent. We demonstrate a technique that facilitates the determination of the degree to which a dataset would benefit from chimeric spectrum analysis. The reSpect tool is free and open source, provided within the TPP and available at the TPP website. Graphical Abstract ᅟ.

  5. First Isochronous Time-of-Flight Mass Measurements of Short-Lived Projectile Fragments in the ESR

    International Nuclear Information System (INIS)

    Stadlmann, J.; Geissel, H.; Hausmann, M.; Nolden, F.; Radon, T.; Schatz, H.; Scheidenberger, C.; Attallah, F.; Beckert, K.; Bosch, F.; Falch, M.; Franczak, B.; Franzke, B.; Kerscher, Th.; Klepper, O.; Kluge, H.J.; Kozhuharov, C.; Loebner, K.E.G.; Muenzenberg, G.; Novikov, Yu.N.; Steck, M.; Sun, Z.; Suemmerer, K.; Weick, H.; Wollnik, H.

    2000-01-01

    A new method for precise mass measurements of short-lived hot nuclei is presented. These nuclei were produced via projectile fragmentation, separated with the FRS and injected into the storage ring ESR being operated in the isochronous mode. The revolution time of the ions is measured with a time-of-flight detector sensitive to single particles. This new method allows access to exotic nuclei with half-lives in the microsecond region. First results from this novel method obtained with measurements on neutron-deficient fragments of a chromium primary beam with half-lives down to 50 ms are reported. A precision of deltam/m ≤ 5 · 10 -6 has been achieved

  6. Atmospheric-pressure solution-cathode glow discharge: A versatile ion source for atomic and molecular mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Andrew J. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Williams, Kelsey L. [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Hieftje, Gary M. [Department of Chemistry, Indiana University, Bloomington, IN, 47405 (United States); Shelley, Jacob T., E-mail: shellj@rpi.edu [Department of Chemistry and Biochemistry, Kent State University, Kent, OH, 44242 (United States); Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY, 12180 (United States)

    2017-01-15

    An atmospheric-pressure solution-cathode glow discharge (SCGD) has been evaluated as an ion source for atomic, molecular, and ambient desorption/ionization mass spectrometry. The SCGD consists of a direct-current plasma, supported in the ambient air in the absence of gas flows, and sustained upon the surface of a flowing liquid cathode. Analytes introduced in the flowing liquid, as an ambient gas, or as a solid held near the plasma are vaporized and ionized by interactions within or near the discharge. Introduction of acidic solutions containing metal salts produced bare elemental ions as well as H{sub 2}O, OH{sup −} and NO{sub 3}{sup −} adducts. Detection limits for these elemental species ranged from 0.1 to 4 ppb, working curves spanned more than 4 orders of linear dynamic range, and precision varied between 5 and 16% relative standard deviation. Small organic molecules were also efficiently ionized from solution, and both the intact molecular ion and fragments were observed in the resulting SCGD mass spectra. Fragmentation of molecular species was found to be tunable; high discharge currents led to harder ionization, while low discharge currents produced stronger molecular-ion signals. Ambient gases and solids, desorbed by the plasma from a glass probe, were also readily ionized by the SCGD. Indeed, strong analyte signals were obtained from solid samples placed at least 2 cm from the plasma. These findings indicate that the SCGD might be useful also for ambient desorption/ionization mass spectrometry. Combined with earlier results that showed the SCGD is useful for ionization of labile biomolecules, the results here indicate that the SCGD is a highly versatile ion source capable of providing both elemental and molecular mass-spectral information. - Highlights: • Solution-cathode glow discharge used as an ionization source for mass spectrometry. • SCGD-MS can provide atomic as well as intact molecular mass spectra. • Atomic limits of detection range

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

    Science.gov (United States)

    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.

  8. Mass spectrometric comparison of swift heavy ion-induced and anaerobic thermal degradation of polymers

    Science.gov (United States)

    Lima, V.; Hossain, U. H.; Walbert, T.; Seidl, T.; Ensinger, W.

    2018-03-01

    The study of polymers irradiated by highly energetic ions and the resulting radiation-induced degradation is of major importance for space and particle accelerator applications. The mechanism of ion-induced molecular fragmentation of polyethylene, polyethyleneimine and polyamide was investigated by means of mass spectrometry and infrared spectroscopy. The results show that the introduction of nitrogen and oxygen into the polymer influences the stability rendering aliphatic polymers with heteroatoms less stable. A comparison to thermal decomposition data from literature reveals that ion-induced degradation is different in its bond fracture mechanism. While thermal degradation starts at the weakest bond, which is usually the carbon-heteroatom bond, energetic ion irradiation leads in the first step to scission of all types of bonds creating smaller molecular fragments. This is due to the localized extreme energy input under non-equilibrium conditions when the ions transfer kinetic energy onto electrons. These findings are of relevance for the choice of polymers for long-term application in both space and accelerator facilities.

  9. Jet fragmentation function moments in heavy ion collisions

    Energy Technology Data Exchange (ETDEWEB)

    Cacciari, Matteo [UPMC Univ. Paris 6 et CNRS UMR 7589, LPTHE, Paris (France); Universite Paris Diderot, Paris (France); Quiroga-Arias, Paloma [UPMC Univ. Paris 6 et CNRS UMR 7589, LPTHE, Paris (France); Salam, Gavin P. [UPMC Univ. Paris 6 et CNRS UMR 7589, LPTHE, Paris (France); CERN, Department of Physics, Theory Unit, Geneva 23 (Switzerland); Princeton University, Department of Physics, Princeton, NJ (United States); Soyez, Gregory [CNRS URA 2306, Institut de Physique Theorique, CEA Saclay, Gif-sur-Yvette (France)

    2013-03-15

    The nature of a jet's fragmentation in heavy-ion collisions has the potential to cast light on the mechanism of jet quenching. However, the presence of the huge underlying event complicates the reconstruction of the jet fragmentation function as a function of the momentum fraction z of hadrons in the jet. Here we propose the use of moments of the fragmentation function. These quantities appear to be as sensitive to quenching modifications as the fragmentation function directly in z. We show that they are amenable to background subtraction using the same jet-area-based techniques proposed in the past for jet p{sub t} 's. Furthermore, complications due to correlations between background-fluctuation contributions to the jet's p{sub t} and to its particle content are easily corrected for. (orig.)

  10. Jet fragmentation function moments in heavy ion collisions

    International Nuclear Information System (INIS)

    Cacciari, Matteo; Quiroga-Arias, Paloma; Salam, Gavin P.; Soyez, Gregory

    2013-01-01

    The nature of a jet's fragmentation in heavy-ion collisions has the potential to cast light on the mechanism of jet quenching. However, the presence of the huge underlying event complicates the reconstruction of the jet fragmentation function as a function of the momentum fraction z of hadrons in the jet. Here we propose the use of moments of the fragmentation function. These quantities appear to be as sensitive to quenching modifications as the fragmentation function directly in z. We show that they are amenable to background subtraction using the same jet-area-based techniques proposed in the past for jet p t 's. Furthermore, complications due to correlations between background-fluctuation contributions to the jet's p t and to its particle content are easily corrected for. (orig.)

  11. Detection of sputtered molecular doubly charged anions: a comparison of secondary-ion mass spectrometry (SIMS) and accelerator mass spectrometry (AMS)

    International Nuclear Information System (INIS)

    Gnaser, Hubert; Golser, Robin; Kutschera, Walter; Priller, Alfred; Steier, Peter; Vockenhuber, Christof

    2004-01-01

    The detection of small molecular dianions by secondary-ion mass spectrometry (SIMS) and by accelerator mass spectrometry (AMS) is compared. In SIMS, the existence of these dianions can be identified safely if the total mass number of the molecule is odd and the dianion is hence detected at a half-integral mass number. The occurrence of fragmentation processes which may interfere with this scheme, is illustrated by means of the energy spectra of singly and doubly charged negative cluster ions. As compared to SIMS, AMS can rely, in addition, on the break-up of molecular species in the stripping process: this allows to monitor the simultaneous arrival of several atomic constituents with a clear energetic pattern in coincidence at the detector. This feature is exemplified for the C 10 2- dianion

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

    Science.gov (United States)

    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.

  13. Solution of the Boltzmann equation for primary light ions and the transport of their fragments

    Directory of Open Access Journals (Sweden)

    J. Kempe

    2010-10-01

    Full Text Available The Boltzmann equation for the transport of pencil beams of light ions in semi-infinite uniform media has been calculated. The equation is solved for the practically important generalized 3D case of Gaussian incident primary light ion beams of arbitrary mean square radius, mean square angular spread, and covariance. The transport of the associated fragments in three dimensions is derived based on the known transport of the primary particles, taking the mean square angular spread of their production processes, as well as their energy loss and multiple scattering, into account. The analytical pencil and broad beam depth fluence and absorbed dose distributions are accurately expressed using recently derived analytical energy and range formulas. The contributions from low and high linear energy transfer (LET dose components were separately identified using analytical expressions. The analytical results are compared with SHIELD-HIT Monte Carlo (MC calculations and found to be in very good agreement. The pencil beam fluence and absorbed dose distributions of the primary particles are mainly influenced by an exponential loss of the primary ions combined with an increasing lateral spread due to multiple scattering and energy loss with increasing penetration depth. The associated fluence of heavy fragments is concentrated at small radii and so is the LET and absorbed dose distribution. Their transport is also characterized by the buildup of a slowing down spectrum which is quite similar to that of the primaries but with a wider energy and angular spread at increasing penetration depths. The range of the fragments is shorter or longer depending on their nuclear mass to charge ratio relative to that of the primary ions. The absorbed dose of the heavier fragments is fairly similar to that of the primary ions and also influenced by a rapidly increasing energy loss towards the end of their ranges. The present analytical solution of the Boltzmann equation

  14. Complementary b/y fragment ion pairs from post-source decay of metastable YahO for calibration of MALDI-TOF-TOF-MS/MS

    Science.gov (United States)

    Complementary b/y fragment ion pairs from post-source decay (PSD) of metastable YahO protein ion were evaluated for use in the calibration of MALDI-TOF-TOF for tandem mass spectrometry (MS/MS). The yahO gene from pathogenic Escherichia coli O157:H7 strain EDL933 was cloned into a pBAD18 plasmid vect...

  15. FIRST experiment: Fragmentation of Ions Relevant for Space and Therapy

    International Nuclear Information System (INIS)

    Agodi, C; Bondì, M; Cavallaro, M; Carbone, D; Cirrone, G A P; Cuttone, G; Abou-Haidar, Z; Alvarez, M A G; Bocci, A; Aumann, T; Durante, M; Balestra, F; Battistoni, G; Bohlen, T T; Boudard, A; Brunetti, A; Carpinelli, M; Cappuzzello, F; Cortes-Giraldo, M A; Napoli, M De

    2013-01-01

    Nuclear fragmentation processes are relevant in different fields of basic research and applied physics and are of particular interest for tumor therapy and for space radiation protection applications. The FIRST (Fragmentation of Ions Relevant for Space and Therapy) experiment at SIS accelerator of GSI laboratory in Darmstadt, has been designed for the measurement of different ions fragmentation cross sections at different energies between 100 and 1000 MeV/nucleon. The experiment is performed by an international collaboration made of institutions from Germany, France, Italy and Spain. The experimental apparatus is partly based on an already existing setup made of the ALADIN magnet, the MUSIC IV TPC, the LAND2 neutron detector and the TOFWALL scintillator TOF system, integrated with newly designed detectors in the interaction Region (IR) around the carbon removable target: a scintillator Start Counter, a Beam Monitor drift chamber, a silicon Vertex Detector and a Proton Tagger for detection of light fragments emitted at large angles (KENTROS). The scientific program of the FIRST experiment started on summer 2011 with the study of the 400 MeV/nucleon 12C beam fragmentation on thin (8 mm) carbon target.

  16. FIRST experiment: Fragmentation of Ions Relevant for Space and Therapy

    Science.gov (United States)

    Agodi, C.; Abou-Haidar, Z.; Alvarez, M. A. G.; Aumann, T.; Balestra, F.; Battistoni, G.; Bocci, A.; Bohlen, T. T.; Bondì, M.; Boudard, A.; Brunetti, A.; Carpinelli, M.; Cappuzzello, F.; Cavallaro, M.; Carbone, D.; Cirrone, G. A. P.; Cortes-Giraldo, M. A.; Cuttone, G.; De Napoli, M.; Durante, M.; Fernandez-Garcia, J. P.; Finck, C.; Foti, A.; Gallardo, M. I.; Golosio, B.; Iarocci, E.; Iazzi, F.; Ickert, G.; Introzzi, R.; Juliani, D.; Krimmer, J.; Kurz, N.; Labalme, M.; Lavagno, A.; Leifels, Y.; Le Fevre, A.; Leray, S.; Marchetto, F.; Monaco, V.; Morone, M. C.; Nicolosi, D.; Oliva, P.; Paoloni, A.; Patera, V.; Piersanti, L.; Pleskac, R.; Quesada, J. M.; Randazzo, N.; Romano, F.; Rossi, D.; Rosso, V.; Rousseau, M.; Sacchi, R.; Sala, P.; Sarti, A.; Scheidenberger, C.; Schuy, C.; Sciubba, A.; Sfienti, C.; Simon, H.; Sipala, V.; Spiriti, E.; Stuttge, L.; Tropea, S.; Younis, H.

    2013-03-01

    Nuclear fragmentation processes are relevant in different fields of basic research and applied physics and are of particular interest for tumor therapy and for space radiation protection applications. The FIRST (Fragmentation of Ions Relevant for Space and Therapy) experiment at SIS accelerator of GSI laboratory in Darmstadt, has been designed for the measurement of different ions fragmentation cross sections at different energies between 100 and 1000 MeV/nucleon. The experiment is performed by an international collaboration made of institutions from Germany, France, Italy and Spain. The experimental apparatus is partly based on an already existing setup made of the ALADIN magnet, the MUSIC IV TPC, the LAND2 neutron detector and the TOFWALL scintillator TOF system, integrated with newly designed detectors in the interaction Region (IR) around the carbon removable target: a scintillator Start Counter, a Beam Monitor drift chamber, a silicon Vertex Detector and a Proton Tagger for detection of light fragments emitted at large angles (KENTROS). The scientific program of the FIRST experiment started on summer 2011 with the study of the 400 MeV/nucleon 12C beam fragmentation on thin (8mm) carbon target.

  17. Low Mass MS/MS Fragments of Protonated Amino Acids Used for Distinction of Their 13C- Isotopomers in Metabolic Studies

    Science.gov (United States)

    Ma, Xin; Dagan, Shai; Somogyi, Árpád; Wysocki, Vicki H.; Scaraffia, Patricia Y.

    2013-04-01

    Glu, Gln, Pro, and Ala are the main amino acids involved in ammonia detoxification in mosquitoes. In order to develop a tandem mass spectrometry method (MS2) to monitor each carbon of the above isotopically-labeled 13C-amino acids for metabolic studies, the compositions and origins of atoms in fragments of the protonated amino acid should be first elucidated. Thus, various electrospray (ESI)-based MS2 tools were employed to study the fragmentation of these unlabeled and isotopically-labeled amino acids and better understand their dissociation pathways. A broad range of fragments, including previously-undescribed low m/z fragments was revealed. The formulae of the fragments (from m/z 130 down to m/z 27) were confirmed by their accurate masses. The structures and conformations of the larger fragments of Glu were also explored by ion mobility mass spectrometry (IM-MS) and gas-phase hydrogen/deuterium exchange (HDX) experiments. It was found that some low m/z fragments ( m/z 27-30) are common to Glu, Gln, Pro, and Ala. The origins of carbons in these small fragments are discussed and additional collision induced dissociation (CID) MS2 fragmentation pathways are proposed for them. It was also found that small fragments (≤ m/z 84) of protonated, methylated Glu, and methylated Gln are the same as those of the underivatized Glu and Gln. Taken together, the new approach of utilizing low m/z fragments can be applied to distinguish, identify, and quantify 13C-amino acids labeled at various positions, either in the backbone or side chain.

  18. Three-body fragmentation of methane dications produced by slow A r8 + -ion impact

    Science.gov (United States)

    Zhang, Y.; Jiang, T.; Wei, L.; Luo, D.; Wang, X.; Yu, W.; Hutton, R.; Zou, Y.; Wei, B.

    2018-02-01

    The three-body fragmentation dynamics of CH4 2 + dications induced by single-electron capture of slow (3-keV/u) A r8 + ions is investigated. The experiment is performed on a newly built, highly charged ion collision platform which consists of an electron cyclotron resonance ion source and a cold target recoil ion momentum spectroscopy (COLTRIMS) setup. Using the COLTRIMS methodology, the complete kinematical information is determined for two three-body breakup channels, CH4 2 +→H++CH2 ++H and CH4 2 +→H2 ++C H++H . Then analyzing the complete kinematics with the Dalitz plot, very different fragmentation mechanisms (e.g., sequential and/or concerted pathway) are clearly identified for the two channels. To confirm the existence of some possible fragmentation pathways, we also simulate corresponding Dalitz plots employing a simple classical mechanical model. For the H++CH2 ++H channel, the dependence of the fragmentation pathway on its kinetic energy release is studied, which reflects the different nature of the corresponding states of CH4 2 + dications. Furthermore, the kinetic energy ratio of two ionic fragments is analyzed to infer the three-body fragmentation mechanism of CH4 2 + dications.

  19. Cs+ ion source for secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Bentz, B.L.; Weiss, H.; Liebl, H.

    1981-12-01

    Various types of cesium ionization sources currently used in secondary ion mass spectrometry are briefly reviewed, followed by a description of the design and performance of a novel, thermal surface ionization Cs + source developed in this laboratory. The source was evaluated for secondary ion mass spectrometry applications using the COALA ion microprobe mass analyzer. (orig.)

  20. Correlation of precursor and product ions in single-stage high resolution mass spectrometry. A tool for detecting diagnostic ions and improving the precursor elemental composition elucidation

    Energy Technology Data Exchange (ETDEWEB)

    Borràs, S. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Kaufmann, A., E-mail: anton.kaufmann@klzh.ch [Official Food Control Authority, Fehrenstrasse 15, 8032 Zürich (Switzerland); Companyó, R. [Departament de Química Analítica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)

    2013-04-15

    Highlights: ► We are describing a technique to spot ions which are derived from each other. ► Single stage high resolution data is used. ► This “in silicon” technique is compared to conventional precursor scan. ► Some applications for this technique are presented. -- Abstract: Monitoring of common diagnostic fragments is essential for recognizing molecules which are members of a particular compound class. Up to now, unit resolving tandem quadrupole mass spectrometers, operating in the precursor ion scan mode, have been typically used to perform such analysis. By means of high-resolution mass spectrometry (HRMS) a much more sensitive and selective detection can be achieved. However, using a single-stage HRMS instrument, there is no unequivocal link to the corresponding precursor ion, since such instrumentation does not permit a previous precursor selection. Thus, to address this limitation, an in silico approach to locate precursor ions, based on diagnostic fragments, was developed. Implemented as an Excel macro, the algorithm rapidly assembles and surveys exact mass data to provide a list of feasible precursor candidates according to the correlation of the chromatographic peak shape profile and other additional filtering criteria (e.g. neutral losses and isotopes). The macro was tested with two families of veterinary drugs, sulfonamides and penicillins, which are known to yield diagnostic product ions when fragmented. Data sets obtained from different food matrices (fish and liver), both at high and low concentration of the target compounds, were investigated in order to evaluate the capabilities and limitations of the reported approach. Finally, other possible applications of this technique, such as the elucidation of elemental compositions based on product ions and corresponding neutral losses, were also presented and discussed.

  1. Correlation of precursor and product ions in single-stage high resolution mass spectrometry. A tool for detecting diagnostic ions and improving the precursor elemental composition elucidation

    International Nuclear Information System (INIS)

    Borràs, S.; Kaufmann, A.; Companyó, R.

    2013-01-01

    Highlights: ► We are describing a technique to spot ions which are derived from each other. ► Single stage high resolution data is used. ► This “in silicon” technique is compared to conventional precursor scan. ► Some applications for this technique are presented. -- Abstract: Monitoring of common diagnostic fragments is essential for recognizing molecules which are members of a particular compound class. Up to now, unit resolving tandem quadrupole mass spectrometers, operating in the precursor ion scan mode, have been typically used to perform such analysis. By means of high-resolution mass spectrometry (HRMS) a much more sensitive and selective detection can be achieved. However, using a single-stage HRMS instrument, there is no unequivocal link to the corresponding precursor ion, since such instrumentation does not permit a previous precursor selection. Thus, to address this limitation, an in silico approach to locate precursor ions, based on diagnostic fragments, was developed. Implemented as an Excel macro, the algorithm rapidly assembles and surveys exact mass data to provide a list of feasible precursor candidates according to the correlation of the chromatographic peak shape profile and other additional filtering criteria (e.g. neutral losses and isotopes). The macro was tested with two families of veterinary drugs, sulfonamides and penicillins, which are known to yield diagnostic product ions when fragmented. Data sets obtained from different food matrices (fish and liver), both at high and low concentration of the target compounds, were investigated in order to evaluate the capabilities and limitations of the reported approach. Finally, other possible applications of this technique, such as the elucidation of elemental compositions based on product ions and corresponding neutral losses, were also presented and discussed

  2. Fragmentations and rearrangements of metastable [C2H5OS]+ ions

    NARCIS (Netherlands)

    de Vries, Marcel; Oudman, D; Weringa, WD

    1992-01-01

    Several [C2H5OS]+ ions with different structures were generated from the appropriate precursors and their metastable ion spectra were determined. Deuterium labelled analogues of some of the [C2H5OS]+ ions were used to elucidate the nature of the observed fragmentations and their mechanisms.

  3. Quantification and micron-scale imaging of spatial distribution of trace beryllium in shrapnel fragments and metallurgic samples with correlative fluorescence detection method and secondary ion mass spectrometry (SIMS).

    Science.gov (United States)

    Abraham, J L; Chandra, S; Agrawal, A

    2014-11-01

    Recently, a report raised the possibility of shrapnel-induced chronic beryllium disease from long-term exposure to the surface of retained aluminum shrapnel fragments in the body. Since the shrapnel fragments contained trace beryllium, methodological developments were needed for beryllium quantification and to study its spatial distribution in relation to other matrix elements, such as aluminum and iron, in metallurgic samples. In this work, we developed methodology for quantification of trace beryllium in samples of shrapnel fragments and other metallurgic sample-types with main matrix of aluminum (aluminum cans from soda, beer, carbonated water and aluminum foil). Sample preparation procedures were developed for dissolving beryllium for its quantification with the fluorescence detection method for homogenized measurements. The spatial distribution of trace beryllium on the sample surface and in 3D was imaged with a dynamic secondary ion mass spectrometry instrument, CAMECA IMS 3f secondary ion mass spectrometry ion microscope. The beryllium content of shrapnel (∼100 ppb) was the same as the trace quantities of beryllium found in aluminum cans. The beryllium content of aluminum foil (∼25 ppb) was significantly lower than cans. SIMS imaging analysis revealed beryllium to be distributed in the form of low micron-sized particles and clusters distributed randomly in X-Y- and Z dimensions, and often in association with iron, in the main aluminum matrix of cans. These observations indicate a plausible formation of Be-Fe or Al-Be alloy in the matrix of cans. Further observations were made on fluids (carbonated water) for understanding if trace beryllium in cans leached out and contaminated the food product. A direct comparison of carbonated water in aluminum cans and plastic bottles revealed that beryllium was below the detection limits of the fluorescence detection method (∼0.01 ppb). These observations indicate that beryllium present in aluminum matrix was either

  4. Fragmentation and momentum correlations in heavy-ion collisions

    Indian Academy of Sciences (India)

    The role of momentum correlations in the production of light and medium mass fragments is studied by imposing momentum cut in the clusterization of the phase space. Our detailed investigation shows that momentum cut has a major role to play in the emission of fragments. A comparison with the experimental data is also ...

  5. Direct determination of recoil ion detection efficiency for coincidence time-of-flight studies of molecular fragmentation

    International Nuclear Information System (INIS)

    Ben-Itzhak, I.; Carnes, K.D.; Ginther, S.G.; Johnson, D.T.; Norris, P.J.; Weaver, O.L.

    1993-01-01

    Molecular fragmentation of diatomic and small polyatomic molecules caused by fast ion impact has been studied. The evaluation of the cross sections of the different fragmentation channels depends strongly on the recoil ion detection efficiency, ε r (single ions proportional to ε r , and ion pairs to ε 2 r , etc.). A method is suggested for the direct determination of this detection efficiency. This method is based on the fact that fast H + + CH 4 collisions produce C 2+ fragments only in coincidence with H + and H + 2 fragments, that is, there is a negligible number of C 2+ singles, if any. The measured yield of C 2+ singles is therefore due to events in which the H + m of the H + m + C 2+ ion pair was not detected and thus is proportional to 1 - ε r . Methane fragmentation caused by 1 MeV proton impact is used to evaluate directly the recoil ion detection efficiency and to demonstrate the method of deriving the cross sections of all breakup channels. (orig.)

  6. Production of pions and anomalous projectile fragments in heavy ion collisions

    International Nuclear Information System (INIS)

    Noren, B.

    1988-05-01

    Results are presented from investigations of the mean free path (mfp) of multiply charged fragments, produced by 1.8 A GeV argon nuclei. The mfp's have been studied experimentally, and no dependence of the mfp on the distance from the preceeding collision is observed. In a Monte Carlo simulation, the mfp estimators are investigated for different statistics, with or without an enhanced reaction probability. Intermediate energy heavy ion collisions have been studied using the carbon beam produced at the CERN SC-accelerator. Cross-sections for pion + and pion - have been measured over a wide range of angles and targets. Also, coincidence measurements with projectile-like fragments have been performed. The pion - /pion + ratio has been studied for C+Li, C+C, C+Pb, C+ 116 Sn and C+ 124 Sn. Inconsistencies in the target mass dependence of the pion yield disappear if a correction for reabsorption in the target nucleus is included. The projectile breakup is significantly stronger for pion producing collisions than for the average collision, thus indicating a much stronger abundance of central collisions. (With 32 refs.) (author)

  7. Mini ion trap mass spectrometer

    Science.gov (United States)

    Dietrich, D.D.; Keville, R.F.

    1995-09-19

    An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

  8. Physics of projectile fragments

    International Nuclear Information System (INIS)

    Minamisono, Tadanori

    1982-01-01

    This is a study report on the polarization phenomena of the projectile fragments produced by heavy ion reactions, and the beta decay of fragments. The experimental project by using heavy ions with the energy from 50 MeV/amu to 250 MeV/amu was designed. Construction of an angle-dispersion spectrograph for projectile fragments was proposed. This is a two-stage spectrograph. The first stage is a QQDQQ type separator, and the second stage is QDQD type. Estimation shows that Co-66 may be separated from the nuclei with mass of 65 and 67. The orientation of fragments can be measured by detecting beta-ray. The apparatus consists of a uniform field magnet, an energy absorber, a stopper, a RF coil and a beta-ray hodoscope. This system can be used for not only this purpose but also for the measurement of hyperfine structure. (Kato, T.)

  9. Fragmentation of deuteronated aromatic derivatives: The role of ion-neutral complexes

    Science.gov (United States)

    Harrison, Alex G.; Wang, Jian-Yao

    1997-01-01

    The low-energy collision-induced dissociation reactions of the MD+ ions of a number of alkyl phenyl ethers, alkylbenzenes, acetophenones and benzaldehyde have been studied as a function of collision energy to establish qualitatively the dependence of the fragmentation reactions observed on internal energy. Deuteronated alkyl phenyl ethers (ROC6H5·D+, R = C3H7, C4H9) fragment at low collision energies to form C6H5OHD+ + (R-H), the thermochemically favoured products; with increasing collision energy (and, hence, internal energy) formation of the alkyl ion R+ increases significantly in importance. Deuteronated alkylbenzenes (RC6H5, RC6H4R', R = C2H5, C3H7) similarly form the deuteronated benzene (the thermochemically favoured product) at low collision energies with formation of the alkyl ion R+ being observed at higher collision energies. The results for both systems are consistent with a fragmentation mechanism involving initial formation of an R+/aromatic ion/neutral complex. At low internal energies proton transfer occurs within this complex to form an ion/neutral complex consisting of the deuteronated aromatic and a neutral olefin; this complex fragments to the thermochemically favoured products. Since the transition state leading to these products is a "tight" transition state involving loss of rotational degrees of freedom, the proton transfer reaction is unfavourable entropically with respect to simple dissociation of the R+/aromatic complex to R+ + ArD. Consequently, these products increase in importance as the internal energy is increased. The fragmentation of deuteronated aromatic carbonyl compounds can also be rationalized by similar mechanisms involving the intermediacy of ion/neutral complexes. Deuteronated acetophenone forms only CH3CO+ at all collision energies; this is both the thermochemically and entropically favoured product. However, deuteronated p-aminoacetophenone forms deuteronated aniline, the thermochemically favoured product at low collision

  10. Unimolecular and collisionally induced ion reactions

    International Nuclear Information System (INIS)

    Beynon, J.H.; Boyd, R.K.

    1978-01-01

    The subject is reviewed under the following headings: introduction (mass spectroscopy and the study of fragmentation reactions of gaseous positive ions); techniques and methods (ion sources, detection systems, analysis of ions, data reduction); collision-induced reactions of ions and unimolecular fragmentations of metastable ions; applications (ion structure, energetic measurements, analytical applications, other applications). 305 references. (U.K.)

  11. Mass distribution of fission fragments within the Born-Oppenheimer approximation

    Energy Technology Data Exchange (ETDEWEB)

    Pomorski, K.; Nerlo-Pomorska, B. [M.C.S. University, Department of Theoretical Physics, Lublin (Poland); Ivanyuk, F.A. [Institute for Nuclear Research, Kiev (Ukraine)

    2017-03-15

    The fission fragments mass-yield of {sup 236} U is obtained by an approximate solution of the eigenvalue problem of the collective Hamiltonian that describes the dynamics of the fission process whose degrees of freedom are: the fission (elongation), the neck and mass-asymmetry modes. The macroscopic-microscopic method is used to evaluate the potential energy surface. The macroscopic energy part is calculated using the liquid drop model and the microscopic corrections are obtained using a Woods-Saxon single-particle levels. The four-dimensional modified Cassini ovals shape parametrization is used to describe the shape of the fissioning nucleus. The mass tensor is taken within a cranking-type approximation. The final fragment mass distribution is obtained by weighting the adiabatic density distribution in the collective space with the neck-dependent fission probability. The neck degree of freedom is found to play a significant role in determining the final fragment mass distribution. (orig.)

  12. Fragmentation study of isolated and nano-solvated biomolecules induced by collision with multiply charged ions and neutral particles

    International Nuclear Information System (INIS)

    Bernigaud, V.

    2009-01-01

    This thesis concerns a gas phase study of the fragmentation of bio-molecular systems induced by slow collisions with multiply charged ions (in the keV-region), alkali atoms and rare gases. The main objective was to study the physical processes involved in the dissociation of highly electronically excited systems. In order to elucidate the intrinsic properties of certain biomolecules (porphyrins and amino acids) we have performed experiments in the gas phase with isolated systems. The obtained results demonstrate the high stability of porphyrins after electron removal and attachment. Furthermore, a dependence of the fragmentation pattern produced by multiply charged ions on the isomeric structure of the alanine molecule has been shown. In a second part of the thesis, a strong influence of the environment of the biomolecule on the fragmentation channels, their modification and their new opening, has been clearly proven. This phenomenon occurs in the presence of other surrounding biomolecules (clusters of nucleobases) as well as for molecules of a solvent (molecules of water, methanol and acetonitrile) in which the biomolecule is embedded. In order to extend these studies to larger systems, a new experimental set-up, based on an electro-spray ion source combined with a quadrupole mass filter has been developed. Due to the successful tests and proposed improvements of the device future experiments will become available concerning the fragmentation of large charged and solvated bio-molecular systems induced by collision processes. (author) [fr

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

    Science.gov (United States)

    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.

  14. Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

    Science.gov (United States)

    Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

    2011-10-01

    When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

  15. Fragmentation analysis of water-soluble atmospheric organic matter using ultrahigh-resolution FT-ICR mass spectrometry.

    Science.gov (United States)

    Leclair, Jeffrey P; Collett, Jeffrey L; Mazzoleni, Lynn R

    2012-04-17

    Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

  16. Ionization, evaporation and fragmentation of C{sub 60} in collisions with highly charged C, O and F ions-effect of projectile charge state

    Energy Technology Data Exchange (ETDEWEB)

    Kelkar, A H; Misra, D; Tribedi, L C [Tata Institute of Fundamental Research, Colaba, Mumbai -5 (India)

    2007-09-15

    We study the various inelastic processes such ionization, fragmentation and evaporation of C{sub 60} 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 C{sub 60}{sup r+} ions were detected for maximum r = 4. The projectile charge state (q{sub p}) dependence of the single and double ionization cross sections is well reproduced by a model based on the giant dipole plasmon resonance (GDPR). The q{sub p}-dependence of the fragmentation yields, was found to be linear. Variation of relative yields of the evaporation products of C{sub 60}{sup 2+} (i.e. C{sub 58}{sup 2+}, C{sub 56}{sup 2+} etc) and C{sub 60}{sup 3+} (i.e. C{sub 58}{sup 3+}, C{sub 56}{sup 3+} etc) with q{sub p} has also been investigated for various projectiles.

  17. Nuclear Fragmentation in Clinical Heavy Ion Beams, Should We Worry?

    DEFF Research Database (Denmark)

    Bassler, Niels; Hansen, David Christoffer; Toftegaard, Jakob

    2012-01-01

    Particle therapy with fast ions is increasingly applied as a treatment option for localized inoperable tumour sites. One of the reasons for the increased complications of understanding heavy ion dosimetry and radiobiology stems from the mixed particle spectrum which occurs due to nuclear fragment......Particle therapy with fast ions is increasingly applied as a treatment option for localized inoperable tumour sites. One of the reasons for the increased complications of understanding heavy ion dosimetry and radiobiology stems from the mixed particle spectrum which occurs due to nuclear....... The concept of relative biological effectiveness (RBE) translates the physical dose to a biological effective dose which is iso-effective to photon radiation. Radiobiological models based on amorphous track structure such as the Local Effect Model, but also microdosimetry based models both rely on a full...... the sensitivity on the three fields mentioned above, including: turning off nuclear fragmentation entirely, changing all ineleastic cross sections +/- 20%, changing key parameters in the Fermi-Breakup (FB) model. Results show nuclear effects have their largest impact on the dose distribution. Stopping power...

  18. Competitive fragmentation pathways of acetic acid dimer explored by synchrotron VUV photoionization mass spectrometry and electronic structure calculations.

    Science.gov (United States)

    Guan, Jiwen; Hu, Yongjun; Zou, Hao; Cao, Lanlan; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

    2012-09-28

    In present study, photoionization and dissociation of acetic acid dimers have been studied with the synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. Besides the intense signal corresponding to protonated cluster ions (CH(3)COOH)(n)·H(+), the feature related to the fragment ions (CH(3)COOH)H(+)·COO (105 amu) via β-carbon-carbon bond cleavage is observed. By scanning photoionization efficiency spectra, appearance energies of the fragments (CH(3)COOH)·H(+) and (CH(3)COOH)H(+)·COO are obtained. With the aid of theoretical calculations, seven fragmentation channels of acetic acid dimer cations were discussed, where five cation isomers of acetic acid dimer are involved. While four of them are found to generate the protonated species, only one of them can dissociate into a C-C bond cleavage product (CH(3)COOH)H(+)·COO. After surmounting the methyl hydrogen-transfer barrier 10.84 ± 0.05 eV, the opening of dissociative channel to produce ions (CH(3)COOH)(+) becomes the most competitive path. When photon energy increases to 12.4 eV, we also found dimer cations can be fragmented and generate new cations (CH(3)COOH)·CH(3)CO(+). Kinetics, thermodynamics, and entropy factors for these competitive dissociation pathways are discussed. The present report provides a clear picture of the photoionization and dissociation processes of the acetic acid dimer in the range of the photon energy 9-15 eV.

  19. Competitive fragmentation pathways of acetic acid dimer explored by synchrotron VUV photoionization mass spectrometry and electronic structure calculations

    Science.gov (United States)

    Guan, Jiwen; Hu, Yongjun; Zou, Hao; Cao, Lanlan; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

    2012-09-01

    In present study, photoionization and dissociation of acetic acid dimers have been studied with the synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. Besides the intense signal corresponding to protonated cluster ions (CH3COOH)n.H+, the feature related to the fragment ions (CH3COOH)H+.COO (105 amu) via β-carbon-carbon bond cleavage is observed. By scanning photoionization efficiency spectra, appearance energies of the fragments (CH3COOH).H+ and (CH3COOH)H+.COO are obtained. With the aid of theoretical calculations, seven fragmentation channels of acetic acid dimer cations were discussed, where five cation isomers of acetic acid dimer are involved. While four of them are found to generate the protonated species, only one of them can dissociate into a C-C bond cleavage product (CH3COOH)H+.COO. After surmounting the methyl hydrogen-transfer barrier 10.84 ± 0.05 eV, the opening of dissociative channel to produce ions (CH3COOH)+ becomes the most competitive path. When photon energy increases to 12.4 eV, we also found dimer cations can be fragmented and generate new cations (CH3COOH).CH3CO+. Kinetics, thermodynamics, and entropy factors for these competitive dissociation pathways are discussed. The present report provides a clear picture of the photoionization and dissociation processes of the acetic acid dimer in the range of the photon energy 9-15 eV.

  20. Fragment formation in light-ion induced reactions

    International Nuclear Information System (INIS)

    Hirata, Yuichi

    2001-01-01

    The intermediate mass fragment (IMF) formation in the 12 GeV proton induced reaction on Au target is analyzed by the quantum molecular dynamics model combined with the JAM hadronic cascade model and the non-equilibrated percolation model. We show that the sideward peaked angular distribution of IMF occur in the multifragmentation at very short time scale around 20 fm/c where non-equilibrated features of the residual nucleus fluctuates the nucleon density and fragments in the repulsive Coulomb force are pushed for the sideward direction. (author)

  1. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Science.gov (United States)

    Dickel, T.; Plaß, W. R.; Ayet San Andres, S.; Ebert, J.; Geissel, H.; Haettner, E.; Hornung, C.; Miskun, I.; Pietri, S.; Purushothaman, S.; Reiter, M. P.; Rink, A.-K.; Scheidenberger, C.; Weick, H.; Dendooven, P.; Diwisch, M.; Greiner, F.; Heiße, F.; Knöbel, R.; Lippert, W.; Moore, I. D.; Pohjalainen, I.; Prochazka, A.; Ranjan, M.; Takechi, M.; Winfield, J. S.; Xu, X.

    2015-05-01

    211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  2. Study of Photoionization and Fragmentation on CHClF2 : Experiments and Calculations

    International Nuclear Information System (INIS)

    Sheng, L.; Yang, B.; Huang, C.; Qi, F.; Zhang, Y.; Wang, Z.; Zhou, S.

    2004-01-01

    Full text: The photoionization and fragmentation of CHClF 2 are studied with VUV radiation and photoionization mass spectroscopy at NSRL. Ionization potential of Parent molecule CHClF 2 , appearance energies of some fragment ions, and dissociative energy of some fragmentation process are obtained from photoionization efficiency spectroscopy. Dissociative photoionization channels for formation of some fragment ions are proposed on comparison of determined appearance energies and energies predicted with Gaussian-98 calculation

  3. Ion Mass Determination

    DEFF Research Database (Denmark)

    2010-01-01

    An apparatus (100) is described for determining the mass of ions, the apparatus configured to hold a plasma (101 ) having a plasma potential. The apparatus (100) comprises an electrode (102) having a surface extending in a surface plane and an insulator (104) interfacing with the electrode (102......, and a processing unit (108) configured to interpret the detected impact locations in terms of the mass of the impacting ions....

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

    International Nuclear Information System (INIS)

    Shukla, Anil; Bogdanov, Bogdan

    2015-01-01

    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 2 ). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi) n Li + , (HCOOLi) n Li m m+ , (HCOOLi) n HCOO − , and (HCOOLi) n (HCOO) m 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) 3 Li + being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi) 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) 3 Li + 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

  5. Fragmentation patterns involving ammonium adduct fragment ions: A comparison of the determination of metaldehyde in human blood by HPLC-QqQ-MS/MS and UHPLC-Q-TOF-MS.

    Science.gov (United States)

    Szpot, Paweł; Buszewicz, Grzegorz; Jurek, Tomasz; Teresiński, Grzegorz

    2018-05-15

    This paper presents a rapid, sensitive and precise method for the determination of metaldehyde in human blood, using ultra-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and high-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry. Separation was performed with a Poroshell 120 EC-C18 column; 2.7 μm atrazine‑d5 (IS) and 200 mg NaCl were added to the blood sample. Proteins in human blood were precipitated using acetonitrile; the supernatant was then analyzed with the UHPLC-Q-TOF-MS or HPLC-QqQ-MS/MS system. The results of selectivity, linearity, accuracy, precision, limits of quantification, recovery, and matrix effects were sufficient to enable the measurement of metaldehyde in human blood samples. In addition, we proposed a fragmentation pathway involving ammonium adduct fragment ions for metaldehyde. Copyright © 2018. Published by Elsevier B.V.

  6. Time of flight secondary ion mass spectrometry: A powerful high throughput screening tool

    International Nuclear Information System (INIS)

    Smentkowski, Vincent S.; Ostrowski, Sara G.

    2007-01-01

    Combinatorial materials libraries are becoming more complicated; successful screening of these libraries requires the development of new high throughput screening methodologies. Time of flight secondary ion mass spectrometry (ToF-SIMS) is a surface analytical technique that is able to detect and image all elements (including hydrogen which is problematic for many other analysis instruments) and molecular fragments, with high mass resolution, during a single measurement. Commercial ToF-SIMS instruments can image 500 μm areas by rastering the primary ion beam over the region of interest. In this work, we will show that large area analysis can be performed, in one single measurement, by rastering the sample under the ion beam. We show that an entire 70 mm diameter wafer can be imaged in less than 90 min using ToF-SIMS stage (macro)rastering techniques. ToF-SIMS data sets contain a wealth of information since an entire high mass resolution mass spectrum is saved at each pixel in an ion image. Multivariate statistical analysis (MVSA) tools are being used in the ToF-SIMS community to assist with data interpretation; we will demonstrate that MVSA tools provide details that were not obtained using manual (univariate) analysis

  7. Protein Analysis by Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Cindic, M.

    2008-04-01

    Full Text Available Soft ionization techniques, electrospray (ESI and matrix-assisted laser desorption/ionization (MALDI make the analysis of biomolecules by mass spectrometry (MS possible. MS is used for determination of the molecular weight of peptides and protein, sequence analysis, characterization of protein-ligand interactions etc. The detection limit, resolution and mass accuracy depend on instrument used (Table 1. Impurities (buffers, salts, detergents can reduce the ion intensities or even totally suppress them, so a separation method (chromatography, 2D-gel electrophoresis must be used for purification of the sample.Molecular mass of intact protein can be determined by ESI or MALDI MS. Multiply charged ions are produced by ESI MS, while singly charged ions are predominant in MALDI spectra (Fig. 2.Sequence analysis of proteins by MS can be performed using peptide mass fingerprint. In this method, proteins are separated by 2-D gel electrophoresis and digested with specific protease (Table 2 or digested and then separated by two-dimensional chromatography (Fig. 1. The obtained peptide mixtures are analyzed by MS or MALDI-TOF technique. The masses determined by MS are compared with calculated masses from database entries. Different algorithms have been developed for protein identification. Example of posttranslational modifications (N- and O-glycosylation and protein sequence complex analysis after dual digestion (endoproteinase digestion followed by endoglycosidase digestion is shown in Fig. 3.It is known that detection of peptides by MS is influenced by intrinsic properties like amino acid composition, the basicity of the C-terminal amino acid, hydrophobicity, etc. Arginine-containing peptides dominate in MS spectra of tryptic digest, so the chemical derivatization of lysine terminal residue by O-methilisourea or 2-methoxy-4,5-1H-imidazole was suggested (Fig. 4.The peptide mass fingerprint method can be improved further by peptide fragmentation using tandem

  8. Densities and temperatures at fragment formation in heavy-ion collision

    Energy Technology Data Exchange (ETDEWEB)

    Ohnishi, Akira [Hokkaido Univ., Sapporo (Japan)

    1998-07-01

    In order to clarify whether the liquid-gas phase transition is relevant to the multi-fragment formation found in intermediate energy heavy-ion collisions, we estimate the densities and temperatures at fragment formation in Au+Au collisions at incident energies of 150 MeV/A and 400 MeV/A within the Quantum Molecular Dynamics (QMD) model with and without quantum fluctuations implemented according to the Quantal Langevin (QL) model. The calculated results show that the IMFs are mainly produced inside the unstable region of nuclear matter, which supports the idea of the fragment formation from supercooled nuclear matter. (author)

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

    Science.gov (United States)

    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.

  10. Interaction of energetic particles with polymer surfaces: surface morphology development and sputtered polymer-fragment ion analysis

    International Nuclear Information System (INIS)

    Michael, R.S.

    1987-01-01

    The core of this thesis is based on a series of papers that have been published or will soon be published in which the various processes taking place in the energetic particle-polymer surface interaction scene is investigated. Results presented show different developments on polymer surfaces when compared to the vast experimental data on energetic particle-metal surface interactions. The surface morphology development depends on the physical characteristics of the polymer. Sputtering yields of fluoropolymers were several orders higher than the sputtering yields of aliphatic and aromatic polymers. Depending on the chemical nature of the polymer, the surface morphology development was dependent upon the extent of radiation-damage accumulation. Fast Atom Bombardment Mass Spectrometry at low and high resolution was applied to the characterization of sputtered polymer fragment ions. Fragment ions and their intensities were used to identify polymer samples, observe radiation damage accumulation and probe polymer-polymer interface of a polymer-polymer sandwich structure. A model was proposed which attempts to explain the nature of processes involved in the energetic particle-polymer surface interaction region

  11. Simultaneous investigation of fission fragments and neutrons in 252Cf(s,f)

    International Nuclear Information System (INIS)

    Budtz-Joergensen, C.; Knitter, H.H.

    1986-01-01

    The gridded twin ion chamber developed at CBNM is used to measure the kinetic energy-, mass- and angular distributions of the fission fragments of 252 Cf in an advantageous 4π-geometry. Together with a neutron time-of-flight detector this experimental arrangement permits to measure the correlation between neutron emission, fragment angle, mass and energy in the spontaneous fission of 252 Cf. With the present experimental set-up a mass resolution for fission fragments of 0.5 a.m.u., an angular resolution of Δcosθ = 0.05 and a timing resolution of 0.7 ns FWHM were observed. Preliminary evaluations of the raw experimental data are presented for the fission fragment mass distribution, the average total kinetic energy and their variance as function of mass, the angular distribution between fragments and neutrons, the number of neutrons emitted per fragment as function of fragment mass, the average neutron emission energies as function of mass, and the prompt fission neutron spectrum averaged over all fragments. (author)

  12. Cluster secondary ion mass spectrometry microscope mode mass spectrometry imaging.

    Science.gov (United States)

    Kiss, András; Smith, Donald F; Jungmann, Julia H; Heeren, Ron M A

    2013-12-30

    Microscope mode imaging for secondary ion mass spectrometry is a technique with the promise of simultaneous high spatial resolution and high-speed imaging of biomolecules from complex surfaces. Technological developments such as new position-sensitive detectors, in combination with polyatomic primary ion sources, are required to exploit the full potential of microscope mode mass spectrometry imaging, i.e. to efficiently push the limits of ultra-high spatial resolution, sample throughput and sensitivity. In this work, a C60 primary source was combined with a commercial mass microscope for microscope mode secondary ion mass spectrometry imaging. The detector setup is a pixelated detector from the Medipix/Timepix family with high-voltage post-acceleration capabilities. The system's mass spectral and imaging performance is tested with various benchmark samples and thin tissue sections. The high secondary ion yield (with respect to 'traditional' monatomic primary ion sources) of the C60 primary ion source and the increased sensitivity of the high voltage detector setup improve microscope mode secondary ion mass spectrometry imaging. The analysis time and the signal-to-noise ratio are improved compared with other microscope mode imaging systems, all at high spatial resolution. We have demonstrated the unique capabilities of a C60 ion microscope with a Timepix detector for high spatial resolution microscope mode secondary ion mass spectrometry imaging. Copyright © 2013 John Wiley & Sons, Ltd.

  13. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    Energy Technology Data Exchange (ETDEWEB)

    Lentz, Nicholas B. [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

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

    Science.gov (United States)

    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.

  15. Collision induced fragmentation of fast molecular ions in solids and gases

    International Nuclear Information System (INIS)

    Gemmell, D.S.

    1979-01-01

    A brief review is given of recent high resolution measurements on fragments arising from the collision-induced dissociation of fast (MeV) molecular ions. For solid targets, strong wake effects are observed. For gaseous targets, excited electronic states of the projectile ions play an important role. Measurements of this type provide useful information on the charge states of fast ions traversing matter. The experimental techniques show promise as a unique method for determining the geometrical structures of the molecular-ion projectiles. 41 references

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

    Science.gov (United States)

    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.

  17. On-line mass spectometry of nuclear reactions induced by heavy ions

    International Nuclear Information System (INIS)

    Saint Simon, M. de.

    1977-01-01

    The adaptation of the on-line mass-spectrometric technique to the special conditions of heavy ion induced reactions is described. The method is very selective about A and Z, even for the very heavy reaction products in counterpart of the limitation of its applications to the alkaline elements only. This method is used in order to study the effects of angular momentum brought by the projectile in the complete fusion process and in the following neutron evaporation. The analysis of excitation functions shows that the increase in mass of the projectile has not always the effect of increasing the rotation energy of the compound nucleus. The on-line mass spectrometry has allowed to study heavy ion induced fission. Measurements of complementary isotopic distributions of fission products make it possible to explain that the total number of neutrons emitted per fission can be always deduced from the fragment excitation energy. The study of the isotope distribution variance shows that the statistical model for fission is in good agreement with experimental results after taking into account the non-fusion processes [fr

  18. The Wolff rearrangement of cyclic 2-diazo-1,3-diketones in electron impact - mass spectrometry - controlling the molecular fragmentation by means of low-energy electrons 18 to 70 eV

    International Nuclear Information System (INIS)

    Kuruc, J.; Kardosova, E.; Nikolaev, V. A.

    2016-01-01

    The electron-impact-induced fragmentations (the mass spectra, 17 - 70 eV) of cyclic 2-diazo-1,3-diketones were studied. As the suitable compounds were selected the following cyclic 2-diazo-1,3-diketones: 2-diazo-1,3-cyclohexanedione, Ia; 2-diazo-4,4-dimethyl-1,3-cyclohexanedione, Ib; 2-diazo-5,5-dimethyl-1,3-cyclohexanedione, Ic; 2-diazo-4,6-dioxa-5,5-dimethyl-1,3-cyclohexanedione, Id; and 2-diazo-5-phenyl-1,3-cyclohexanedione, Ie). The mass spectra were measured with Varian MAT 111 instrument with direct introduction of samples, with a source temperature of 120 grad C, energy of ionising electrons was in the range (17 - 70) eV. The elimination of the diazo group is the typical reaction of the fragmentation of the cyclic diazo-1,3-diketones after ionization of molecules by electron impact. All our studied cyclic diazo-1,3-diketones have a molecular ion with a relative intensity from 0.7 to 86.4%. Typical ions are [M]"+·, [M-N"_2]"+"·, [M-N_2-CO]"+"·, [M-N_2-CO-CH_2]"+"·, [M-N_2-CO-CH_3]"+"·. For all treatment cyclic diazo-1,3-diketones have been registered 3D mass spectra, for each cyclic diazo-1,3-diketone was proposed fragmentation scheme, including the general fragmentation scheme. The Wolff rearrangement is observed in all studied cyclic diazo-1,3-diketones after cleavage of nitrogen molecules. The energy of ionizing electrons ∼20 eV in the case of compounds Ib, Id - Ie dominating ions are fragments of the [M-N_2]"+"·, in the compound Ia at 18 and 20 eV is dominant fragment [M-N_2-CO-C_2H_2-H]"+"· and for the Ic at 30 eV becomes a dominant fragment [M-N_2-CH_3]"+"· (m/z = 123) but at (25 - 18) eV the most intensive ion is [M-N_2]"+"· (m/z = 138). (authors)

  19. Distinguishing Aspartic and Isoaspartic Acids in Peptides by Several Mass Spectrometric Fragmentation Methods

    Science.gov (United States)

    DeGraan-Weber, Nick; Zhang, Jun; Reilly, James P.

    2016-12-01

    Six ion fragmentation techniques that can distinguish aspartic acid from its isomer, isoaspartic acid, were compared. MALDI post-source decay (PSD), MALDI 157 nm photodissociation, tris(2,4,6-trimethoxyphenyl)phosphonium bromide (TMPP) charge tagging in PSD and photodissociation, ESI collision-induced dissociation (CID), electron transfer dissociation (ETD), and free-radical initiated peptide sequencing (FRIPS) with CID were applied to peptides containing either aspartic or isoaspartic acid. Diagnostic ions, such as the y-46 and b+H2O, are present in PSD, photodissociation, and charge tagging. c•+57 and z-57 ions are observed in ETD and FRIPS experiments. For some molecules, aspartic and isoaspartic acid yield ion fragments with significantly different intensities. ETD and charge tagging appear to be most effective at distinguishing these residues.

  20. Practical aspects of trapped ion mass spectrometry, 5 applications of ion trapping devices

    CERN Document Server

    March, Raymond E

    2009-01-01

    Examines ion/neutral and ion/ion reactions, ion spectroscopy, and the structural characterization of proteins and peptides using quadropole ion trap mass spectrometry, Fourier transform - ion cyclotron resonance (FT-ICR) mass spectrometry, and traveling wave ion mobility mass spectrometry.

  1. Using fragmentation trees and mass spectral trees for identifying unknown compounds in metabolomics.

    Science.gov (United States)

    Vaniya, Arpana; Fiehn, Oliver

    2015-06-01

    Identification of unknown metabolites is the bottleneck in advancing metabolomics, leaving interpretation of metabolomics results ambiguous. The chemical diversity of metabolism is vast, making structure identification arduous and time consuming. Currently, comprehensive analysis of mass spectra in metabolomics is limited to library matching, but tandem mass spectral libraries are small compared to the large number of compounds found in the biosphere, including xenobiotics. Resolving this bottleneck requires richer data acquisition and better computational tools. Multi-stage mass spectrometry (MSn) trees show promise to aid in this regard. Fragmentation trees explore the fragmentation process, generate fragmentation rules and aid in sub-structure identification, while mass spectral trees delineate the dependencies in multi-stage MS of collision-induced dissociations. This review covers advancements over the past 10 years as a tool for metabolite identification, including algorithms, software and databases used to build and to implement fragmentation trees and mass spectral annotations.

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

    Science.gov (United States)

    Sun, Jianghao; Baker, Andrew; Chen, Pei

    2011-09-30

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

  3. Fragmentation of water on swift {sup 3}He{sup 2+} ion impact

    Energy Technology Data Exchange (ETDEWEB)

    Sabin, John R. [Quantum Theory Project, Departments of Chemistry and Physics, P.O. Box 118435, University of Florida, Gainesville, FL 32611-8435 (United States); Institut for Fysik og Kemi, Suddansk Universitet, 5230 Odense M (Denmark)], E-mail: sabin@qtp.ufl.edu; Cabrerra-Trujillo, Remigio [Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico, Apartado Postal 48-3, Cuernavaca, Morelos 62251 (Mexico); Stolterfoht, Nikolaus [Hahn-Meitner Institut, Glienickerstrasse 100, D-14109 Berlin (Germany); Deumens, Erik; Ohrn, Yngve [Quantum Theory Project, Departments of Chemistry and Physics, P.O. Box 118435, University of Florida, Gainesville, FL 32611-8435 (United States)

    2009-01-15

    Charge exchange and fragmentation are the usual results in ion-molecule collision systems, and the specifics of the fragmentation process determine the chemical destiny of the target system. In this paper, we report recent progress on calculations of the fragmentation patterns for the model system He{sup 2+} + H{sub 2}O for projectile energies of a few keV. The calculations are obtained using the electron-nuclear dynamics (END) method for solution of the time-dependent Schroedinger equation.

  4. Jet mass dependence of fragmentation in positron-proton collisions

    Energy Technology Data Exchange (ETDEWEB)

    Urmossy, K. [Shandong University, School of Physics and Key Laboratory of Particle Physics and Particle Irradiation (MOE), Jinan, Shandong (China)

    2017-02-15

    We propose the characterization of fragmentation functions by the energy fraction x a hadron takes away from the energy of the jet measured in the frame co-moving with the jet. Besides, we propose the usage of the jet mass as the fragmentation scale Q. We show that these two Lorentz-invariant variables emerge naturally in a microcanonical ensemble with conserved four-momentum. Then, we construct a statistical hadronisation model, in which, two features of the hadronic final states in various high-energy reactions (power law spectra and negative-binomial multiplicity distributions) can be connected simply. Finally, we analyse the scale dependence of the parameters of the model (power of the spectrum and mean energy per hadron) in the φ{sup 3} theory. Fitting fragmentation functions in diffractive positron-proton collisions, we obtain a prediction for the jet mass dependence of the hadron multiplicity distribution inside jets. (orig.)

  5. Fission fragment yields from heavy-ion-induced reactions measured with a fragment separator

    Science.gov (United States)

    Tarasov, O. B.; Delaune, O.; Farget, F.; Morrissey, D. J.; Amthor, A. M.; Bastin, B.; Bazin, D.; Blank, B.; Cacéres, L.; Chbihi, A.; Fernández-Dominguez, B.; Grévy, S.; Kamalou, O.; Lukyanov, S. M.; Mittig, W.; Pereira, J.; Perrot, L.; Saint-Laurent, M.-G.; Savajols, H.; Sherrill, B. M.; Stodel, C.; Thomas, J. C.; Villari, A. C.

    2018-04-01

    The systematic study of fission fragment yields under different initial conditions has provided valuable experimental data for benchmarking models of fission product yields. Nuclear reactions using inverse kinematics coupled to the use of a high-resolution spectrometer with good fragment identification are shown here to be a powerful tool to measure the inclusive isotopic yields of fission fragments. In-flight fusion-fission was used in this work to produce secondary beams of neutron-rich isotopes in the collisions of a 238U beam at 24 MeV/u with 9Be and 12C targets at GANIL using the LISE3 fragment separator. Unique identification of the A, Z, and atomic charge state, q, of fission products was attained with the Δ E- TKE-B ρ- ToF measurement technique. Mass, and atomic number distributions are reported for the two reactions. The results show the importance of different reaction mechanisms in the two cases. The optimal target material for higher yields of neutron-rich high- Z isotopes produced in fusion-fission reactions as a function of projectile energy is discussed.

  6. Nanoelectrospray with ion-trap mass spectrometry for the determination of beta-casomorphins in derived milk products.

    Science.gov (United States)

    Juan-García, Ana; Font, Guillermina; Juan, Cristina; Picó, Yolanda

    2009-11-15

    Beta-casomorphins (b-CMs) are bioactive peptides derived from casein with opioid agonist effects similar to morphine. The use of electrospray (ESI) with quadrupole ion-trap mass spectrometry (QIT-MS) for these compounds in two matrices, cheese and milk, was examined. It was compared to a liquid chromatography (LC) coupled to mass spectrometry (LC-MS), and a "soft" ionisation technique, NanoMate, with selected ion monitoring (SIM), which are unreliable for the determination of trace casomorphins in derived milk products. b-CM mass fragmentation pathways were done for the four most common b-CMs: beta-casomorphin (1-5) bovine (b-CM-5), beta-casomorphin (1-7) bovine (b-CM-7), [D-Ala2, D-Pro4,Tyr5]-beta-casomorphin (1-5) amide (b-CM-10) and beta-casomorphin (1-5) amide [D-Ala2,Hyp4,Tyr5] (b-CM-11). The major product ions obtained in QIT-MS were used to construct fragmentation pathways for b-CMs. The different collision energies using automated nanoelectrospray ion source NanoMate and conventional LC in QIT-MS were studied. Calibration data for b-CMs, using spiked milk or cheese samples (10 g or 10 mL), were: NanoMate/MS (25-1000 microg/L), r(2)=0.998; NanoMate/MS(2) (5-1000 microg/L), r(2)=0.9992; NanoMate/MS(3) (2.5-1000 microg/L), r(2)=0.9998. Reproducibility data (% RSD, N=5) for NanoMate/MS(n) mode ranged between 2.0 at 500 microg/L and 7.0 at 10 microg/L.

  7. Soft ionization of saturated hydrocarbons, alcohols and nonpolar compounds by negative-ion direct analysis in real-time mass spectrometry.

    Science.gov (United States)

    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.

  8. An ultra-sensitive instrument for collision activated dissociation mass spectrometry with high mass resolution

    International Nuclear Information System (INIS)

    Louter, G.J.

    1982-01-01

    During the last decade Collision Activated Dissociation Mass Spectrometry (CAD-MS) has developed into an important and sometimes unique technique for the structure elucidation of ions. An extensive description of the double stage MS is given, which has been especially devloped for CAD-MS. A high mass resolution and a very high sensitivity are obtained by application of special techniques like post-acceleration of fragment ions, quadrupole (Q-pole) lenses and an electro-optical, simultaneous ion detection system. The operation of the rather complex ion-optics is demonstrated by application of a computer simulation of the tandem MS. Special attention is given to the action of the four Q-pole lenses and the second sector magnet upon curvature and position of the mass focal plane. Two mass calibration methods are described for the fragment spectra. The so-called polynomial-method applies a fifth-order polynomial approximation of the functional relation between position on the detector and corresponding relative momentum of fragment ions. The second method uses the matrix model of the instrument. The detector consists of two channelplates (CEMA), a fibre optics slab, coated with a phosphor layer, a camera objective and a 1024-channels photodiode-array. A bio-chemical and an organic-chemical application of the instrument are given. As bio-chemical application the peak m/z 59 in the pyrolysis mass spectrum of complete mycobacteria is identified. As an example of organic-chemical application the fragmentation process of 2,3-butadienoic acid has been investigated. (Auth.)

  9. Mass distribution of fission fragments using SSNTDs based image analysis system

    International Nuclear Information System (INIS)

    Kolekar, R.V.; Sharma, D.N.

    2006-01-01

    Lexan polycarbonate track detector was used to obtain mass distribution of fission fragments from 252 Cf planchette source, Normally, if the fission fragments are incident perpendicular to the lexan surface, the diameter of heavy fragment is greater than that of lighter fragment. In practical problems fission fragments are incident on the detector at all angles. So, in the present experiment, lexan detector was exposed to 252 Cf planchette source in 2π geometry. Fission fragments were incident on the detector with various angles. So the projected fission track length for fission fragment of same energy is different because of different angle of incidence. Image analysis software was used to measure the projected track length. But the problem is that for fission fragment having greater angle of incidence the entire track length is not focused on the surface. So reduced track length is measured. This problem is solved by taking two images, one at the surface and one at the tip of track and then overlapping both the images using image analysis software. The projected track length and the depth of the track were used to get the angle of incidence. Fission track lengths were measured for same angle of incidence. In all 500 track lengths were measured and plot for mass distribution for fission fragment was obtained.(author)

  10. Secondary ion mass spectroscopy (SIMS)

    International Nuclear Information System (INIS)

    Naik, P.K.

    1975-01-01

    Secondary Ion Mass Spectrometry (SIMS) which is primarily a method for investigating the chemical composition of the uppermost atomic layer of solid surfaces is explained. In this method, the specimen is bombarded with a primary positive ion beam of small current density monolayer. Positive and negative ions sputtered from the specimen are mass analysed to give the surface chemical composition. The analytical system which consists of a primary ion source, a target manipulator and a mass spectrometer housed in an ultrahigh vacuum system is described. This method can also be used for profile measurements in thin films by using higher current densities of the primary ions. Fields of application such as surface reactions, semiconductors, thin films emission processes, chemistry, metallurgy are touched upon. Various aspects of this method such as the sputtering process, instrumentation, and applications are discussed. (K.B.)

  11. Analysis of supramolecular surface nanostructures using secondary ion mass spectrometry (poster)

    International Nuclear Information System (INIS)

    Halaszova, S.; Velic, D.

    2013-01-01

    Our system consists of host molecules β-cyclodextrin (C 42 H 70 O 35 ), of implemented Iron nanoparticles (guest). Whole supramolecular complex is placed on a gold substrate. In our project we work with monotiolated β-cyclodextrin (C 42 H 70 O 34 S), consisting of seven α-D-1-4 glucopyranose units. Cyclodextrins have been selected deliberately because of their ability to form inclusion complexes .They are also capable of forming structures similar to self-assembly monolayers. To study the formation of these supramolecular surface nanostructures mass secondary ion spectrometry is used. With this technique fragmentation of monotiolated β-cyclodextrin and the presence of the supramolecular complex on a gold surface can be examined. The observed fragments of monotiolated cyclodextrines films can be divided into three groups: Au X H Y S Z , fragments originating from cyclodextrin molecules associated with Au. Fragments as (C 42 H 70 O 34 S)Na + , (C 42 H 70 O 35 )Na + and (AuC 42 H 69 O 34 S)Na + were identified as well as fragments thereof in cationized form with K + . The main objective of the project is a detailed study and preparation of supramolecular nanostructures consisting of complex guest-host monotiolated β-cyclodextrin host-iron), and a gold substrate. (Authors)

  12. Fragmentation pathways and structural characterization of organophosphorus compounds related to the Chemical Weapons Convention by electron ionization and electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Hosseini, Seyed Esmaeil; Saeidian, Hamid; Amozadeh, Ali; Naseri, Mohammad Taghi; Babri, Mehran

    2016-12-30

    For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  13. A model for projectile fragmentation

    International Nuclear Information System (INIS)

    Chaudhuri, G; Mallik, S; Gupta, S Das

    2013-01-01

    A model for projectile fragmentation is developed whose origin can be traced back to the Bevalac era. The model positions itself between the phenomenological EPAX parametrization and transport models like 'Heavy Ion Phase Space Exploration' (HIPSE) model and antisymmetrised molecular dynamics (AMD) model. A very simple impact parameter dependence of input temperature is incorporated in the model which helps to analyze the more peripheral collisions. The model is applied to calculate the charge, isotopic distributions, average number of intermediate mass fragments and the average size of largest cluster at different Z bound of different projectile fragmentation reactions at different energies.

  14. Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

    Science.gov (United States)

    Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

    2004-05-01

    The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

  15. Tandem mass spectrometric analysis of cyclophosphamide, ifosfamide and their metabolites.

    Science.gov (United States)

    Liu, Zhongfa; Chan, Kenneth K; Wang, Jeffrey J

    2005-01-01

    A detailed multi-stage (MSn) fragmentation study of cyclophosphamide (CP), ifosfamide (IF) and their major metabolites, using an ion-trap mass spectrometer and a Q-TOF mass spectrometer, was performed with the aid of specifically deuterium-labeled analogs. The analytes showed good responses in positive-ion electrospray mass spectrometry as [MH]+ ions. Tandem mass spectra revealed a wealth of structurally specific ions, allowing characterization of the fragmentation pathways of these analytes. The major fragmentation pathways of the protonated CP and IF are elimination of ethylene from C5 and C6 of 1,3,2-oxazaphosphorine-2-oxide via a McLafferty rearrangement, and cleavage of the P-N bond. However, their activated 4-OOH and 4-OH metabolites primarily underwent hydrogen peroxide elimination and dehydration, respectively, followed by fragmentation pathways similar to those of CP and IF. These results should prove useful in structural elucidation of future analogs of CP and IF, and/or of their metabolites. Copyright (c) 2005 John Wiley & Sons, Ltd.

  16. FRAGMENTATION STUDIES OF D6,7-ANHIDROERITROMISIN-A BY LIQUID CHROMATOGRAPHY-MASS SPECTROSCOPY (LC-MS

    Directory of Open Access Journals (Sweden)

    Khairan Khairan

    2010-06-01

    Full Text Available Semisynthesis of D6,7-Anhydroerythromycin-A was done by biomodification technique by addition of 0.2% INH into a culture fermentation of Saccharopolyspora erythraea ATCC 11635 in medium Hutchinson. The aim of this research is to studies of fragmentation pattern from new matabolite of D6,7-Anhydroerythromycin-A by Liquid Chromatography-Mass Spectroscopy (LC-MS and the ionization of mass spectroscopy is use by ESI (Electrospray Ionization pattern. The FT-IR spectrometric analyzes showed a stretching vibration of C=C conjugated group at wave number 1602.7 cm-1. This C=C conjugated vibration indicated the existence of double bond between C6 and C7 (D6,7, this confirmed that isolate contained D6,7-Anhydroerythromycin-A (the possibility of D6,7 was positive. For complementation, a LC-MS (Liquid Chromatography-Mass Spectroscopy analyzes using ESI-MS (Electrospray Ionization-Mass Spectroscopy ionization pattern was conducted to the isolate which resulted Quassimolecular ions [M+H]+ of D7,8- and D6,7-Anhydroerythromycin-A. LC-MS spectrogram of the isolate, which gave two peaks of m/z 732.2460 and m/z 716.2522, confirmed that the m/z 732.2460 possibly was D7,8-Anhydroerythromycin-A, while the m/z 716.2502 and m/z 715.2522 possibly were D6,7-Anhydroerythromycin-A.   Keywords: isoniazid, enoyl reduction, D6,7-Anhidroeritromisin-A, fragmentation, LC-MS.

  17. Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

    Energy Technology Data Exchange (ETDEWEB)

    Neustetter, M.; Jabbour Al Maalouf, E.; Denifl, S., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt [Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstrasse 25, A-6020 Innsbruck (Austria); Limão-Vieira, P., E-mail: Stephan.Denifl@uibk.ac.at, E-mail: plimaovieira@fct.unl.pt [Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstrasse 25, A-6020 Innsbruck (Austria); Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica (Portugal)

    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 ≤ 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.

  18. Low Mass Ions in Laser Desorption/Ionization Mass Spectrometry of 1-Methoxy-5-aminotetrazole

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Soo Gyeong; Bae, Kwang Tae; Goh, Eun Mee; Bae, Se Won [Agency for Defense Development, Daejeon (Korea, Republic of); Shin, Ik-Soo [Soongsil University, Seoul (Korea, Republic of)

    2016-01-15

    The development of novel energetic molecules (EMs) with high power, good safety features, great chemical stability, and environmentally less harmful nature is of great interest in the satellite launcher, missile warhead, ammunition, and pyrotechnic researches. Recently, many researchers have focused on aromatic nitrogen heterocycles such as pyrazole, imidazole, triazole, tetrazole, and pentazole as promising candidates to replace the current EMs used in civilian and military applications. We performed MALDI and LDI experiments with energetic tetrazole derivatives which were of great interest for the application of high performance explosives and fast burning propellants. Particularly, LDI experiments provided low mass ion peaks from decomposition of MAT, which were useful to analyze decomposition mechanism of tetrazoles at TOF MS in high vacuum. The LDI experiments showed various decomposed ion products, which implied several decomposition mechanisms including the detachment of side function groups and the fragmentation of tetrazole ring. The high-level DFT calculations also supported the peaks obtained from LDI experiments.

  19. Analysis of organic compounds by secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS)

    International Nuclear Information System (INIS)

    Ewinger, H.P.

    1993-05-01

    This study is about the use of secondary neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS) as analytical techniques with depth resolution in determining organic components in environmental solid microparticles. The first application of plasma SNMS to organic compounds revealed the spectra to be composed mainly of signals from the atoms of all participating elements, such as C, H, O, N, S, P, and Cl. In addition, signals produced by multi-atomic clusters can be detected, such as CH, C 2 , CH 2 , C 2 H, and C 3 , as well as signals indicating the presence of organic compounds with hetero elements, such as OH, NH, and CN. Their intensity decreases very markedly with increasing numbers of atoms. Among the signals from bi-atomic clusters, those coming from elements with large mass differences are most intense. The use of plasma SNMS with organic compounds has shown that, except for spurious chemical reactions induced by ion bombardment and photodesorption by the photons of the plasma, it is possible to analyze with resolution in depth, elements of organic solids. A more detailed molecular characterization of organic compounds is possible by means of SIMS on the basis of multi-atomic fragments and by comparison with suitable signal patterns. (orig./BBR) [de

  20. Present and future isochronous mass spectrometry at GSI-FAIR. 25 new masses of fission fragments novel analysis method design of a new time-of-flight detector system

    Energy Technology Data Exchange (ETDEWEB)

    Diwisch, Marcel

    2015-07-01

    In this work the basic features of isochronous mass spectroscopy (IMS) for the present facilities at GSI and also for the future experiments at FAIR have been experimentally and theoretically investigated. The prospects and limitations of IMS have been carefully studied with calculations and experiments. The data of two different previous IMS experiments at GSI have been combined and analyzed with a novel correlation-matrix method (CMM). Both experiments were performed with the fragment separator FRS and the experimental ion storage ring ESR. In both experiments fission fragments, created by {sup 238}U projectiles in a beryllium target at the entrance of the FRS, were spatially separated and injected into the isochronous ESR. In the first experiment the full Bρ acceptance of the ESR was used whereas in the second one the Bρ of each fragment was defined by slits in the dispersive central focal plane of the FRS. In this way the magnetic rigidity was well-determined for all injected fragments to ΔBρ/Bρ=1.5.10{sup -4}. The harvest of this analysis is 25 new masses near and at the N=82 shell closure. The comparison of the experimental results with the AME extrapolation and different theoretical models reveal significant differences due to the low theoretical prediction power of the calculations in this mass range. In this respect one has to emphasize that due to the novel analysis method in this work these 25 new masses could be extracted additional to our previously already published results. It is almost needless to mention that the new mass values will contribute to improved r-process calculations which are in progress. In the present analysis the existing matrix method was extended with a variable scaling factor (s). The scaling factor was determined for each mass-to-charge ratio (m/q) of the measured ions and implemented as a function of m/q in the analysis. This has extended the accessible m/q range. The revolution time was determined via a 3rd-order fit of

  1. Present and future isochronous mass spectrometry at GSI-FAIR. 25 new masses of fission fragments novel analysis method design of a new time-of-flight detector system

    International Nuclear Information System (INIS)

    Diwisch, Marcel

    2015-01-01

    In this work the basic features of isochronous mass spectroscopy (IMS) for the present facilities at GSI and also for the future experiments at FAIR have been experimentally and theoretically investigated. The prospects and limitations of IMS have been carefully studied with calculations and experiments. The data of two different previous IMS experiments at GSI have been combined and analyzed with a novel correlation-matrix method (CMM). Both experiments were performed with the fragment separator FRS and the experimental ion storage ring ESR. In both experiments fission fragments, created by 238 U projectiles in a beryllium target at the entrance of the FRS, were spatially separated and injected into the isochronous ESR. In the first experiment the full Bρ acceptance of the ESR was used whereas in the second one the Bρ of each fragment was defined by slits in the dispersive central focal plane of the FRS. In this way the magnetic rigidity was well-determined for all injected fragments to ΔBρ/Bρ=1.5.10 -4 . The harvest of this analysis is 25 new masses near and at the N=82 shell closure. The comparison of the experimental results with the AME extrapolation and different theoretical models reveal significant differences due to the low theoretical prediction power of the calculations in this mass range. In this respect one has to emphasize that due to the novel analysis method in this work these 25 new masses could be extracted additional to our previously already published results. It is almost needless to mention that the new mass values will contribute to improved r-process calculations which are in progress. In the present analysis the existing matrix method was extended with a variable scaling factor (s). The scaling factor was determined for each mass-to-charge ratio (m/q) of the measured ions and implemented as a function of m/q in the analysis. This has extended the accessible m/q range. The revolution time was determined via a 3rd-order fit of the time

  2. Ranking Fragment Ions Based on Outlier Detection for Improved Label-Free Quantification in Data-Independent Acquisition LC-MS/MS

    Science.gov (United States)

    Bilbao, Aivett; Zhang, Ying; Varesio, Emmanuel; Luban, Jeremy; Strambio-De-Castillia, Caterina; Lisacek, Frédérique; Hopfgartner, Gérard

    2016-01-01

    Data-independent acquisition LC-MS/MS techniques complement supervised methods for peptide quantification. However, due to the wide precursor isolation windows, these techniques are prone to interference at the fragment ion level, which in turn is detrimental for accurate quantification. The “non-outlier fragment ion” (NOFI) ranking algorithm has been developed to assign low priority to fragment ions affected by interference. By using the optimal subset of high priority fragment ions these interfered fragment ions are effectively excluded from quantification. NOFI represents each fragment ion as a vector of four dimensions related to chromatographic and MS fragmentation attributes and applies multivariate outlier detection techniques. Benchmarking conducted on a well-defined quantitative dataset (i.e. the SWATH Gold Standard), indicates that NOFI on average is able to accurately quantify 11-25% more peptides than the commonly used Top-N library intensity ranking method. The sum of the area of the Top3-5 NOFIs produces similar coefficients of variation as compared to the library intensity method but with more accurate quantification results. On a biologically relevant human dendritic cell digest dataset, NOFI properly assigns low priority ranks to 85% of annotated interferences, resulting in sensitivity values between 0.92 and 0.80 against 0.76 for the Spectronaut interference detection algorithm. PMID:26412574

  3. Fragment mass distribution of proton-induced spallation reaction with intermediate energy

    International Nuclear Information System (INIS)

    Fan Sheng; Ye Yanlin; Xu Chuncheng; Chen Tao; Sobolevsky, N.M.

    2000-01-01

    The test of part benchmark of SHIELD code is finished. The fragment cross section and mass distribution and excitation function of the residual nuclei from proton-induced spallation reaction on thin Pb target with intermediate energy have been calculated by SHIELD code. And the results are in good agreement with measured data. The fragment mass distribution of the residual nuclei from proton-induced spallation reaction on thick Pb target with incident energy 1.6 GeV have been simulated

  4. Ion induced fragmentation of biomolecular systems at low collision energies

    International Nuclear Information System (INIS)

    Bernigaud, V; Adoui, L; Chesnel, J Y; Rangama, J; Huber, B A; Manil, B; Alvarado, F; Bari, S; Hoekstra, R; Postma, J; Schlathoelter, T

    2009-01-01

    In this paper, we present results of different collision experiments between multiply charged ions at low collision energies (in the keV-region) and biomolecular systems. This kind of interaction allows to remove electrons form the biomolecule without transferring a large amount of vibrational excitation energy. Nevertheless, following the ionization of the target, fragmentation of biomolecular species may occur. It is the main objective of this work to study the physical processes involved in the dissociation of highly electronically excited systems. In order to elucidate the intrinsic properties of certain biomolecules (porphyrins and amino acids) we have performed experiments in the gas phase with isolated systems. The obtained results demonstrate the high stability of porphyrins after electron removal. Furthermore, a dependence of the fragmentation pattern produced by multiply charged ions on the isomeric structure of the alanine molecule has been shown. By considering the presence of other surrounding biomolecules (clusters of nucleobases), a strong influence of the environment of the biomolecule on the fragmentation channels and their modification, has been clearly proven. This result is explained, in the thymine and uracil case, by the formation of hydrogen bonds between O and H atoms, which is known to favor planar cluster geometries.

  5. Kriterijum efikasnosti i optimizacija mase fragmenta projektila parčadnog dejstva / Efficiency criterion and optimization of fragment mass in fragmentation projectiles

    Directory of Open Access Journals (Sweden)

    Predrag Elek

    2003-07-01

    Full Text Available U radu se razmatra problem optimizacije mase parčadi koja nastaju fragmentacijom projektila parčadnog dejstva. Pokazano je da optimalna masa parčeta prvenstveno zavisi od njegovih kinetičkih karakteristika na cilju kao i od usvojenog kriterijuma efikasnosti. Proračuni pokazuju da su postojeći kriterijumi, minimalna zahtevana kinetička energija fragmenta odnosno minimalna kinetička energija po jedinici napadne površine, nesaglasni - odnosno da daju bitno različite vrednosti optimalne mase. Zaključeno je da kriterijum specifične energije parčeta podrazumeva manju masu optimalnog parčeta i ukazuje na značaj parčadi veoma male mase sa stanovišta efikasnosti. Jasno je da ovako određena optimalna masa efikasnog parčeta predstavlja veoma važan parametar projektila parčadnog dejstva, pa je neophodna eksperimentalna verifikacija dobijenih teorijskih rezultata. / This paper considers the problem of optimizing the mass of HE projectile fragments. It is shown that the optimum fragment mass is a function of its kinetic characteristics at the target and an adopted efficiency criterion. Computations show that the most prominent criteria, minimum required kinetic energy and minimum kinetic energy per unit of cross--sectional area, are incompatible - i. e. they provide significantly different values of the optimum mass. It is concluded that the criterion of specific kinetic energy corresponds to a lower optimum fragment mass, which indicates the importance of fragments of low masses from the aspect of efficiency. The theoretically determined optimum fragment mass represents a very significant parameter for design optimization of fragmentation projectiles, but experimental verification of obtained results is essentially important as well.

  6. Double-arm time-of-flight mass-spectrometer of nuclear fragments

    International Nuclear Information System (INIS)

    Ajvazian, G.M.; Astabatyan, R.A.

    1995-01-01

    A double-arm time-of-flight spectrometer of nuclear fragments for the investigation of heavy nuclei photofission in the intermediate energy range is described. The calibration results and working characteristics of the spectrometer, obtained using 252 Cf as a source of spontaneous fission, are presented. A mass resolution of σ m ∼2-3 a.m.u. was obtained within the registered fragments mass range of 80-160 a.m.u. The spectrometer was tested in the experiment on the investigation of 238 U nuclei fission by Bremsstahlung photons with Eγ max=1.75 GeV

  7. Critical Evaluation of Native Electrospray Ionization Mass Spectrometry for Fragment-Based Screening.

    Science.gov (United States)

    Göth, Melanie; Badock, Volker; Weiske, Jörg; Pagel, Kevin; Kuropka, Benno

    2017-08-08

    Fragment-based screening presents a promising alternative to high-throughput screening and has gained great attention in recent years. So far, only a few studies have discussed mass spectrometry as a screening technology for fragments. Herein, we report the application of native electrospray ionization mass spectrometry (MS) for screening defined sets of fragments against four different target proteins. Fragments were selected from a primary screening conducted with a thermal shift assay (TSA) and represented different binding categories. Our data indicated that, beside specific complex formation, many fragments show extensive multiple binding and also charge-state shifts. Both of these factors complicate automated data analysis and decrease the attractiveness of native MS as a primary screening tool for fragments. A comparison of the hits identified by native MS and TSA showed good agreement for two of the proteins. Furthermore, we discuss general challenges, including the determination of an optimal fragment concentration and the question of how to rank fragment hits according to their affinity. In conclusion, we consider native MS to be a highly valuable tool for the validation and deeper investigation of promising fragment hits rather than a method for primary screening. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Fission before mass equilibration in heavy ion reactions

    International Nuclear Information System (INIS)

    Yadav, C.; Thomas, R.G.; Mohanty, A.K.

    2013-01-01

    For compound nucleus (CN) fission, it is expected that the width of the fragment mass distribution is independent of the entrance channel. In quasifission reaction, however, recent experiments reported anomalous broadening of mass distribution for more symmetric systems forming the same compound nucleus in fissile (fissility ∼ 0.8) and less fissile (fissility ∼ 0.7) systems. These measurements have not shown any mass-angle correlation, but width of fission fragment mass distribution was found to be consistently higher than that expected for fusion-fission

  9. Probing peptide fragment ion structures by combining sustained off-resonance collision-induced dissociation and gas-phase H/D exchange (SORI-HDX) in Fourier transform ion-cyclotron resonance (FT-ICR) instruments.

    Science.gov (United States)

    Somogyi, Arpád

    2008-12-01

    The usefulness of gas-phase H/D exchange is demonstrated to probe heterogeneous fragment and parent ion populations. Singly and multiply protonated peptides/proteins were fragmented by using sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The fragments and the surviving precursor ions then all undergo H/D exchange in the gas-phase with either D(2)O or CD(3)OD under the same experimental conditions. Usually, 10 to 60 s of reaction time is adequate to monitor characteristic differences in the H/D exchange kinetic rates. These differences are then correlated to isomeric ion structures. The SORI-HDX method can be used to rapidly test fragment ion structures and provides useful insights into peptide fragmentation mechanisms.

  10. Fragmentation of C2H4 by charge-changing collisions of O2+ ions

    International Nuclear Information System (INIS)

    Sato, S.; Mizuno, T.; Yamada, T.; Imai, M.; Shibata, H.; Itoh, A.; Tsuchida, H.

    2009-01-01

    We investigated molecular fragmentation of C 2 H 4 in charge-changing collisions of 1.14MeV O 2+ ions. Branching ratios associated with decaying from temporary produced (C 2 H 4 ) r+ ions into various fragment channels were obtained. Dissociation via a C-C bond breaking is preferential in 1-electron loss collisions in comparison with 1-electron capture collisions. We confirmed that multiple ionization and dissociation rarely occur in electron capture collisions, while they occur rather strongly in electron loss collisions. (author)

  11. Spatial and energy distributions of the fragments resulting from the dissociation of swift molecular ions in solids

    International Nuclear Information System (INIS)

    Heredia-Avalos, Santiago; Garcia-Molina, Rafael; Abril, Isabel

    2002-01-01

    We have simulated the spatial evolution and energy loss of the fragments that result when swift molecular ions dissociate inside solid targets. In our calculations we have considered that these fragments undergo the following interactions: Coulomb repulsion (among like charged particles), stopping and wake forces (due to electronic excitations induced in the target), and nuclear scattering (with the target nuclei). We study the case of silicon targets irradiated with boron molecular or atomic ions; our results show that the main differences in the energy and spatial distributions of molecular fragments or atomic ions appear at shallow regions, and these tend to disappear at deeper depths

  12. [Determination of strobilurin fungicides in fruits and their mass fragmentation routes by ultra performance liquid chromatography-tandem mass spectrometry].

    Science.gov (United States)

    Zhou, Yao; Yang, Huiqin; Shi, Yiyin; Chen, Jiaxian; Zhu, Jian; Deng, Xiaojun; Guo, Dehua

    2017-09-08

    A method was developed for the simultaneous determination of six strobilurin fungicide ( E -metominostrobin, azoxystrobin, kresoxim-methyl, picoxystrobin, pyraclostrobin and trifloxystrobin) residues in orange, banana, apple and pineapple samples by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The fragmentation routes of all the compounds were explained by the aid of a fragment predicting software ACD Lab/MS Fragmenter. The samples were extracted by acetonitrile, then cleaned up by amino solid phase extraction cartridges (SupelClean LC-NH 2 ). The extracts were separated on a ACQUITY UPLC BEH C 18 column (50 mm×2.1 mm, 1.7 μm) with gradient elution. Acetonitrile containing 0.1% (v/v) formic acid and 10 mmol/L ammonium acetate containing 0.1% (v/v) formic acid were used as mobile phases. The samples were detected by electrospray ionization (ESI)-MS/MS in positive ion and multiple reaction monitoring (MRM) mode, quantified by external standard method. Good linearities were obtained in the range of 5-100 μg/L (for pyraclostrobin, 1-20 μg/L) with correlation coefficients ( r 2 ) greater than 0.999. The recoveries ranged from 60.4% to 120% with the relative standard deviations between 2.15% and 15.1% ( n =6). The developed method can meet the inspection of the six strobilurin residues in the orange, banana, apple and pineapple samples.

  13. Exploring ECD on a Benchtop Q Exactive Orbitrap Mass Spectrometer

    DEFF Research Database (Denmark)

    Fort, Kyle L; Cramer, Christian N; Voinov, Valery G

    2018-01-01

    As the application of mass spectrometry intensifies in scope and diversity, the need for advanced instrumentation addressing a wide variety of analytical needs also increases. To this end, many modern, top-end mass spectrometers are designed or modified to include a wider range of fragmentation...... applications including middle-down proteomics, top-down proteomics, glycoproteomics, and disulfide bond mapping. We describe the modification of the popular Q Exactive Orbitrap mass spectrometer to extend its fragmentation capabilities to include ECD. We show that this modification allows ≥85% matched ion...... intensity to originate from ECD fragment ion types as well as provides high sequence coverage (≥60%) of intact proteins and high fragment identification rates with ∼70% of ion signals matched. Finally, the ECD implementation promotes selective disulfide bond dissociation, facilitating the identification...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Mass spectrometry and tandem mass spectrometry of citrus limonoids.

    Science.gov (United States)

    Tian, Qingguo; Schwartz, Steven J

    2003-10-15

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

  17. Ion detection in mass spectrometry

    International Nuclear Information System (INIS)

    Bolbach, Gerard

    2016-03-01

    This course aims at providing some elements for a better understanding of ion detectors used in mass spectrometers, of their operations, and of their limitations. A first part addresses the functions and properties of an ideal detector, how to detect ions in gas phase, and particle detectors and ion detectors used in mass spectrometry. The second part proposes an overview of currently used detectors with respect to their operation principle: detection from the ion charge (Faraday cylinder), detection by inductive effects (FTICR, Fourier Transform Ion Cyclotron Resonance), and detection by secondary electron emission. The third part discusses the specificities of secondary electron emission. The fourth one addresses operating modes and parameters related to detectors. The sixth part proposes a prospective view on future detectors by addressing the following issues: cryo-detector, inductive effect and charge detectors, ion detection and nano materials

  18. Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China); Ho, Hingman; Han, Quanbin [School of Chinese Medicine, Hong Kong Baptist University, 7 Baptist University Road, Kowloon Tong, Hong Kong (China); Fan, Xiaohui [College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058 (China); Zuo, Zhong, E-mail: joanzuo@cuhk.edu.hk [School of Pharmacy, Faculty of Medicine, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong (China)

    2015-01-01

    Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA.

  19. Novel algorithm for simultaneous component detection and pseudo-molecular ion characterization in liquid chromatography–mass spectrometry

    International Nuclear Information System (INIS)

    Zhang, Yufeng; Wang, Xiaoan; Wo, Siukwan; Ho, Hingman; Han, Quanbin; Fan, Xiaohui; Zuo, Zhong

    2015-01-01

    Highlights: • Novel stepwise component detection algorithm (SCDA) for LC–MS datasets. • New isotopic distribution and adduct-ion models for mass spectra. • Automatic component classification based on adduct-ion and isotopic distributions. - Abstract: Resolving components and determining their pseudo-molecular ions (PMIs) are crucial steps in identifying complex herbal mixtures by liquid chromatography–mass spectrometry. To tackle such labor-intensive steps, we present here a novel algorithm for simultaneous detection of components and their PMIs. Our method consists of three steps: (1) obtaining a simplified dataset containing only mono-isotopic masses by removal of background noise and isotopic cluster ions based on the isotopic distribution model derived from all the reported natural compounds in dictionary of natural products; (2) stepwise resolving and removing all features of the highest abundant component from current simplified dataset and calculating PMI of each component according to an adduct-ion model, in which all non-fragment ions in a mass spectrum are considered as PMI plus one or several neutral species; (3) visual classification of detected components by principal component analysis (PCA) to exclude possible non-natural compounds (such as pharmaceutical excipients). This algorithm has been successfully applied to a standard mixture and three herbal extract/preparations. It indicated that our algorithm could detect components’ features as a whole and report their PMI with an accuracy of more than 98%. Furthermore, components originated from excipients/contaminants could be easily separated from those natural components in the bi-plots of PCA

  20. Following the Ions through a Mass Spectrometer with Atmospheric Pressure Interface: Simulation of Complete Ion Trajectories from Ion Source to Mass Analyzer.

    Science.gov (United States)

    Zhou, Xiaoyu; Ouyang, Zheng

    2016-07-19

    Ion trajectory simulation is an important and useful tool in instrumentation development for mass spectrometry. Accurate simulation of the ion motion through the mass spectrometer with atmospheric pressure ionization source has been extremely challenging, due to the complexity in gas hydrodynamic flow field across a wide pressure range as well as the computational burden. In this study, we developed a method of generating the gas flow field for an entire mass spectrometer with an atmospheric pressure interface. In combination with the electric force, for the first time simulation of ion trajectories from an atmospheric pressure ion source to a mass analyzer in vacuum has been enabled. A stage-by-stage ion repopulation method has also been implemented for the simulation, which helped to avoid an intolerable computational burden for simulations at high pressure regions while it allowed statistically meaningful results obtained for the mass analyzer. It has been demonstrated to be suitable to identify a joint point for combining the high and low pressure fields solved individually. Experimental characterization has also been done to validate the new method for simulation. Good agreement was obtained between simulated and experimental results for ion transfer though an atmospheric pressure interface with a curtain gas.

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

    Science.gov (United States)

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

    2017-06-05

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

  2. Scaling of C{sub 60} ionization and fragmentation with the energy deposited in collisions with H{sup +}, H{sub 2}{sup +}, H{sub 3}{sup +} and He{sup +} ions (2-130 keV)

    Energy Technology Data Exchange (ETDEWEB)

    Bordenave-Montesquieu, D. [LCAR, IRSAMC, UMR 5589 CNRS, Universite Paul Sabatier, Toulouse (France)]. E-mail: dbm@yosemite.ups-tlse.fr; Moretto-Capelle, P.; Bordenave-Montesquieu, A.; Rentenier, A. [LCAR, IRSAMC, UMR 5589 CNRS, Universite Paul Sabatier, Toulouse (France)

    2001-03-14

    Fragmentation, ionization and C{sub 2} fragment evaporation of the C{sub 60} molecule induced by collisions with H{sup +}, H{sub 2}{sup +}, H{sub 3}{sup +} and He{sup +} monocharged ions have been measured in coincidence with the electron emission in the 2-130 keV projectile energy range. The time-of-flight mass spectra were found to vary strongly with the collision energy or velocity and the projectile. On the other hand, they scale rather nicely with the energy deposited in the molecule. Relative weights of the total multi-fragmentation into small C{sub n}{sup +} fragments (n=1-14), individual multi-fragmentation (n=1,7 and 11), double ionization of the intact molecule and evaporation of C{sub 2} molecules associated with the doubly charged fullerene ion, are used to illustrate our finding quantitatively. (author). Letter-to-the-editor.

  3. Angular distribution measurement of fragment ions from a molecule using a new beamline consisting of a Grasshopper monochromator

    Science.gov (United States)

    Saito, Norio; Suzuki, Isao H.; Onuki, Hideo; Nishi, Morotake

    1989-07-01

    Optical characteristics of a new beamline consisting of a premirror, a Grasshopper monochromator, and a refocusing mirror have been investigated. The intensity of the monochromatic soft x-ray was estimated to be about 108 photons/(s 100 mA) at 500 eV with the storage electron energy of 600 MeV and the minimum slit width. This slit width provides a resolution of about 500. Angular distributions of fragment ions from an inner-shell excited nitrogen molecule have been measured with a rotatable time-of-flight mass spectrometer by using this beamline.

  4. Angular distribution measurement of fragment ions from a molecule using a new beamline consisting of a Grasshopper monochromator

    International Nuclear Information System (INIS)

    Saito, N.; Suzuki, I.H.; Onuki, H.; Nishi, M.

    1989-01-01

    Optical characteristics of a new beamline consisting of a premirror, a Grasshopper monochromator, and a refocusing mirror have been investigated. The intensity of the monochromatic soft x-ray was estimated to be about 10 8 photons/(s 100 mA) at 500 eV with the storage electron energy of 600 MeV and the minimum slit width. This slit width provides a resolution of about 500. Angular distributions of fragment ions from an inner-shell excited nitrogen molecule have been measured with a rotatable time-of-flight mass spectrometer by using this beamline

  5. A heavy ion spectrometer system for the measurement of projectile fragmentation of relativistic heavy ions

    International Nuclear Information System (INIS)

    Engelage, J.; Crawford, H.J.; Greiner, L.; Kuo, C.

    1996-06-01

    The Heavy Ion Spectrometer System (HISS) at the LBL Bevalac provided a unique facility for measuring projectile fragmentation cross sections important in deconvolving the Galactic Cosmic Ray (GCR) source composition. The general characteristics of the apparatus specific to this application are described and the main features of the event reconstruction and analysis used in the TRANSPORT experiment are discussed

  6. Using In Silico Fragmentation to Improve Routine Residue Screening in Complex Matrices

    Science.gov (United States)

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

    2017-12-01

    Targeted residue screening requires the use of reference substances in order to identify potential residues. This becomes a difficult issue when using multi-residue methods capable of analyzing several hundreds of analytes. Therefore, the capability of in silico fragmentation based on a structure database ("suspect screening") instead of physical reference substances for routine targeted residue screening was investigated. The detection of fragment ions that can be predicted or explained by in silico software was utilized to reduce the number of false positives. These "proof of principle" experiments were done with a tool that is integrated into a commercial MS vendor instrument operating software (UNIFI) as well as with a platform-independent MS tool (Mass Frontier). A total of 97 analytes belonging to different chemical families were separated by reversed phase liquid chromatography and detected in a data-independent acquisition (DIA) mode using ion mobility hyphenated with quadrupole time of flight mass spectrometry. The instrument was operated in the MSE mode with alternating low and high energy traces. The fragments observed from product ion spectra were investigated using a "chopping" bond disconnection algorithm and a rule-based algorithm. The bond disconnection algorithm clearly explained more analyte product ions and a greater percentage of the spectral abundance than the rule-based software (92 out of the 97 compounds produced ≥1 explainable fragment ions). On the other hand, tests with a complex blank matrix (bovine liver extract) indicated that the chopping algorithm reports significantly more false positive fragments than the rule based software. [Figure not available: see fulltext.

  7. Radiocarbon positive-ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Freeman, Stewart P.H.T.; Shanks, Richard P. [Scottish Universities Environmental Research Centre (SUERC), Scottish Enterprise Technology Park, East Kilbride G75 0QF (United Kingdom); Donzel, Xavier; Gaubert, Gabriel [Pantechnik S.A., 13 Rue de la Résistance, 14400 Bayeux (France)

    2015-10-15

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  8. Radiocarbon positive-ion mass spectrometry

    International Nuclear Information System (INIS)

    Freeman, Stewart P.H.T.; Shanks, Richard P.; Donzel, Xavier; Gaubert, Gabriel

    2015-01-01

    Proof-of-principle of a new mass spectrometric technique for radiocarbon measurement is demonstrated. Interfering nitrogen and hydrocarbon molecules are largely eliminated in a charge-exchange cell operating on non-metallic gas. The positive-to-negative ion conversion is the reverse of that conventionally used in accelerator mass spectrometry (AMS) and is compatible with plasma ion sources that may be significantly more efficient and capable of greater output than are AMS sputter ion sources. The Nanogan electron cyclotron resonance (ECR) ion source employed exhibited no sample memory and the >50 kyrs age range of AMS was reproduced. A bespoke prototype new instrument is now required to optimise the plasma and cell physics and to realise hypothetical performance gains over AMS.

  9. Mass distribution law of systems of protocluster fragments

    Energy Technology Data Exchange (ETDEWEB)

    Ferraioli, F; Virgopia, N [Rome Univ. (Italy). Ist. di Matematica

    1979-02-01

    Starting from the hypothesis of coalescence through inelastic collisions of small fast moving interstellar gas clouds, an attempt has been made to study the evolutionary mass distribution of a system of fragments simulating a protocluster. The assumption of a mass spectrum with a continuous injection of newly formed entities into the primeval system, and the condition of gravitational reduction of the impact cross-section, have been considered. Comparisons of numerical experiments with the mass spectrum in some well-known young galactic clusters, confirm the mass distribution power-law already obtained by other authors. The empirical Schmidt's law concerning the rate of star formation is also confirmed. The hypothesis of the universal validity of the luminosity function, should not be 'a priori' rejected.

  10. Fragmentation of pure and hydrated clusters of 5Br-uracil by low energy carbon ions: observation of hydrated fragments

    Czech Academy of Sciences Publication Activity Database

    Castrovilli, M. C.; Markush, P.; Bolognesi, P.; Rousseau, P.; Maclot, S.; Cartoni, A.; Delaunay, R.; Domaracka, A.; Kočišek, Jaroslav; Huber, B. A.; Avaldi, L.

    2017-01-01

    Roč. 19, č. 30 (2017), s. 19807-19814 ISSN 1463-9076 Institutional support: RVO:61388955 Keywords : fragmentation * nano-hydrated 5BrU clusters * low energy carbon ions Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

  11. Multiphoton ionization and fragmentation study of acetone using 308 nm laser radiation

    Science.gov (United States)

    Liu Houxiang, Li Shutao, Han Jingcheng, Zhu Rong, Guan Yifu, Wu Cunkai

    1988-10-01

    Multiphoton ionization and fragmentation (MPI-F) of acetone molecules using 308 nm laser radiation was studied by using a molecular beam and quadrupole mass spectrometer. The ion peaks of acetone molecule appear at m/e=15 and 43, corresponding to the two fragments CH3+ and CH3CO+. It is considered that these two ions are, respectively, formed by direct (2+1) and 2-photon ionization of methyl and acetyl radicals, generated by photodissociation of acetone molecule.

  12. A novel ion imager for secondary ion mass spectrometry

    International Nuclear Information System (INIS)

    Matsumoto, Kazuya; Miyata, Kenji; Nakamura, Tsutomu

    1993-01-01

    This paper describes a new area detector for secondary ion mass spectrometry (SIMS) ion microscope, and its performance. The operational principle is based on detecting the change in potential of a floating photodiode caused by the ion-induced secondary-electron emission and the incoming ion itself. The experiments demonstrated that 10 1 -10 5 aluminum ions per pixel can be detected with good linear response. Moreover, relative ion sensitivities from hydrogen to lead were constant within a factor of 2. The performance of this area detector provides the potential for detection of kiloelectronvolt ion images with current ion microscopy

  13. Kinetic energies of charged fragments resulting from multifragmentation and asymmetric fission of the C60 molecule in collisions with monocharged ions (2-130 keV)

    International Nuclear Information System (INIS)

    Rentenier, A; Bordenave-Montesquieu, D; Moretto-Capelle, P; Bordenave-Montesquieu, A

    2003-01-01

    Multifragmentation and asymmetric fission (AF) of the C 60 molecule induced by H + , H 2 + , H 3 + and He + ions at medium collision energies (2-130 keV) are considered. Momenta and kinetic energies of C n + fragment ions (n = 1- 12) are deduced from an analysis of time-of-flight spectra. In multifragmentation processes, momenta are found to be approximately constant when n > 2, a behaviour which explains that the most probable kinetic energy, as well as the width of the kinetic energy distributions, is found to be inversely proportional to the fragment size n; both momenta and kinetic energies are independent of the velocity and nature of the projectile, and hence of the energy deposit. A specific study of the AF shows that the kinetic energies of C 2 + , C 4 + and C 6 + fragments are also independent of the collision velocity and projectile species; a quantitative agreement is found with values deduced from kinetic energy release measurements by another group in electron impact experiments, and the observed decrease when the mass of the light fragment increases is also reproduced. A quantitative comparison of AF and multifragmentation for the n = 2, 4 and 6 fragment ions shows that kinetic energies in AF exceed that in multifragmentation, a result which explains the oscillations observed when momenta or kinetic energies of fragments are plotted against the n-value. The AF yield is also found to scale with the energy deposit in the collision velocity range extending below the velocity at the maximum of the electronic stopping power; except for protons, it remains negligible with respect to multifragmentation as soon as the total energy deposit exceeds about 100 eV

  14. The Adsorption of n-Octanohydroxamate Collector on Cu and Fe Oxide Minerals Investigated by Static Secondary Ion Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Alan N. Buckley

    2012-12-01

    Full Text Available The feasibility of investigating the adsorption of n-octanohydroxamate collector on copper and iron oxide minerals with static secondary ion mass spectrometry has been assessed. Secondary ion mass spectra were determined for abraded surfaces of air-exposed copper metal, malachite, pseudomalachite and magnetite that had been conditioned in aqueous potassium hydrogen n-octanohydroxamate solution, as well as for the corresponding bulk CuII and FeIII complexes. In each case, the chemical species present at the solid/vacuum interface of a similarly prepared surface were established by X-ray photoelectron spectroscopy. The most abundant positive and negative metal-containing fragment ions identified for the bulk complexes were also found to be diagnostic secondary ions for the collector adsorbed on the oxide surfaces. The relative abundances of those diagnostic ions varied with, and could be rationalised by, the monolayer or multilayer coverage of the adsorbed collector. However, the precise mass values for the diagnostic ions were not able to corroborate the different bonding in the copper and iron hydroxamate systems that had been deduced from photoelectron and vibrational spectra. Parent secondary ions were able to provide supporting information on the co-adsorption of hydroxamic acid at each conditioned surface.

  15. Frequency-scanning MALDI linear ion trap mass spectrometer for large biomolecular ion detection.

    Science.gov (United States)

    Lu, I-Chung; Lin, Jung Lee; Lai, Szu-Hsueh; Chen, Chung-Hsuan

    2011-11-01

    This study presents the first report on the development of a matrix-assisted laser desorption ionization (MALDI) linear ion trap mass spectrometer for large biomolecular ion detection by frequency scan. We designed, installed, and tested this radio frequency (RF) scan linear ion trap mass spectrometer and its associated electronics to dramatically extend the mass region to be detected. The RF circuit can be adjusted from 300 to 10 kHz with a set of operation amplifiers. To trap the ions produced by MALDI, a high pressure of helium buffer gas was employed to quench extra kinetic energy of the heavy ions produced by MALDI. The successful detection of the singly charged secretory immunoglobulin A ions indicates that the detectable mass-to-charge ratio (m/z) of this system can reach ~385 000 or beyond.

  16. Fragmentation processes in nuclear reactions

    International Nuclear Information System (INIS)

    Legrain, R.

    1984-08-01

    Projectile and nuclear fragmentation are defined and processes referred to are recalled. The two different aspects of fragmentation are considered but the emphasis is also put on heavy ion induced reactions. The preliminary results of an experiment performed at GANIL to study peripheral heavy ions induced reactions at intermediate energy are presented. The results of this experiment will illustrate the characteristics of projectile fragmentation and this will also give the opportunity to study projectile fragmentation in the transition region. Then nuclear fragmentation is considered which is associated with more central collisions in the case of heavy ion induced reactions. This aspect of fragmentation is also ilustrated with two heavy ion experiments in which fragments emitted at large angle have been observed

  17. Pinpointing Phosphorylation Sites: Quantitative Filtering and a Novel Site-specific x-Ion Fragment

    DEFF Research Database (Denmark)

    Kelstrup, Christian D; Hekmat, Omid; Francavilla, Chiara

    2011-01-01

    Phosphoproteomics deals with the identification and quantification of thousands of phosphopeptides. Localizing the phosphorylation site is however much more difficult than establishing the identity of a phosphorylated peptide. Further, recent findings have raised doubts of the validity of the site......-phase phosphate rearrangement reactions during collision-induced dissociation (CID) and used these spectra to devise a quantitative filter that by comparing signal intensities of putative phosphorylated fragment ions with their nonphosphorylated counterparts allowed us to accurately pinpoint which fragment ions...... contain a phosphorylated residue and which ones do not. We also evaluated higher-energy collisional dissociation (HCD) and found this to be an accurate method for correct phosphorylation site localization with no gas-phase rearrangements observed above noise level. Analyzing a large set of HCD spectra...

  18. In silico fragmentation for computer assisted identification of metabolite mass spectra

    Directory of Open Access Journals (Sweden)

    Müller-Hannemann Matthias

    2010-03-01

    Full Text Available Abstract Background Mass spectrometry has become the analytical method of choice in metabolomics research. The identification of unknown compounds is the main bottleneck. In addition to the precursor mass, tandem MS spectra carry informative fragment peaks, but the coverage of spectral libraries of measured reference compounds are far from covering the complete chemical space. Compound libraries such as PubChem or KEGG describe a larger number of compounds, which can be used to compare their in silico fragmentation with spectra of unknown metabolites. Results We created the MetFrag suite to obtain a candidate list from compound libraries based on the precursor mass, subsequently ranked by the agreement between measured and in silico fragments. In the evaluation MetFrag was able to rank most of the correct compounds within the top 3 candidates returned by an exact mass query in KEGG. Compared to a previously published study, MetFrag obtained better results than the commercial MassFrontier software. Especially for large compound libraries, the candidates with a good score show a high structural similarity or just different stereochemistry, a subsequent clustering based on chemical distances reduces this redundancy. The in silico fragmentation requires less than a second to process a molecule, and MetFrag performs a search in KEGG or PubChem on average within 30 to 300 seconds, respectively, on an average desktop PC. Conclusions We presented a method that is able to identify small molecules from tandem MS measurements, even without spectral reference data or a large set of fragmentation rules. With today's massive general purpose compound libraries we obtain dozens of very similar candidates, which still allows a confident estimate of the correct compound class. Our tool MetFrag improves the identification of unknown substances from tandem MS spectra and delivers better results than comparable commercial software. MetFrag is available through a web

  19. Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O+232Th reaction

    Directory of Open Access Journals (Sweden)

    R. Léguillon

    2016-10-01

    Full Text Available It is shown that the multinucleon transfer reactions is a powerful tool to study fission of exotic neutron-rich actinide nuclei, which cannot be accessed by particle-capture or heavy-ion fusion reactions. In this work, multinucleon transfer channels of the 18O+232Th reaction are used to study fission of fourteen nuclei 231,232,233,234Th, 232,233,234,235,236Pa, and 234,235,236,237,238U. Identification of fissioning nuclei and of their excitation energy is performed on an event-by-event basis, through the measurement of outgoing ejectile particle in coincidence with fission fragments. Fission fragment mass distributions are measured for each transfer channel, in selected bins of excitation energy. In particular, the mass distributions of 231,234Th and 234,235,236Pa are measured for the first time. Predominantly asymmetric fission is observed at low excitation energies for all studied cases, with a gradual increase of the symmetric mode towards higher excitation energy. The experimental distributions are found to be in general agreement with predictions of the fluctuation–dissipation model.

  20. Ion trajectories quadrupole mass filters

    International Nuclear Information System (INIS)

    Ursu, D.; Lupsa, N.; Muntean, F.

    1994-01-01

    The present paper aims at bringing some contributions to the understanding of ion motion in quadrupole mass filters. The theoretical treatment of quadrupole mass filter is intended to be a concise derivation of the important physical relationships using Mathieu functions. A simple iterative method of numerical computation has been used to simulate ion trajectories in an ideal quadrupole field. Finally, some examples of calculation are presented with the aid of computer graphics. (Author) 14 Figs., 1 Tab., 20 Refs

  1. Development of Fragmented Low-Z Ion Beams for the NA61 Experiment at the CERN SPS

    CERN Document Server

    Efthymiopoulos, I; Bohl, T; Breuker, H; Calviani, M; Manglunki, D; Mataguez, S; Maury, S; Valderanis, C; Cornelis, K; Spanggaard, J; Cettour-Cave, S; Gazdzicki, M; Seyboth, P; Guber, F; Ivashkin, A

    2011-01-01

    The NA61 experiment, aims to study the properties of the onset of deconfinement at low SPS energies and to find signatures of the critical point of strongly interacting matter. A broad range in T-μB phase diagram will be covered by performing an energy (13A-158AGeV/c) and system size (p+p, Be+Be, Ar+Ca, Xe+La) scan. In a first phase, fragmented ion beams of 7Be or 11C produced as secondaries with the same momentum per nucleon when the incident primary Pb-ion beam hits a thin Be target will be used. The H2 beam line that transports the beam to the experiment acts as a double spectrometer which combined with a new thin target (degrader) where fragments loose energy proportional to the square of their charge allows the separation of the wanted A/Z fragments. Thin scintillators and TOF measurement for the low energy points are used as particle identification devices. In this paper results from the first test of the fragmented ion beam done in 2010 will be presented showing that a pure Be beam can be obtained sa...

  2. Simultaneous ion detection in a mass spectrometer with variable mass dispersion

    International Nuclear Information System (INIS)

    Tuithof, H.H.

    1977-01-01

    This thesis mainly describes the ion-optics of a magnetic mass spectrometer system, especially applied to the projection of a significant part of the mass spectrum onto a flat ion-detector. The complete detector consists of a channeltron electron multiplier array with phosphor screen and a Vidicon-multichannel analyzer combination for simultaneous read-out. In order to optimise the spectral range projected onto the channelplate, by varying the mass dispersion and to rotate the oblique angle of the mass focal plane with respect to the detector surface, the sector magnet has been combined with electrostatic and magnetic quadrupole lenses. This detector will find wide application in the analysis of minute sample quantities, in the recording of extremely short ion events (large molecules) and at collision activation mass-spectrometry studies

  3. The Assessment of Selectivity in Different Quadrupole-Orbitrap Mass Spectrometry Acquisition Modes

    Science.gov (United States)

    Berendsen, Bjorn J. A.; Wegh, Robin S.; Meijer, Thijs; Nielen, Michel W. F.

    2015-02-01

    Selectivity of the confirmation of identity in liquid chromatography (tandem) mass spectrometry using Q-Orbitrap instrumentation was assessed using different acquisition modes based on a representative experimental data set constructed from 108 samples, including six different matrix extracts and containing over 100 analytes each. Single stage full scan, all ion fragmentation, and product ion scanning were applied. By generating reconstructed ion chromatograms using unit mass window in targeted MS2, selected reaction monitoring (SRM), regularly applied using triple-quadrupole instruments, was mimicked. This facilitated the comparison of single stage full scan, all ion fragmentation, (mimicked) SRM, and product ion scanning applying a mass window down to 1 ppm. Single factor Analysis of Variance was carried out on the variance (s2) of the mass error to determine which factors and interactions are significant parameters with respect to selectivity. We conclude that selectivity is related to the target compound (mainly the mass defect), the matrix, sample clean-up, concentration, and mass resolution. Selectivity of the different instrumental configurations was quantified by counting the number of interfering peaks observed in the chromatograms. We conclude that precursor ion selection significantly contributes to selectivity: monitoring of a single product ion at high mass accuracy with a 1 Da precursor ion window proved to be equally selective or better to monitoring two transition products in mimicked SRM. In contrast, monitoring a single fragment in all ion fragmentation mode results in significantly lower selectivity versus mimicked SRM. After a thorough inter-laboratory evaluation study, the results of this study can be used for a critical reassessment of the current identification points system and contribute to the next generation of evidence-based and robust performance criteria in residue analysis and sports doping.

  4. Formation of fission-fragment mass distribution for nuclei lighter than thorium

    International Nuclear Information System (INIS)

    Itkis, M.G.; Mul'gin, S.I.; Rusanov, A.Y.; Okolovich, A.N.; Smirenkin, G.N.

    1986-01-01

    A phenomenological approach to description of fission-fragment mass distribution Y(M) for nuclei in the vicinity of Pb is developed and used to extract from the experimental Y(M) data the nuclear deformation potential energy V(M) and its components: the macroscopic (liquid-drop) part and the shell correction in the transition state. The results of the analysis are compared with the theoretically obtained V(M) and Y(M). The three-hump fragment-mass distributions observed in Ra fission are satisfactorily described within the framework of the approach developed. The properties of the symmetric and asymmetric fission valleys and the related Y(M) components are discussed

  5. Application of Tandem Two-Dimensional Mass Spectrometry for Top-Down Deep Sequencing of Calmodulin.

    Science.gov (United States)

    Floris, Federico; Chiron, Lionel; Lynch, Alice M; Barrow, Mark P; Delsuc, Marc-André; O'Connor, Peter B

    2018-06-04

    Two-dimensional mass spectrometry (2DMS) involves simultaneous acquisition of the fragmentation patterns of all the analytes in a mixture by correlating their precursor and fragment ions by modulating precursor ions systematically through a fragmentation zone. Tandem two-dimensional mass spectrometry (MS/2DMS) unites the ultra-high accuracy of Fourier transform ion cyclotron resonance (FT-ICR) MS/MS and the simultaneous data-independent fragmentation of 2DMS to achieve extensive inter-residue fragmentation of entire proteins. 2DMS was recently developed for top-down proteomics (TDP), and applied to the analysis of calmodulin (CaM), reporting a cleavage coverage of about ~23% using infrared multiphoton dissociation (IRMPD) as fragmentation technique. The goal of this work is to expand the utility of top-down protein analysis using MS/2DMS in order to extend the cleavage coverage in top-down proteomics further into the interior regions of the protein. In this case, using MS/2DMS, the cleavage coverage of CaM increased from ~23% to ~42%. Graphical Abstract Two-dimensional mass spectrometry, when applied to primary fragment ions from the source, allows deep-sequencing of the protein calmodulin.

  6. Mass Spectrometry Instrumentation in Proteomics

    DEFF Research Database (Denmark)

    Sprenger, Richard Remko; Roepstorff, Peter

    2012-01-01

    Mass spectrometry has evolved into a crucial technology for the field of proteomics, enabling the comprehensive study of proteins in biological systems. Innovative developments have yielded flexible and versatile mass spectrometric tools, including quadrupole time-of-flight, linear ion trap......, Orbitrap and ion mobility instruments. Together they offer various and complementary capabilities in terms of ionization, sensitivity, speed, resolution, mass accuracy, dynamic range and methods of fragmentation. Mass spectrometers can acquire qualitative and quantitative information on a large scale...

  7. Experimental study on the fragmentation of Adenine and Porphyrin molecules induced by low energy multicharged ion impact

    International Nuclear Information System (INIS)

    Li, B.

    2010-01-01

    Since the dissociation of small molecules might play key roles in the understanding of radiation induced damages of living tissues at the primary steps and at the molecular levels, fragmentation dynamics of small biomolecules have drawn much attention. The knowledge of the internal energy is of fundamental importance for understanding its fragmentation dynamics following external excitation. For a long time however, it was difficult to measure this parameter in coincidence with the fragmentation patterns until the development of CIDEC (Collision Induced Dissociation under Energy Control) method in 2007. In this work, the CIDEC method was extended to study the fragmentation of gas-phase biomolecules adenine (Ade: H 5 C 5 N 5 ) and porphyrin chloride FeTPPCl (C 44 H 28 N 4 FeCl). The population distribution for each dissociation channel as a function of the excitation energy of the parent molecular ions at a well-determined initial charge state has been experimentally determined, which could shed some light on the fragmentation dynamics of these molecules. In collisions between Cl + and Ade at 3 keV, the fragmentation pattern of Ade 2+ is dominated by the loss of H 2 CN + and the successive emission of HCN. The energy distribution of the parent dication confirms the successive emission dynamics. A specific decay channel is observed, i.e. the emission of a charged H 2 CN + followed by the emission of HC 2 N 2 . The measured mean excitation energies of this channel and other competitive channels are compared. In Kr 8+ - FeTPPCl collisions at 80 keV, parent ions FeTPPCL 1+,2+,3+ are observed, along with the corresponding decay patterns. It is found that, in the first step the dominant low-energy-cost decay channel is the emission of Cl 0 independent of the initial charge state of FeTPPCl r+ . For the resulted dication FeTPP 2+ , the dominant fragmentation channel is the neutral evaporation; for the tri-cation however, the dominant fragmentation channel is the

  8. Projectile rapidity dependence in target fragmentation

    International Nuclear Information System (INIS)

    Haustein, P.E.; Cumming, J.B.; Hseuh, H.C.

    1979-01-01

    The thick-target, thick-catcher technique was used to determine mean kinetic properties of selected products of the fragmentation of Cu by 1 H, 4 He, and 12 C ions (180 to 28,000 MeV/amu). Momentum transfer, as inferred from F/B ratios, is ovserved to occur most efficiently for the lower velocity projectiles. Recoil properties of target fragments vary strongly with product mass, but show only a weak dependence on projectile type. The projectile's rapidity is shown to be a useful variable for quantitative intercomparison of different reactions. These results indicate that E/sub proj//A/sub proj/ is the dominant parameter which governs the mean recoil behavior of target fragments. 20 references

  9. Fourier transform ion cyclotron resonance mass spectrometry

    Science.gov (United States)

    Marshall, Alan G.

    1998-06-01

    As for Fourier transform infrared (FT-IR) interferometry and nuclear magnetic resonance (NMR) spectroscopy, the introduction of pulsed Fourier transform techniques revolutionized ion cyclotron resonance mass spectrometry: increased speed (factor of 10,000), increased sensitivity (factor of 100), increased mass resolution (factor of 10,000-an improvement not shared by the introduction of FT techniques to IR or NMR spectroscopy), increased mass range (factor of 500), and automated operation. FT-ICR mass spectrometry is the most versatile technique for unscrambling and quantifying ion-molecule reaction kinetics and equilibria in the absence of solvent (i.e., the gas phase). In addition, FT-ICR MS has the following analytically important features: speed (~1 second per spectrum); ultrahigh mass resolution and ultrahigh mass accuracy for analysis of mixtures and polymers; attomole sensitivity; MSn with one spectrometer, including two-dimensional FT/FT-ICR/MS; positive and/or negative ions; multiple ion sources (especially MALDI and electrospray); biomolecular molecular weight and sequencing; LC/MS; and single-molecule detection up to 108 Dalton. Here, some basic features and recent developments of FT-ICR mass spectrometry are reviewed, with applications ranging from crude oil to molecular biology.

  10. Liquid chromatography, in combination with a quadrupole time-of-flight instrument (LC QTOF), with sequential window acquisition of all theoretical fragment-ion spectra (SWATH) acquisition: systematic studies on its use for screenings in clinical and forensic toxicology and comparison with information-dependent acquisition (IDA).

    Science.gov (United States)

    Roemmelt, Andreas T; Steuer, Andrea E; Poetzsch, Michael; Kraemer, Thomas

    2014-12-02

    Forensic and clinical toxicological screening procedures are employing liquid chromatography-tandem mass spectrometry (LC-MS/MS) techniques with information-dependent acquisition (IDA) approaches more and more often. It is known that the complexity of a sample and the IDA settings might prevent important compounds from being triggered. Therefore, data-independent acquisition (DIA) methods should be more suitable for systematic toxicological analysis (STA). The DIA method sequential window acquisition of all theoretical fragment-ion spectra (SWATH), which uses Q1 windows of 20-35 Da for data-independent fragmentation, was systematically investigated for its suitability for STA. Quality of SWATH-generated mass spectra were evaluated with regard to mass error, relative abundance of the fragments, and library hits. With the Q1 window set to 20-25 Da, several precursors pass Q1 at the same time and are fragmented, thus impairing the library search algorithms to a different extent: forward fit was less affected than reverse fit and purity fit. Mass error was not affected. The relative abundance of the fragments was concentration dependent for some analytes and was influenced by cofragmentation, especially of deuterated analogues. Also, the detection rate of IDA compared to SWATH was investigated in a forced coelution experiment (up to 20 analytes coeluting). Even using several different IDA settings, it was observed that IDA failed to trigger relevant compounds. Screening results of 382 authentic forensic cases revealed that SWATH's detection rate was superior to IDA, which failed to trigger ∼10% of the analytes.

  11. Vacuum-Ultraviolet Photoionization and Mass Spectrometric Characterization of Lignin Monomers Coniferyl and Sinapyl Alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Lynelle K.; Zhou, Jia; Kostko, Oleg; Golan, Amir; Leone, Stephen R.; Ahmed, Musahid

    2011-02-09

    The fragmentation mechanisms of monolignols under various energetic processes are studied with jet-cooled thermal desorption molecular beam (TDMB) mass spectrometry (MS), 25 keV Bi3+ secondary ion MS (SIMS), synchrotron vacuum-ultraviolet secondary neutral MS (VUV-SNMS) and theoretical methods. Experimental and calculated appearance energies of fragments observed in TDMB MS indicate that the coniferyl alcohol photoionization mass spectra contain the molecular parent and several dissociative photoionization products. Similar results obtained for sinapyl alcohol are also discussed briefly. Ionization energies of 7.60 eV ? 0.05 eV for coniferyl alcohol and<7.4 eV for both sinapyl and dihydrosinapyl alcohols are determined. The positive ion SIMS spectrum of coniferyl alcohol shares few characteristic peaks (m/z = 137 and 151) with the TDMB mass spectra, shows extensive fragmentation, and does not exhibit clear molecular parent signals. VUV-SNMS spectra, on the other hand, are dominated by the parent ion and main fragments also present in the TDMB spectra. Molecular fragmentation in VUV-SNMS spectra can be reduced by increasing the extraction delay time. Some features resembling the SIMS spectra are also observed in the desorbed neutral products. The monolignol VUV-SNMS peaks shared with the TDMB mass spectra suggest that dissociative photoionization of ion-sputtered neutral molecules predominate in the VUV-SNMS mass spectra, despite the extra internal energy imparted in the initial ion impact. The potential applications of these results to imaging mass spectrometry of bio-molecules are discussed.

  12. The Study of Titanium and Zirconium Ions in Water by MPT-LTQ Mass Spectrometry in Negative Mode.

    Science.gov (United States)

    Yang, Junqing; Zheng, Mei; Liu, Qiuju; Yang, Meiling Zhu Chushan; Zhang, Yan; Zhu, Zhiqiang

    2017-09-26

    Microwave plasma torches (MPTs) can be used as simple and low power-consumption ambient ion sources. When MPT-mass spectrometry (MPT-MS) is applied in the detection of some metal elements, the metallic ions exhibit some novel features which are significantly different with those obtained by the traditional inductively coupled plasma (ICP)-mass spectrometry (ICP-MS) and may be helpful for metal element analysis. As the representative elements of group IVA, titanium and zirconium are both of importance and value in modern industry, and they have impacts on human health. Here, we first provide a study on the complex anions of titanium and zirconium in water by using the MPT as ion source and a linear ion trap mass spectrometer (LTQ-MS). These complex anions were produced in the plasma flame by an aqueous solution flowing through the central tube of the MPT, and were introduced into the inlet of the mass spectrometry working in negative ion mode to get the feature mass spectrometric signals. Moreover, the feature fragment patterns of these ions in multi-step collision- induced dissociation processes have been explained. Under the optimized conditions, the limit of detection (LOD) using the MS² (the second tandem mass spectrometry) procedure was estimated to be at the level of 10μg/L for titanium and 20 μg/L for zirconium with linear dynamics ranges that cover at least two orders of magnitude, i.e., between 0-500 μg/L and 20-200 μg/L, respectively. These experimental data demonstrated that the MPT-MS is a promising and useful tool in field analysis of titanium and zirconium ions in water, and can be applied in many fields, such as environmental control, hydrogeology, and water quality inspection. In addition, MPT-MS could also be used as a supplement of ICP-MS for the rapid and on-site analysis of metal ions.

  13. Rate-dependent performance of ion chambers for particle-ID at the GSI fragment separator

    Energy Technology Data Exchange (ETDEWEB)

    Hucka, Jan-Paul; Allred, Timothy; Enders, Joachim [Institut fuer Kernphysik, TU Darmstadt (Germany); Gernhaeuser, Roman; Maurus, Steffen [Physik Department, TU Muenchen (Germany); Nociforo, Chiara; Pietri, Stephane; Prochazka, Andrej [GSI Helmholtzzentrum fuer Schwerionenforschung (Germany)

    2015-07-01

    At the GSI Fragment Separator (FRS), multi-sampling ion chambers (MUSIC) employing a Frisch grid are used for charge identification of secondary ion beams. At the FAIR Super-FRS, higher rates are expected, and an event-by-event determination of the charge of secondary ions will be needed at rates of several 100000 events per second. The comparison of results from test measurements for the MUSIC performance with that of a recently constructed tilted-electrode gas ion chamber (TEGIC), which was designed similar to the one discussed, is presented.

  14. High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

    CERN Document Server

    Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

    2001-01-01

    Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

  15. A Liquid Chromatography-Quadrupole-Time of Flight Mass Spectrometry (LC-Q-TOF MS) Study for Analyzing 35 Corticosteroid Compounds: Elucidation of MS/MS Fragmentation Pathways

    International Nuclear Information System (INIS)

    Noh, Eunyoung; Yoon, Chang-Yong; Lee, Ji Hyun; Baek, Sun-Young; Do, Jung-Ah; Lee, Jung-min; Oh, Han Bin

    2016-01-01

    Corticosteroids have been often found to be added to a dietary supplement for the purpose of illegally improving the effect of their products. Thus, it is imperative to develop or improve a method that enables one to rapidly and reliably analyze corticosteroids in health or dietary supplements, for the safety management purpose. In the present study, results from liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) experiments for the selected 35 corticosteroid compounds are presented, which can be useful for the qualitative screening of corticosteroids in health or dietary supplements. Specifically, retention times, accurate mass data of the protonated steroids, m/z values of major fragment ions are given for the 35 corticosteroids. Further, fragmentation pathways for the selected steroids are also suggested. Based on the suggested fragmentation pathways, it was shown that an unknown steroid compound can be readily identified using the knowledge of a group of unique and specific common skeletal fragments. The high selectivity and sensitivity of the LC-Q-TOF-MS/MS results combined with the knowledge of the fragmentation pathways can offer a new opportunity for rapid and accurate screening of corticosteroids, thus preventing health-related incidents involving adulterated products and clamping down on illegally circulated health products.

  16. A Liquid Chromatography-Quadrupole-Time of Flight Mass Spectrometry (LC-Q-TOF MS) Study for Analyzing 35 Corticosteroid Compounds: Elucidation of MS/MS Fragmentation Pathways

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Eunyoung; Yoon, Chang-Yong; Lee, Ji Hyun; Baek, Sun-Young; Do, Jung-Ah [Ministry of Food and Drug Safety, Cheongju (Korea, Republic of); Lee, Jung-min; Oh, Han Bin [Sogang University, Seoul (Korea, Republic of)

    2016-07-15

    Corticosteroids have been often found to be added to a dietary supplement for the purpose of illegally improving the effect of their products. Thus, it is imperative to develop or improve a method that enables one to rapidly and reliably analyze corticosteroids in health or dietary supplements, for the safety management purpose. In the present study, results from liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS) experiments for the selected 35 corticosteroid compounds are presented, which can be useful for the qualitative screening of corticosteroids in health or dietary supplements. Specifically, retention times, accurate mass data of the protonated steroids, m/z values of major fragment ions are given for the 35 corticosteroids. Further, fragmentation pathways for the selected steroids are also suggested. Based on the suggested fragmentation pathways, it was shown that an unknown steroid compound can be readily identified using the knowledge of a group of unique and specific common skeletal fragments. The high selectivity and sensitivity of the LC-Q-TOF-MS/MS results combined with the knowledge of the fragmentation pathways can offer a new opportunity for rapid and accurate screening of corticosteroids, thus preventing health-related incidents involving adulterated products and clamping down on illegally circulated health products.

  17. Inner-shell excitation and ionic fragmentation of molecules

    International Nuclear Information System (INIS)

    Hitchcock, A.P.; Tyliszczak, T.; Cavell, R.G.

    1997-01-01

    Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can reveal cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF 6 and CO 2 . Their work is illustrated using results from the carborane and PF 3 studies

  18. Inner-shell excitation and ionic fragmentation of molecules

    Energy Technology Data Exchange (ETDEWEB)

    Hitchcock, A.P.; Tyliszczak, T. [McMaster Univ., Hamilton, Ontario (Canada); Cavell, R.G. [Univ. of Alberta, Edmonton (Canada)] [and others

    1997-04-01

    Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can reveal cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.

  19. Proton fragmentation functions considering finite-mass corrections

    Energy Technology Data Exchange (ETDEWEB)

    Moosavi Nejad, S.M. [Yazd University, Faculty of Physics, Yazd (Iran, Islamic Republic of); Institute for Research in Fundamental Sciences (IPM), School of Particles and Accelerators, Tehran (Iran, Islamic Republic of); Soleymaninia, M. [Payame Noor Universtiy, Department of Physics, Tehran (Iran, Islamic Republic of); Maktoubian, A. [Yazd University, Faculty of Physics, Yazd (Iran, Islamic Republic of)

    2016-10-15

    We present new sets of proton fragmentation functions (FFs) describing the production of protons from the gluon and each of the quarks, obtained by the NLO QCD fits to all relevant data sets of single-inclusive electron-positron annihilation. Specifically, we determine their uncertainties using the Gaussian method for error estimation. Our analysis is in good agreement with the e{sup +}e{sup -} annihilation data. We also include finite-mass effects of the proton in our calculations, a topic to which very little attention is paid in the literature. Proton mass effects turn out to be appreciable for gluon and light quark FFs. The inclusion of finite-mass effects tends to improve the overall description of the data by reducing the minimized χ{sup 2} values significantly. As an application, we apply the extracted FFs to make predictions for the scaled-energy distribution of protons inclusively produced in top quark decays at next-to-leading order, relying on the universality and scaling violations of FFs. (orig.)

  20. Mass spectrum of secondary ions knocked-out from copper surface by argon ion beam

    International Nuclear Information System (INIS)

    Koval', A.G.; Bobkov, V.V.; Klimovskij, Yu.A.; Fogel', Ya.M.

    1976-01-01

    The mass-spectrum of secondary ions was studied within a mass range of 1-400. The ions were knocked-out by the beam of ions Ar + from the copper surface with different content of oxygen and sulphur solved in the volume. The studies were conducted at three temperatures of the target. The atomic and molecular ions of the metal matrix, volumetric impurities of metal and ions of chemical compounds molecules of the metal under study with gas particles adsorbed on its surface and atoms of the metal volumetric admixtures may be observed in the mass spectrum. Detection of secondary ions of the copper multi-atomic complexes and ions of these complexes compounds with the adsorbed molecules is of interest

  1. Fragmentation in peripheral heavy-ion collisions: from neck emission to spectator decays

    Energy Technology Data Exchange (ETDEWEB)

    Lukasik, J.; Auger, G.; Begemann-Blaich, M.L.; Bellaize, N.; Bittiger, R.; Bocage, F.; Borderie, B.; Bougault, R.; Bouriquet, B.; Charvet, J.L.; Chbihi, A.; Dayras, R.; Durand, D.; Frankland, J.D.; Galichet, E.; Gourio, D.; Guinet, D.; Hudan, S.; Hurst, B.; Lautesse, P.; Lavaud, F.; Le Fevre, A.; Legrain, R.; Lopez, O.; Lynen, U.; Mueller, W.F.J.; Nalpas, L.; Orth, H.; Plagnol, E.; Rosato, E.; Saija, A.; Schwarz, C.; Sfienti, C.; Steckmeyer, J.C.; Tamain, B.; Trautmann, W.; Trzcinski, A.; Turzo, K.; Vient, E.; Vigilante, M.; Volant, C.; Zwieglinski, B.; Botvina, A.S

    2003-07-24

    Invariant cross sections of intermediate mass fragments in peripheral collisions of {sup 197}Au on {sup 197}Au at incident energies between 40 and 150 MeV per nucleon have been measured with the 4{pi} multi-detector INDRA. The maximum of the fragment production is located near mid-rapidity at the lower energies and moves gradually towards the projectile and target rapidities as the energy is increased. Schematic calculations within an extended Goldhaber model suggest that the observed cross section distributions and their evolution with energy are predominantly the result of the clustering requirement for the emerging fragments and of their Coulomb repulsion from the projectile and target residues. The quantitative comparison with transverse energy spectra and fragment charge distributions emphasizes the role of hard scattered nucleons in the fragmentation process.

  2. A large area position-sensitive ionization chamber for heavy-ion-induced reaction studies

    CERN Document Server

    Pant, L M; Dinesh, B V; Thomas, R G; Saxena, A; Sawant, Y S; Choudhury, R K

    2002-01-01

    A large area position-sensitive ionization chamber with a wide dynamic range has been developed to measure the mass, charge and energy of the heavy ions and the fission fragments produced in heavy-ion-induced reactions. The split anode geometry of the detector makes it suitable for both particle identification and energy measurements for heavy ions and fission fragments. The detector has been tested with alpha particles from sup 2 sup 4 sup 1 Am- sup 2 sup 3 sup 9 Pu source, fission fragments from sup 2 sup 5 sup 2 Cf and the heavy-ion beams from the 14UD Mumbai Pelletron accelerator facility. Using this detector, measurements on mass and total kinetic energy distributions in heavy-ion-induced fusion-fission reactions have been carried out for a wide range of excitation energies. Results on deep inelastic collisions and mass-energy correlations on different systems using this detector setup are discussed.

  3. Quantification and micron-scale imaging of spatial distribution of trace beryllium in shrapnel fragments and metallurgic samples with correlative fluorescence detection method and secondary ion mass spectrometry (SIMS)

    Science.gov (United States)

    Abraham, Jerrold L.; Chandra, Subhash; Agrawal, Anoop

    2014-01-01

    Recently, a report raised the possibility of shrapnel-induced chronic beryllium disease (CBD) from long-term exposure to the surface of retained aluminum shrapnel fragments in the body. Since the shrapnel fragments contained trace beryllium, methodological developments were needed for beryllium quantification and to study its spatial distribution in relation to other matrix elements, such as aluminum and iron, in metallurgic samples. In this work, we developed methodology for quantification of trace beryllium in samples of shrapnel fragments and other metallurgic sample-types with main matrix of aluminum (aluminum cans from soda, beer, carbonated water, and aluminum foil). Sample preparation procedures were developed for dissolving beryllium for its quantification with the fluorescence detection method for homogenized measurements. The spatial distribution of trace beryllium on the sample surface and in 3D was imaged with a dynamic secondary ion mass spectrometry (SIMS) instrument, CAMECA IMS 3f SIMS ion microscope. The beryllium content of shrapnel (~100 ppb) was the same as the trace quantities of beryllium found in aluminum cans. The beryllium content of aluminum foil (~25 ppb) was significantly lower than cans. SIMS imaging analysis revealed beryllium to be distributed in the form of low micron-sized particles and clusters distributed randomly in X-Y-and Z dimensions, and often in association with iron, in the main aluminum matrix of cans. These observations indicate a plausible formation of Be-Fe or Al-Be alloy in the matrix of cans. Further observations were made on fluids (carbonated water) for understanding if trace beryllium in cans leached out and contaminated the food product. A direct comparison of carbonated water in aluminum cans and plastic bottles revealed that beryllium was below the detection limits of the fluorescence detection method (~0.01 ppb). These observations indicate that beryllium present in aluminum matrix was either present in an

  4. Matrix-assisted laser desorption/ionization time-of-flight and nano-electrospray ionization ion trap mass spectrometric characterization of 1-cyano-2-substituted-benz[f]isoindole derivatives of peptides for fluorescence detection

    DEFF Research Database (Denmark)

    Linnemayr, K; Brückner, A; Körner, R

    1999-01-01

    A series of hexa- to decapeptides (molecular mass range 800-1200) were labeled with naphthalene-2,3-dicarboxaldehyde, which preferentially reacts with the primary amino groups of a peptide. A highly stable peptide conjugate is formed, which allows selective analysis by fluorescence at excitation...... and emission wavelengths of 420 and 490 nm, respectively. After removal of unreacted compounds, the peptide conjugates were characterized by matrix-assisted laser desorption/ionization (MALDI) time-of-flight and nano-electrospray ionization (ESI) ion trap mass spectrometry. They readily form both [M + H]+ ions...... by MALDI and both [M + H]+ and [M + 2H]2+ ions by ESI. Furthermore, the fragmentation behavior of the N-terminally tagged peptides, exhibiting an uncharged N-terminus, was investigated applying post-source decay fragmentation with a curved field reflector and collision-induced dissociation...

  5. Final Report - Advanced Ion Trap Mass Spectrometry Program - Oak Ridge National Laboratory - Sandia National Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, W.B.

    2002-12-18

    nonlinear resonances contributed to poor mass resolution and sensitivity and to erratic ion ejection behavior. To correct for these nonlinear effects, the geometry of the toroid ion trap analyzer has been modified to create an asymmetric torus, as first suggested by computer simulations that predicted significantly improved performance and unit mass resolution for this geometry. A reduced-sized version (one-fifth scale) has been fabricated but was not tested within the scope of this project. Chapter 3 describes groundbreaking progress toward the use of ion-ion chemistry to control the charge state of ions formed by the electrospray ionization process, which in turn enables precision analysis of whole proteins. In addition, this technique may offer the unique possibility of a priori identification of unknown biological material when employed with existing proteomics and genomic databases. Ion-ion chemistry within the ion trap was used to reduce the ions in highly charged states to states of +1 and +2 charges. Reduction in charge greatly simplifies identification of molecular weights of fragments from large biological molecules. This technique enables the analysis of whole proteins as biomarkers for the detection and identification of all three classes of biological weapons (bacteria, toxins, and viruses). In addition to methods development, tests were carried out with samples of tap water, local creek water, and soil (local red clay) spiked with melittin (bee venom), cholera toxin, and virus MS2. All three analytes were identified in tap water and soil; however, all three were problematic for detection in creek water at concentrations of 1 nM. More development of methods is needed.

  6. Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates.

    Science.gov (United States)

    Frańska, Magdalena; Zgoła, Agnieszka; Rychłowska, Joanna; Szymański, Andrzej; Łukaszewski, Zenon; Frański, Rafał

    2003-01-01

    Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra.

  7. Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method.

    Science.gov (United States)

    Leveque, Nathalie L; Acheampong, Akwasi; Heron, Sylvie; Tchapla, Alain

    2012-04-13

    The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG((AAB and/or ABA))](+) generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)](+) or the neutral TAG molecule (TAG((AAB and/or ABA))) leading to [ref, Li](+). The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R(iso)), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Negative ion electrospray ionization mass spectrometry of nucleoside phosphoramidate monoesters: elucidation of novel rearrangement mechanisms by multistage mass spectrometry incorporating in-source deuterium labelling.

    Science.gov (United States)

    Xu, Peng-Xiang; Hu, An-Fu; Hu, Dan; Gao, Xiang; Zhao, Yu-Fen

    2008-10-01

    Several O-2',3'-isopropylideneuridine-O-5'-phosphoramidate monoesters were synthesized and analyzed by negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)). Two kinds of novel rearrangement reactions were observed due to the difference in the amino acid in the nucleoside phosphoramidate monoesters, and possible mechanisms were proposed. One involves a five-membered cyclic transition state. The other is formation of a stable five-membered ring intermediate by Michael addition. Results were confirmed by tandem mass spectrometry and isotopically labeled hydrogen atoms. Furthermore, the internal hydrogen exchange between active hydrogen and methyl acrylate in the heated capillary of the mass spectrometer was found. The characteristic fragmentation behavior in ESI-MS may be used to monitor this kind of compounds in the biological metabolism.

  9. Native Mass Spectrometry in Fragment-Based Drug Discovery

    Directory of Open Access Journals (Sweden)

    Liliana Pedro

    2016-07-01

    Full Text Available The advent of native mass spectrometry (MS in 1990 led to the development of new mass spectrometry instrumentation and methodologies for the analysis of noncovalent protein–ligand complexes. Native MS has matured to become a fast, simple, highly sensitive and automatable technique with well-established utility for fragment-based drug discovery (FBDD. Native MS has the capability to directly detect weak ligand binding to proteins, to determine stoichiometry, relative or absolute binding affinities and specificities. Native MS can be used to delineate ligand-binding sites, to elucidate mechanisms of cooperativity and to study the thermodynamics of binding. This review highlights key attributes of native MS for FBDD campaigns.

  10. Native Mass Spectrometry in Fragment-Based Drug Discovery.

    Science.gov (United States)

    Pedro, Liliana; Quinn, Ronald J

    2016-07-28

    The advent of native mass spectrometry (MS) in 1990 led to the development of new mass spectrometry instrumentation and methodologies for the analysis of noncovalent protein-ligand complexes. Native MS has matured to become a fast, simple, highly sensitive and automatable technique with well-established utility for fragment-based drug discovery (FBDD). Native MS has the capability to directly detect weak ligand binding to proteins, to determine stoichiometry, relative or absolute binding affinities and specificities. Native MS can be used to delineate ligand-binding sites, to elucidate mechanisms of cooperativity and to study the thermodynamics of binding. This review highlights key attributes of native MS for FBDD campaigns.

  11. Fragmentation of molecular ions in differential mobility spectrometry as a method for identification of chemical warfare agents.

    Science.gov (United States)

    Maziejuk, M; Puton, J; Szyposzyńska, M; Witkiewicz, Z

    2015-11-01

    The subject of the work is the use of differential mobility spectrometry (DMS) for the detection of chemical warfare agents (CWA). Studies were performed for mustard gas, i.e., bis(2-chloroethyl)sulfide (HD), sarin, i.e., O-isopropyl methylphosphonofluoridate (GB) and methyl salicylate (MS) used as test compounds. Measurements were conducted with two ceramic DMS analyzers of different constructions allowing the generation of an electric field with an intensity of more than 120 Td. Detector signals were measured for positive and negative modes of operation in a temperature range from 0 to 80 °C. Fragmentations of ions containing analyte molecules were observed for all tested compounds. The effective temperatures of fragmentation estimated on the basis of dispersion plots were equal from about 148 °C for GB to 178 °C for MS. It was found that values of separation voltage (SV) and compensation voltage (CV) at which the fragmentation of sample ions is observed may be the parameters improving the certainty of detection for different analytes. The DMS analyzers enabling the observation of ion fragmentation can be successfully used for effective CWA detection. Copyright © 2015. Published by Elsevier B.V.

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

    Science.gov (United States)

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

    2018-06-02

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

  13. Fragmentation cross sections outside the limiting-fragmentation regime

    CERN Document Server

    Sümmerer, K

    2003-01-01

    The empirical parametrization of fragmentation cross sections, EPAX, has been successfully applied to estimate fragment production cross sections in reactions of heavy ions at high incident energies. It is checked whether a similar parametrization can be found for proton-induced spallation around 1 GeV, the range of interest for ISOL-type RIB facilities. The validity of EPAX for medium-energy heavy-ion induced reactions is also checked. Only a few datasets are available, but in general EPAX predicts the cross sections rather well, except for fragments close to the projectile, where the experimental cross sections are found to be larger.

  14. Vitamin D-metabolites from human plasma and mass spectrometric analysis by fast heavy ion induced desorption

    Energy Technology Data Exchange (ETDEWEB)

    Fohlman, J; Peterson, P A [Uppsala Univ. (Sweden). Dept. of Cell Research; Kamensky, I; Hakansson, P; Sundqvist, B [Tandemacceleratorlaboratoriet, Uppsala (Sweden)

    1982-07-01

    D-vitamin metabolites have been isolated from human serum employing chromatographic techniques. The serum carrier protein for vitamin D (DBP) was first isolated by immunosorbent chromatography. Lipid ligands associated with DBP were then extracted with hexane and separated by high pressure liquid chromatography (HPLC). Detection of vitamin D metabolites by their absorbance of ultraviolet light is not sufficiently sensitive to monitor all vitamin D derivatives from a few millilitres of serum. Therefore, further analyses are necessary to quantitative these compounds. We have begun to develop a mass spectrometric method to achieve a reliable, quantitative procedure. As a first step towards this goal a number of pure samples of vitamin D compounds have been studied in a time-of-flight mass spectrometer based on fast heavy ion induced desorption. All vitamin D compounds examined could be detected and identified by their molecular ion and fragment spectra.

  15. Vitamin D-metabolites from human plasma and mass spectrometric analysis by fast heavy ion induced desorption

    International Nuclear Information System (INIS)

    Fohlman, J.; Peterson, P.A.

    1982-01-01

    D-vitamin metabolites have been isolated from human serum employing chromatographic techniques. The serum carrier protein for vitamin D (DBP) was first isolated by immunosorbent chromatography. Lipid ligands associated with DBP were then extracted with hexane and separated by high pressure liquid chromatography (HPLC). Detection of vitamin D metabolites by their absorbance of ultraviolet light is not sufficiently sensitive to monitor all vitamin D derivatives from a few millilitres of serum. Therefore, further analyses are necessary to quantitative these compounds. We have begun to develop a mass spectrometric method to achieve a reliable, quantitative procedure. As a first step towards this goal a number of pure samples of vitamin D compounds have been studied in a time-of-flight mass spectrometer based on fast heavy ion induced desorption. All vitamin D compounds examined could be detected and identified by their molecular ion and fragment spectra. (orig.)

  16. Investigation of Nuclear Fragmentation in Relativistic Heavy Ion Collisions Using Plastic - Nuclear - Track Detectors

    CERN Multimedia

    2002-01-01

    In this experiment CR39 plastic nuclear track detectors will be used which are sensitive to detect relativistic nuclear fragments with charges Z@$>$5. They will be analyzed using an automatic track measuring system which was developed at the University of Siegen.\\\\ \\\\ This allows to measure large quantities of tracks in these passive detectors and to perform high statistics experiments. We intend to measure cross sections for the production of nuclear fragments from heavy ion beams at the SPS. \\\\ \\\\ The energy independence of the cross sections predicted by the idea of limiting fragmentation will be tested at high energies. In exposures with different targets we plan to analyze the factorization of the fragmentation cross sections into a target depending factor and a factor depending on the beam particle and the fragment. The cross sections for one proton remov Coulomb dissociation. \\\\ \\\\ We plan to investigate Coulomb dissociation for different targets and different energies. Fragment and projectile charges ...

  17. Ion optics of a high resolution multipassage mass spectrometer with electrostatic ion mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Sakurai, T [Osaka Univ. (Japan). Dept. of Physics; Baril, M [Departement de Physique, Faculte des Sciences et de Genie, Universite Laval, Ste-Foy, Quebec G1K 7P4 (Canada)

    1995-09-01

    Ion trajectories in an electrostatic ion mirror are calculated. The interferences of the extended fringing fields of the mirror with finite aperture are studied. The results of the calculations are represented by three transfer matrices, which describe ion trajectories under the effects of a fringing field at the entrances, of an idealized mirror region, and of a fringing field at the exit. The focusing effects and ion-optical properties of mass spectrometers with electrostatic ion mirrors can be evaluated by using these transfer matrices. A high performance multipassage mass spectrometer is designed. The system has one magnet and four electrostatic sector analyzers and two ion mirrors. The double focusing condition and stigmatic focusing condition are achieved in any passage of the system. The mass resolution increases linearly with the number of passages in a magnet. (orig.).

  18. Kinetic energies of charged fragments resulting from multifragmentation and asymmetric fission of the C{sub 60} molecule in collisions with monocharged ions (2-130 keV)

    Energy Technology Data Exchange (ETDEWEB)

    Rentenier, A; Bordenave-Montesquieu, D; Moretto-Capelle, P; Bordenave-Montesquieu, A [Laboratoire CAR-IRSAMC, UMR 5589 CNRS - Universite Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse Cedex (France)

    2003-04-28

    Multifragmentation and asymmetric fission (AF) of the C{sub 60} molecule induced by H{sup +}, H{sub 2}{sup +}, H{sub 3}{sup +} and He{sup +} ions at medium collision energies (2-130 keV) are considered. Momenta and kinetic energies of C{sub n}{sup +} fragment ions (n = 1- 12) are deduced from an analysis of time-of-flight spectra. In multifragmentation processes, momenta are found to be approximately constant when n > 2, a behaviour which explains that the most probable kinetic energy, as well as the width of the kinetic energy distributions, is found to be inversely proportional to the fragment size n; both momenta and kinetic energies are independent of the velocity and nature of the projectile, and hence of the energy deposit. A specific study of the AF shows that the kinetic energies of C{sub 2}{sup +}, C{sub 4}{sup +} and C{sub 6}{sup +} fragments are also independent of the collision velocity and projectile species; a quantitative agreement is found with values deduced from kinetic energy release measurements by another group in electron impact experiments, and the observed decrease when the mass of the light fragment increases is also reproduced. A quantitative comparison of AF and multifragmentation for the n = 2, 4 and 6 fragment ions shows that kinetic energies in AF exceed that in multifragmentation, a result which explains the oscillations observed when momenta or kinetic energies of fragments are plotted against the n-value. The AF yield is also found to scale with the energy deposit in the collision velocity range extending below the velocity at the maximum of the electronic stopping power; except for protons, it remains negligible with respect to multifragmentation as soon as the total energy deposit exceeds about 100 eV.

  19. Regularity and mass conservation for discrete coagulation–fragmentation equations with diffusion

    KAUST Repository

    Cañizo, J.A.

    2010-03-01

    We present a new a priori estimate for discrete coagulation-fragmentation systems with size-dependent diffusion within a bounded, regular domain confined by homogeneous Neumann boundary conditions. Following from a duality argument, this a priori estimate provides a global L2 bound on the mass density and was previously used, for instance, in the context of reaction-diffusion equations. In this paper we demonstrate two lines of applications for such an estimate: On the one hand, it enables to simplify parts of the known existence theory and allows to show existence of solutions for generalised models involving collision-induced, quadratic fragmentation terms for which the previous existence theory seems difficult to apply. On the other hand and most prominently, it proves mass conservation (and thus the absence of gelation) for almost all the coagulation coefficients for which mass conservation is known to hold true in the space homogeneous case. © 2009 Elsevier Masson SAS. All rights reserved.

  20. Mass spectrometer and method with improved ion transmission

    International Nuclear Information System (INIS)

    Douglas, D.J.; French, J.B.

    1992-01-01

    This invention relates to a mass analyzer, and to a method of operating a mass analyzer, of the kind in which ions are transmitted through a first rod set for focussing and separation from an accompanying gas, before passing through a mass filter rod set which which permits transmission only of ions of a selected mass to charge ratio. (author). 19 figs

  1. Threshold photoelectron--photonion coincidence mass spectrometric study of ethylene and ethylene-d4

    International Nuclear Information System (INIS)

    Stockbauer, R.; Inghram, M.G.

    1975-01-01

    Experimental curves have been obtained for the fragmentation of ethylene and ethylene-d 4 ions as a function of the internal energy of those ions using threshold photoelectron--photoion coincidence mass spectrometry. The results are compared with the previous results of photoionization mass spectrometry, He I photoelectron--photoion coicidence, charge exchange experiments, and with quasiequilibrium theory (QET) calculations. The discrepancies between results of these previous experiments and QET calculations do not appear in the present data. It is suggested that ion--molecule reactions competing with charge exchange has led to erroneous conclusions in the interpretation of the charge exchange data. It is concluded that QET does describe the fragmentation of ethylene and ethylene-d 4 within the limits of the data and calculations available. The secondary ion fragmentation C 2 H 4 + → C 2 H 3 + +H → C 2 H 2 + +2H is discussed in detail with regard to the C 2 H 3 + fragment ion internal energy distribution

  2. Neutron emission effects on fragment mass and kinetic energy distribution from fission of 239Pu induced by thermal neutrons

    International Nuclear Information System (INIS)

    Montoya, M.; Rojas, J.; Lobato, I.

    2010-01-01

    The average of fragment kinetic energy (E-bar sign*) and the multiplicity of prompt neutrons (ν(bar sign)) as a function of fragment mass (m*), as well as the fragment mass yield (Y(m*)) from thermal neutron-induced fission of 239 Pu have been measured by Tsuchiya et al.. In that work the mass and kinetic energy are calculated from the measured kinetic energy of one fragment and the difference of time of flight of the two complementary fragments. However they do not present their results about the standard deviation σ E *(m*). In this work we have made a numerical simulation of that experiment which reproduces its results, assuming an initial distribution of the primary fragment kinetic energy (E(A)) with a constant value of the standard deviation as function of fragment mass (σ E (A)). As a result of the simulation we obtain the dependence σ E *(m*) which presents an enhancement between m* = 92 and m* = 110, and a peak at m* = 121.

  3. Negative Ion In-Source Decay Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for Sequencing Acidic Peptides

    Science.gov (United States)

    McMillen, Chelsea L.; Wright, Patience M.; Cassady, Carolyn J.

    2016-05-01

    Matrix-assisted laser desorption/ionization (MALDI) in-source decay was studied in the negative ion mode on deprotonated peptides to determine its usefulness for obtaining extensive sequence information for acidic peptides. Eight biological acidic peptides, ranging in size from 11 to 33 residues, were studied by negative ion mode ISD (nISD). The matrices 2,5-dihydroxybenzoic acid, 2-aminobenzoic acid, 2-aminobenzamide, 1,5-diaminonaphthalene, 5-amino-1-naphthol, 3-aminoquinoline, and 9-aminoacridine were used with each peptide. Optimal fragmentation was produced with 1,5-diaminonphthalene (DAN), and extensive sequence informative fragmentation was observed for every peptide except hirudin(54-65). Cleavage at the N-Cα bond of the peptide backbone, producing c' and z' ions, was dominant for all peptides. Cleavage of the N-Cα bond N-terminal to proline residues was not observed. The formation of c and z ions is also found in electron transfer dissociation (ETD), electron capture dissociation (ECD), and positive ion mode ISD, which are considered to be radical-driven techniques. Oxidized insulin chain A, which has four highly acidic oxidized cysteine residues, had less extensive fragmentation. This peptide also exhibited the only charged localized fragmentation, with more pronounced product ion formation adjacent to the highly acidic residues. In addition, spectra were obtained by positive ion mode ISD for each protonated peptide; more sequence informative fragmentation was observed via nISD for all peptides. Three of the peptides studied had no product ion formation in ISD, but extensive sequence informative fragmentation was found in their nISD spectra. The results of this study indicate that nISD can be used to readily obtain sequence information for acidic peptides.

  4. A generic approach for expanding homolog-targeted residue screening of sulfonamides using a fast matrix separation and class-specific fragmentation-dependent acquisition with a hybrid quadrupole-linear ion trap mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Huang Chunlin [Department of Biochemistry and Molecular Biology, School of Pharmacy and Life Science, University of South China, Hengyang 421001 (China); Guo Bin, E-mail: binnguo@126.com [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha 410081 (China); Wang Xiaoying [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha 410081 (China); Li Jie [Department of Biochemistry and Molecular Biology, School of Pharmacy and Life Science, University of South China, Hengyang 421001 (China); Zhu Weitao; Chen Bo [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha 410081 (China); Ouyang Shan [Food Inspection and Quarantine Center, Shenzhen Entry-Exit Inspection and Quarantine Bureau of the People' s Republic of China, Shenzhen 518067 (China); Yao Shouzhuo [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha 410081 (China)

    2012-08-06

    Highlights: Black-Right-Pointing-Pointer Generic homolog-targeted screening approach for multi-residual sulfonamide analogs. Black-Right-Pointing-Pointer Single-tube extraction/partitioning-multifunction adsorption cleanup for direct injection. Black-Right-Pointing-Pointer Class-specific fragmentation for expanding coverage of N{sup 4}-acetyl and N-OH metabolites. Black-Right-Pointing-Pointer PreS-IDA-EPI in LC-QqLIT for simultaneous screening and confirmation of real samples. - Abstract: A generic and efficient homolog-targeted approach was used to expand screening and detection of target class of sulfonamides and structural analogs, based on a fast single-tube extraction/partitioning-multifunction adsorption cleanup (SEP/MAC) for class-specific fragmentation-dependent acquisition with a liquid chromatography-hybrid triple-quadrupole linear ion trap mass spectrometer (LC-QqLIT). By combining the two-stage process conducted in a single tube as one-pot protocol, the straightforward SEP/MAC procedure was optimized to offer clean extracts with reasonable recovery (71-109% with RSDs < 20%) and decreased matrix interferences (-9 to 19%) of multiresidual sulfonamide extraction from different tissue samples. The novel use of neutral loss scan of 66 Da (NLS) or precursor ion scanning of m/z 108 (PreS) in positive ion mode was found to achieve more comprehensive coverage of protonated molecular ions of a wide array of sulfonamides including N{sup 4}-acetyl and hydroxylamine metabolites plus their possible dimers. Moreover, the PreS-triggered automatically enhanced product ion spectral acquisition enabled simultaneous screening, profiling and confirmation of an unlimited number of analytes belonging to the sulfonamide class within a single analysis. The validation and application results of the generic SEP/MAC-based LC-QqLIT strategy consistently demonstrated favorable performances with acceptable accuracy (67-116%), precision (RSDs < 25%), and sensitivity (LOQs {<=} 7.5 ng

  5. Baryon production and the centrality dependence of limiting fragmentation in heavy ion collision

    International Nuclear Information System (INIS)

    Mondal, M.M.; Chattopadhyay, S.

    2006-01-01

    In experiments with the relativistic heavy ion collisions the primary goals is to study the particle distribution in pseudorapidity variable. From the study of the distribution information of the collision mechanism such as the study of hypothesis of limiting fragmentation can be made

  6. Multiple-ion-beam time-of-flight mass spectrometer

    International Nuclear Information System (INIS)

    Rohrbacher, Andreas; Continetti, Robert E.

    2001-01-01

    An innovative approach to increase the throughput of mass spectrometric analyses using a multiple-ion-beam mass spectrometer is described. Two sample spots were applied onto a laser desorption/ionization target and each spot was simultaneously irradiated by a beam of quadrupled Nd:YLF laser radiation (261.75 nm) to produce ions by laser-desorption ionization. Acceleration of the ions in an electric field created parallel ion beams that were focused by two parallel einzel lens systems. After a flight path of 2.34 m, the ions were detected with a microchannel plate-phosphor screen assembly coupled with a charge coupled device camera that showed two resolved ion beams. Time-of-flight mass spectra were also obtained with this detector. Experiments were performed using both metal atom cations (Ti + and Cr + ) produced by laser desorption/ionization and the molecular ions of two different proteins (myoglobin and lysozyme), created by matrix assisted laser desorption/ionization using an excess of nicotinic acid as matrix

  7. Structural Characterization of Neutral Saccharides by Negative Ion MALDI Mass Spectrometry Using a Superbasic Proton Sponge as Deprotonating Matrix

    Science.gov (United States)

    Calvano, Cosima Damiana; Cataldi, Tommaso R. I.; Kögel, Julius F.; Monopoli, Antonio; Palmisano, Francesco; Sundermeyer, Jorge

    2017-08-01

    The superbasic proton sponge 1,8-bis(tripyrrolidinylphosphazenyl)naphthalene (TPPN) has been successfully employed for the structural characterization of neutral saccharides, cyclodextrins, and saccharide alditols by matrix assisted laser desorption/ionization tandem mass spectrometry (MALDI-MS/MS). Owing to its inherently high basicity, TPPN is capable of deprotonating neutral carbohydrates (M) providing an efficient and simple way to produce gas-phase [M - H]- ions. Highly informative negative ions MS/MS spectra showing several diagnostic fragment ions were obtained, mainly A-type cross-ring and C-type glycosidic cleavages. Indeed, cross-ring cleavages of monosaccharides with formation of 0,2A, 0,3A, 2,4A, 2,5A, 3,5A, and 0,3X product ions dominate the MS/MS spectra. A significant difference between reducing (e.g., lactose, maltose) and non-reducing disaccharides (e.g., sucrose, trehalose) was observed. Though disaccharides with the anomeric positions blocked give rise to deprotonated molecules, [M - H]-, at m/ z 341.1, reducing ones exhibited a peak at m/ z 340.1, most likely as radical anion, [M - H•- H]-•. The superiority of TPPN was clearly demonstrated by comparison with well recognized matrices, such as 2,5-dihydroxybenzoic acid and 2',4',6'-trihydroxyacetophenone (positive ion mode) and nor-harman (negative ion mode). MALDI MS/MS experiments on isotopically labeled sugars have greatly supported the interpretation of plausible fragmentation pathways.

  8. Correlations of intermediate mass fragments from Fe+Ta, Au, and Th collisions

    International Nuclear Information System (INIS)

    Sangster, T.C.; Begemann-Blaich, M.; Blaich, T.; Britt, H.C.; Hansen, L.F.; Namboodiri, M.N.; Peilert, G.

    1995-01-01

    Charge, velocity, and angular correlations between intermediate mass fragments (IMF) are presented for 50 and 100 MeV/nucleon Fe bombardments of Ta, Au, and Th targets. Correlation functions generated as a function of the relative velocity and the opening angle between two IMF's are qualitatively independent of the projectile energy and target mass and show a suppression at small relative velocities and opening angles due to the Coulomb repulsion between the fragments. The correlations are consistent with IMF's emitted primarily from a highly excited target residue following a rapid preequilibrium cascade. The correlation data are compared to model calculations using the event generator MENEKA and the quantum molecular dynamics (QMD) code with a statistical deexcitation of residual fragments utilizing the multifragmentation code SMM. All data are consistent with a simultaneous multifragmentation at a freeze-out density of 0.1--0.3 times normal nuclear matter density or a more sequential emission with time constant τ≤500 fm/c

  9. Differential cross section study of fragment production, at small angle, in relativistic heavy ion collisions. Application at a calculation of heavy ion beam transport in the matter

    International Nuclear Information System (INIS)

    Morel, P.

    1992-02-01

    Relativistic heavy ion collisions present the opportunity of creating in laboratory small volumes of hot, dense nuclear matter. On the experimental point of view, the collision events are characterized by a great number of fragments, especially in the direction of the projectile. The first part is devoted to a survey of relativistic heavy ion physics. Then, we present two experimental set-ups which permit, in particular, the analyse of light fragment production at small angles. We present experimental results concerning light projectiles on Ca, Nb, Pb targets, with energies from 200 A.MeV up to 600 A.MeV. Different aspects of the collision are put in evidence. Momentum and charge differential cross section are extrapolated to other projectile/target systems; that is used in a transport calculation of Ne ions in a target of biological interest (water), with a collimator. We show that nuclear fragmentation produces a dispersion in the spatial and energy distributions, and that one light fragments have a range greater than the projectile range. That last point causes a distortion of the Bragg curve, and that distortion must be taken into account for the application of heavy ions to radiotherapy problems. 95 figs., 8 tabs

  10. Neutron emission effects on final fragments mass and kinetic energy distribution from low energy fission of 234U

    International Nuclear Information System (INIS)

    Montoya, M.; Rojas, J.; Lobato, I.

    2008-01-01

    The standard deviation of the final kinetic energy distribution (σ e ) as a function of mass of final fragments (m) from low energy fission of 234 U, measured with the Lohengrin spectrometer by Belhafaf et al., presents a peak around m = 109 and another around m = 122. The authors attribute the first peak to the evaporation of a large number of neutrons around the corresponding mass number, i.e. there is no peak on the standard deviation of the primary kinetic energy distribution (σ E ) as a function of primary fragment mass (A). The second peak is attributed to a real peak on σ E (A). However, theoretical calculations related to primary distributions made by H.R. Faust and Z. Bao do not suggest any peak on σ E (A). In order to clarify this apparent controversy, we have made a numerical experiment in which the masses and the kinetic energy of final fragments are calculated, assuming an initial distribution of the kinetic energy without structures on the standard deviation as function of fragment mass. As a result we obtain a pronounced peak on σ e (m) curve around m = 109, a depletion from m = 121 to m = 129, and an small peak around m = 122, which is not as great as that measured by Belhafaf et al. Our simulation also reproduces the experimental results on the yield of the final mass Y(m), the average number of emitted neutrons as a function of the provisional mass (calculated from the values of the final kinetic energy of the complementary fragments) and the average value of fragment kinetic energy as a function of the final mass. From our results we conclude that there are no peaks on the σ E (A) curve, and the observed peaks on σ e (m) are due to the emitted neutron multiplicity and the variation of the average fragment kinetic energy as a function of primary fragment mass. (Author)

  11. Fragmentation of the C60 molecule in collision with light ions studied by a multi-correlation technique. Cross-sections, electron spectroscopy; Fragmentation de la molecule C60 par impact d'ions legers etudiee en multicorrelation. Sections efficaces, spectroscopie d'electrons

    Energy Technology Data Exchange (ETDEWEB)

    Rentenier, A

    2004-04-01

    A quantitative study of the C60 fullerenes fragmentation in collision with light ions (H{sub n}{sup +} with n=1,2,3, He{sup q+} with q=1,2) in the velocity range 0,1 - 2,3 u.a.) is presented. The multi-correlation technique, developed between fragment ions and electrons with well defined energy, has enlightened some of the dependences and properties of fragmentation mechanisms (cross sections, electron spectroscopy, size distributions, kinetic energy of fragment ions, Campi's scatter plot, activation energies). The deposited energy hence appeared as an important parameter. Cross sections have been measured, for the first time, for all the collisional processes. Ionisation and capture only depends on the collision velocity. On the other hand, scaling laws with the deposited energy have been observed for the cross sections of multifragmentation, which depends on the collision energy and the nature of the projectile. The deposited energy has also been found as an essential parameter to understand the evolution of the charged fragment size distributions. The electron spectroscopy, achieved at an emission angle of 35 degrees, showed spectra peaked at important energies (from 5 to 20 eV). The spectra shape depends on the collision velocity. A first theoretical analysis points out the link between the observed energy distribution and the presence of a centrifugal potential barrier. Finally, correlation experiments between produced ions and electron energy reveal that electron energy increases with internal energy. (author)

  12. The kick-out mass selection technique for ions stored in an Electrostatic Ion Beam Trap

    International Nuclear Information System (INIS)

    Toker, Y; Altstein, N; Aviv, O; Rappaport, M L; Heber, O; Schwalm, D; Strasser, D; Zajfman, D

    2009-01-01

    A simple mass selection technique which allows one to clean a keV ion beam of undesirable masses while stored in an Electrostatic Ion Beam Trap (EIBT) is described. The technique is based on the time-of-flight principle and takes advantage of the long storage times and self-bunching that are possible in this type of traps (self bunching being the effect that keeps ions of the same mass bunched in spite of their finite distributions of velocities and trajectories). As the oscillation period is proportional to the square root of the ion mass, bunches containing ions of different masses will separate in space with increasing storage time and can be kicked out by a pulsed deflector mounted inside the trap. A mass selector of this type has been implemented successfully in an EIBT connected to an Even-Lavie supersonic expansion source and is routinely used in ongoing cluster experiments.

  13. Mass spectrometry for fragment screening.

    Science.gov (United States)

    Chan, Daniel Shiu-Hin; Whitehouse, Andrew J; Coyne, Anthony G; Abell, Chris

    2017-11-08

    Fragment-based approaches in chemical biology and drug discovery have been widely adopted worldwide in both academia and industry. Fragment hits tend to interact weakly with their targets, necessitating the use of sensitive biophysical techniques to detect their binding. Common fragment screening techniques include differential scanning fluorimetry (DSF) and ligand-observed NMR. Validation and characterization of hits is usually performed using a combination of protein-observed NMR, isothermal titration calorimetry (ITC) and X-ray crystallography. In this context, MS is a relatively underutilized technique in fragment screening for drug discovery. MS-based techniques have the advantage of high sensitivity, low sample consumption and being label-free. This review highlights recent examples of the emerging use of MS-based techniques in fragment screening. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

  14. Coincidence measurements of intermediate mass fragments produced in /sup 32/S-induced reactions on Ag at E/A = 22.5 MeV

    International Nuclear Information System (INIS)

    Fields, D.J.; Lynch, W.G.; Nayak, T.K.

    1986-01-01

    Single- and two-particle inclusive cross sections for the production of light nuclei and intermediate mass fragments, 3< or =Z< or =24, were measured at angles well beyond the grazing angle for /sup 32/S-induced reactions on Ag at 720 MeV. Information about fragment multiplicities and reaction dynamics was extracted from measurements of light particles, intermediate mass fragments, and targetlike residues in coincidence with intermediate mass fragments. Incomplete linear momentum transfer and non-compound-particle emission are important features of collisions producing intermediate mass fragments. About half of the incident kinetic energy in these collisions is converted into internal excitation. The mean multiplicity of intermediate mass fragments is of the order of 1. Particle correlations are strongly enhanced in the plane which contains the intermediate mass fragment and the beam axis

  15. The formation of [M-H]+ ions in N-alkyl-substituted thieno[3,4-c]-pyrrole-4,6-dione derivatives during atmospheric pressure photoionization mass spectrometry

    KAUST Repository

    Sioud, Salim

    2014-10-09

    RESULTS [M-H]+ ions were observed under APPI conditions. The type of dopant and the length of the alkyl chain affected the formation of these ions. MS/MS fragmentation of [M-H]+ and [M + H]+ ions exhibited completely different patterns. Theoretical calculations revealed that the loss of hydrogen molecules from the [M + H]+ ions is the most favourable condition under which to form [M-H]+ ions.CONCLUSIONS [M-H]+ ions were detected in all the TPD derivatives studied here under the special experimental conditions during APPI, using a halogenated benzene dopant, and TPD containing substituted N-alkyl side chains with a minimum of four carbon atoms. Density functional theory calculations showed that for [M-H]+ ions to be formed under these conditions, the loss of hydrogen molecules from the [M + H]+ ions is proposed to be necessary.RATIONALE The formation of ions during atmospheric pressure photoionization (APPI) mass spectrometry in the positive mode usually provides radical cations and/or protonated species. Intriguingly, during the analysis of some N-alkyl-substituted thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives synthesized in our laboratory, unusual [M-H]+ ion peaks were observed. In this work we investigate the formation of [M-H]+ ions observed under APPI conditions.METHODS Multiple experimental parameters, including the type of ionization source, the composition of the solvent, the type of dopant, the infusion flow rate, and the length of the alkyl side chain were investigated to determine their effects on the formation of [M-H]+ ions. In addition, a comparison study of the gas-phase tandem mass spectrometric (MS/MS) fragmentation of [M + H]+ vs [M-H]+ ions and computational approaches were used.

  16. Fission fragment mass and total kinetic energy distributions of spontaneously fissioning plutonium isotopes

    Science.gov (United States)

    Pomorski, K.; Nerlo-Pomorska, B.; Bartel, J.; Schmitt, C.

    2018-03-01

    The fission-fragment mass and total kinetic energy (TKE) distributions are evaluated in a quantum mechanical framework using elongation, mass asymmetry, neck degree of freedom as the relevant collective parameters in the Fourier shape parametrization recently developed by us. The potential energy surfaces (PES) are calculated within the macroscopic-microscopic model based on the Lublin-Strasbourg Drop (LSD), the Yukawa-folded (YF) single-particle potential and a monopole pairing force. The PES are presented and analysed in detail for even-even Plutonium isotopes with A = 236-246. They reveal deep asymmetric valleys. The fission-fragment mass and TKE distributions are obtained from the ground state of a collective Hamiltonian computed within the Born-Oppenheimer approximation, in the WKB approach by introducing a neck-dependent fission probability. The calculated mass and total kinetic energy distributions are found in good agreement with the data.

  17. Native State Mass Spectrometry, Surface Plasmon Resonance, and X-ray Crystallography Correlate Strongly as a Fragment Screening Combination.

    Science.gov (United States)

    Woods, Lucy A; Dolezal, Olan; Ren, Bin; Ryan, John H; Peat, Thomas S; Poulsen, Sally-Ann

    2016-03-10

    Fragment-based drug discovery (FBDD) is contingent on the development of analytical methods to identify weak protein-fragment noncovalent interactions. Herein we have combined an underutilized fragment screening method, native state mass spectrometry, together with two proven and popular fragment screening methods, surface plasmon resonance and X-ray crystallography, in a fragment screening campaign against human carbonic anhydrase II (CA II). In an initial fragment screen against a 720-member fragment library (the "CSIRO Fragment Library") seven CA II binding fragments, including a selection of nonclassical CA II binding chemotypes, were identified. A further 70 compounds that comprised the initial hit chemotypes were subsequently sourced from the full CSIRO compound collection and screened. The fragment results were extremely well correlated across the three methods. Our findings demonstrate that there is a tremendous opportunity to apply native state mass spectrometry as a complementary fragment screening method to accelerate drug discovery.

  18. Fragmentation characteristics of hydroxycinnamic acids in ESI-MSn by density functional theory.

    Science.gov (United States)

    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.

  19. Approach to the study of flavone di-C-glycosides by high performance liquid chromatography-tandem ion trap mass spectrometry and its application to characterization of flavonoid composition in Viola yedoensis.

    Science.gov (United States)

    Cao, Jie; Yin, Chengle; Qin, Yan; Cheng, Zhihong; Chen, Daofeng

    2014-10-01

    The mass spectrometric (MS) analysis of flavone di-C-glycosides has been a difficult task due to pure standards being unavailable commercially and to that the reported relative intensities of some diagnostic ions varied with MS instruments. In this study, five flavone di-C-glycoside standards from Viola yedoensis have been systematically studied by high performance liquid chromatography-electrospray ionization-tandem ion trap mass spectrometry (HPLC-ESI-IT-MS(n)) in the negative ion mode to analyze their fragmentation patterns. A new MS(2) and MS(3) hierarchical fragmentation for the identification of the sugar nature (hexoses or pentoses) at C-6 and C-8 is presented based on previously established rules of fragmentation. Here, for the first time, we report that the MS(2) and MS(3) structure-diagnostic fragments about the glycosylation types and positions are highly dependent on the configuration of the sugars at C-6 and C-8. The base peak ((0,2) X1 (0,2) X(2)(-) ion) in MS(3) spectra of di-C-glycosides could be used as a diagnostic ion for flavone aglycones. These newly proposed fragmentation behaviors have been successfully applied to the characterization of flavone di-C-glycosides found in V. yedoensis. A total of 35 flavonoid glycosides, including 1 flavone mono-C-hexoside, 2 flavone 6,8-di-C-hexosides, 11 flavone 6,8-di-C-pentosides, 13 flavone 6,8-C-hexosyl-C-pentosides, 5 acetylated flavone C-glycosides and 3 flavonol O-glycosides, were identified or tentatively identified on the base of their UV profiles, MS and MS(n) (n = 5) data, or by comparing with reference substances. Among these, the acetylated flavone C-glycosides were reported from V. yedoensis for the first time. Copyright © 2014 John Wiley & Sons, Ltd.

  20. Biomaterial imaging with MeV-energy heavy ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Seki, Toshio, E-mail: seki@sakura.nucleng.kyoto-u.ac.jp [Department of Nuclear Engineering, Kyoto Univ., Uji, Kyoto 611-0011 (Japan); CREST, Japan Science and Technology Agency (JST), Chiyoda, Tokyo 102-0075 (Japan); Wakamatsu, Yoshinobu; Nakagawa, Shunichiro [Department of Nuclear Engineering, Kyoto Univ., Uji, Kyoto 611-0011 (Japan); Aoki, Takaaki [Department of Electronic Science and Engineering, Kyoto Univ., Nishikyo, Kyoto 615-8510 (Japan); CREST, Japan Science and Technology Agency (JST), Chiyoda, Tokyo 102-0075 (Japan); Ishihara, Akihiko [Laboratory of Cell Biology and Life Science, Graduate School of Human and Environmental Studies, Kyoto Univ., Sakyo, Kyoto 606-8501 (Japan); Matsuo, Jiro [Quantum Science and Engineering Center, Kyoto Univ., Uji, Kyoto 611-0011 (Japan); CREST, Japan Science and Technology Agency (JST), Chiyoda, Tokyo 102-0075 (Japan)

    2014-08-01

    The spatial distribution of several chemical compounds in biological tissues and cells can be obtained with mass spectrometry imaging (MSI). In conventional secondary ion mass spectrometry (SIMS) with keV-energy ion beams, elastic collisions occur between projectiles and atoms of constituent molecules. The collisions produce fragments, making the acquisition of molecular information difficult. In contrast, ion beams with MeV-energy excite near-surface electrons and enhance the ionization of high-mass molecules; hence, SIMS spectra of fragment-suppressed ionized molecules can be obtained with MeV-SIMS. To compare between MeV and conventional SIMS, we used the two methods based on MeV and Bi{sub 3}-keV ions, respectively, to obtain molecular images of rat cerebellum. Conventional SIMS images of m/z 184 were clearly observed, but with the Bi{sub 3} ion, the distribution of the molecule with m/z 772.5 could be observed with much difficulty. This effect was attributed to the low secondary ion yields and we could not get many signal counts with keV-energy beam. On the other hand, intact molecular ion distributions of lipids were clearly observed with MeV-SIMS, although the mass of all lipid molecules was higher than 500 Da. The peaks of intact molecular ions in MeV-SIMS spectra allowed us to assign the mass. The high secondary ion sensitivity with MeV-energy heavy ions is very useful in biomaterial analysis.

  1. Biomaterial imaging with MeV-energy heavy ion beams

    International Nuclear Information System (INIS)

    Seki, Toshio; Wakamatsu, Yoshinobu; Nakagawa, Shunichiro; Aoki, Takaaki; Ishihara, Akihiko; Matsuo, Jiro

    2014-01-01

    The spatial distribution of several chemical compounds in biological tissues and cells can be obtained with mass spectrometry imaging (MSI). In conventional secondary ion mass spectrometry (SIMS) with keV-energy ion beams, elastic collisions occur between projectiles and atoms of constituent molecules. The collisions produce fragments, making the acquisition of molecular information difficult. In contrast, ion beams with MeV-energy excite near-surface electrons and enhance the ionization of high-mass molecules; hence, SIMS spectra of fragment-suppressed ionized molecules can be obtained with MeV-SIMS. To compare between MeV and conventional SIMS, we used the two methods based on MeV and Bi 3 -keV ions, respectively, to obtain molecular images of rat cerebellum. Conventional SIMS images of m/z 184 were clearly observed, but with the Bi 3 ion, the distribution of the molecule with m/z 772.5 could be observed with much difficulty. This effect was attributed to the low secondary ion yields and we could not get many signal counts with keV-energy beam. On the other hand, intact molecular ion distributions of lipids were clearly observed with MeV-SIMS, although the mass of all lipid molecules was higher than 500 Da. The peaks of intact molecular ions in MeV-SIMS spectra allowed us to assign the mass. The high secondary ion sensitivity with MeV-energy heavy ions is very useful in biomaterial analysis

  2. Detection of gold cluster ions by ion-to-ion conversion using a CsI-converter

    International Nuclear Information System (INIS)

    Nguyen, V.-T.; Novilkov, A.C.; Obnorskii, V.V.

    1997-01-01

    Gold cluster ions in the m/z range of 10 4 -2 x 10 6 u were produced by bombarding a thin film of gold with 252 Cf-fission fragments. The gold covering a C-Al substrate formed islets having a mean diameter of 44 A. Their size- and mass-distribution was determined by means of electron microscopy. The main task was to measure the m/z distribution of the cluster ions ejected from the sample surface. For this purpose we built a time-of-flight (TOF) mass spectrometer, which could be used as a linear TOF instrument or, alternatively, as a tandem-TOF instrument being equipped with an ion-to-ion converter. Combining the results obtained in both modes, it turned out that the linear TOF instrument equipped with micro-channel plates had a mean detection efficiency for 20 keV cluster ions of about 40%. In the tandem mode, the cluster ions hit a CsI converter with energies of 40z keV (z = charge state), from where secondary ions - mainly Cs + and (CsI) n Cs + cluster ions - were ejected. These ions were used to measure the TOF spectrum of the gold cluster ions. The detection efficiency of the cluster ions was found to vary in the available mass range from 99.7% to 96.5%. The complete mass distribution between 4 x 10 4 and 4 x 10 6 u was determined and compared with the corresponding mass distribution of the gold islets covering the substrate. (orig.)

  3. Contributions of secondary fragmentation by carbon ion beams in water phantom: Monte Carlo simulation

    International Nuclear Information System (INIS)

    Ying, C K; Bolst, David; Tran, Linh T.; Guatelli, Susanna; Rosenfeld, A. B.; Kamil, W A

    2017-01-01

    Heavy-particle therapy such as carbon ion therapy is currently very popular because of its superior conformality in terms of dose distribution and higher Relative Biological Effectiveness (RBE). However, carbon ion beams produce a complex mixed radiation field, which needs to be fully characterised. In this study, the fragmentation of a 290 MeV/u primary carbon ion beam was studied using the Geant4 Monte Carlo Toolkit. When the primary carbon ion beam interacts with water, secondary light charged particles (H, He, Li, Be, B) and fast neutrons are produced, contributing to the dose, especially after the distal edge of the Bragg peak. (paper)

  4. Ionic fragmentation channels in electron collisions of small molecular ions

    International Nuclear Information System (INIS)

    Hoffmann, Jens

    2009-01-01

    Dissociative Recombination (DR) is one of the most important loss processes of molecular ions in the interstellar medium (IM). Ion storage rings allow to investigate these processes under realistic conditions. At the Heidelberg test storage ring TSR a new detector system was installed within the present work in order to study the DR sub-process of ion pair formation (IPF). The new detector expands the existing electron target setup by the possibility to measure strongly deflected negative ionic fragments. At the TSR such measurements can be performed with a uniquely high energy resolution by independently merging two electron beams with the ion beam. In this work IPF of HD + , H 3 + and HF + has been studied. In the case of HD + the result of the high resolution experiment shows quantum interferences. Analysis of the quantum oscillations leads to a new understanding of the reaction dynamics. For H 3 + it was for the first time possible to distinguish different IPF channels and to detect quantum interferences in the data. Finally the IPF of HF + was investigated in an energy range, where in previous experiments no conclusive results could be obtained. (orig.)

  5. Effect of excitation energy and angular momentum on the characteristics of 208Po and 210Po compound nucleus fission fragments

    International Nuclear Information System (INIS)

    Itkis, M.G.; Kalpakchieva, R.; Okolovich, V.N.; Penionzhkevich, Yu.Eh.; Tolstikov, V.N.

    1982-01-01

    To study characteristics of fissioning nucleus fragments, investigated were reactiiiiiiiiiiiiiiiH8Pt+ 12 C → 210 Po in the 12 C ion energy range of 86-110.5 MeV, of 192 Os+ 16 O → 208 Po in 90-131 MeV range, 204 Pb+ 3 He → 207 Po, 206 Pb+ 3 He → 209 Po, 207 Pb+ 3 He → 210 Po with 60 MeV 3 He ion energy. Using a correlation technique for measuring energies of two fragments mass and energy distributions of fission fragments of 208 Po and 210 Po compound nuclei produced in the reactions have been studied. Mass and energy distributions of fragments from fission of 208 Po and 210 Po in the reactions with ions 16 O, 12 C and 3 He were investigated in an ample energy range, using the correlational techniques for measurement of energies of two fragments. An increase in the total kinetic energy with rise of the angular momentum was observed, the fact indicating a weak coupling of one-particle and collective modes of motion in the fissile nucleus resulting in that the rolational energy is transfered mainly to translation energies of the fragments

  6. Interaction mean free path measurements for relativistic heavy ion fragments using CR39 plastic track detectors

    International Nuclear Information System (INIS)

    Drechsel, H.; Brechtmann, C.; Dreute, J.; Sonntag, S.; Trakowski, W.; Beer, J.; Heinrich, W.

    1984-01-01

    This paper describes an experiment measuring the interaction mean free paths for charge changing nuclear collisions of relativistic heavy ion fragments. We use a stack of CR39 plastic nuclear track detectors that was irradiated with 1.8 GeV/nucleon 40 Ar ions at the Berkeley Bevalac. About 1.5 x 10 7 etch cones were measured in this experiment using an automatic measuring system. By tracing the etch cones over successive plastic foils the particle trajectories in the stack were reconstructed. For 14185 trajectories with 6444 nuclear collisions of fragments with charge 9-15 the interaction mean free path in the plastic was determined. (orig.)

  7. Improved single ion cyclotron resonance mass spectroscopy

    International Nuclear Information System (INIS)

    Boyce, K.R.

    1993-01-01

    The author has improved the state of the art for precision mass spectroscopy of a mass doublet to below one part in 10 10 . By alternately loading single ions into a Penning trap, the author has determined the mass ratio M(CO + )/M(N + 2 ) = 0.999 598 887 74(11), an accuracy of 1 x 10 -10 . This is a factor of 4 improvement over previous measurements, and a factor of 10 better than the 1985 atomic mass table adjustment [WAA85a]. Much of the author's apparatus has been rebuilt, increasing the signal-to-noise ratio and improving the reliability of the machine. The typical time needed to make and cool a single ion has been reduced from about half an hour to under 5 minutes. This was done by a combination of faster ion-making and a much faster procedure for driving out ions of the wrong species. The improved S/N, in combination with a much better signal processing algorithm to extract the ion phase and frequency from the author's data, has substantially reduced the time required for the actual measurements. This is important now that the measurement time is a substantial fraction of the cycle time (the time to make a new ion and measure it). The improvements allow over 30 comparisons in one night, compared to 2 per night previously. This not only improves the statistics, but eliminates the possibility of large non-Gaussian errors due to sudden magnetic field shifts

  8. Mass spectrometry with ionization induced by 252Cf fission fragments

    International Nuclear Information System (INIS)

    Sysoev, A.A.; Artaev, V.B.

    1991-01-01

    The review deals with mass-spectrometry with ionization induced by 252 Cf fission fragments. Equipment and technique of the analysis, analytic possibilities of the method are considered. The method permits to determine molecular masses of large nonvolatile biological molecules. The method is practically nondestructive, it possesses a high resolution over the depth and surface, which permits to use it for the analysis of surface of semiconductors, dielectrics, catalysts, for the study of formation kinetics of complex unstable molecules on the surface

  9. Multiple H3+ fragment production in single collision of fast Hn+ clusters with He atoms

    International Nuclear Information System (INIS)

    Farizon, B.; Farizon, M.; Gaillard, M.J.; Gerlic, E.; Ouaskit, S.

    1994-09-01

    The production of H 3 + ions resulting from single collisions of mass-selected ionic hydrogen clusters, H n + (n=9,25,31), with helium at high velocity (1.55 times the Bohr velocity) has been studied. A strong double H 3 + ion production resulting from one incident cluster is observed. Moreover, evidence for a triple H 3 + fragment production is presented for n=25 and 31. Thus, in this energy range, the collision gives rise to multifragmentation processes. The formation of H 3 + ions takes place in the fragmentation of the multicharged cluster resulting from the collision. (authors)

  10. Fast Biological Modeling for Voxel-based Heavy Ion Treatment Planning Using the Mechanistic Repair-Misrepair-Fixation Model and Nuclear Fragment Spectra

    Energy Technology Data Exchange (ETDEWEB)

    Kamp, Florian [Department of Therapeutic Radiology, Yale University School of Medicine, New Haven, Connecticut (United States); Department of Radiation Oncology, Technische Universität München, Klinikum Rechts der Isar, München (Germany); Physik-Department, Technische Universität München, Garching (Germany); Cabal, Gonzalo [Experimental Physics–Medical Physics, Ludwig Maximilians University Munich, Garching (Germany); Mairani, Andrea [Medical Physics Unit, Centro Nazionale Adroterapia Oncologica (CNAO), Pavia (Italy); Heidelberg Ion-Beam Therapy Center, Heidelberg (Germany); Parodi, Katia [Experimental Physics–Medical Physics, Ludwig Maximilians University Munich, Garching (Germany); Wilkens, Jan J. [Department of Radiation Oncology, Technische Universität München, Klinikum Rechts der Isar, München (Germany); Physik-Department, Technische Universität München, Garching (Germany); Carlson, David J., E-mail: david.j.carlson@yale.edu [Department of Therapeutic Radiology, Yale University School of Medicine, New Haven, Connecticut (United States)

    2015-11-01

    Purpose: The physical and biological differences between heavy ions and photons have not been fully exploited and could improve treatment outcomes. In carbon ion therapy, treatment planning must account for physical properties, such as the absorbed dose and nuclear fragmentation, and for differences in the relative biological effectiveness (RBE) of ions compared with photons. We combined the mechanistic repair-misrepair-fixation (RMF) model with Monte Carlo-generated fragmentation spectra for biological optimization of carbon ion treatment plans. Methods and Materials: Relative changes in double-strand break yields and radiosensitivity parameters with particle type and energy were determined using the independently benchmarked Monte Carlo damage simulation and the RMF model to estimate the RBE values for primary carbon ions and secondary fragments. Depth-dependent energy spectra were generated with the Monte Carlo code FLUKA for clinically relevant initial carbon ion energies. The predicted trends in RBE were compared with the published experimental data. Biological optimization for carbon ions was implemented in a 3-dimensional research treatment planning tool. Results: We compared the RBE and RBE-weighted dose (RWD) distributions of different carbon ion treatment scenarios with and without nuclear fragments. The inclusion of fragments in the simulations led to smaller RBE predictions. A validation of RMF against measured cell survival data reported in published studies showed reasonable agreement. We calculated and optimized the RWD distributions on patient data and compared the RMF predictions with those from other biological models. The RBE values in an astrocytoma tumor ranged from 2.2 to 4.9 (mean 2.8) for a RWD of 3 Gy(RBE) assuming (α/β){sub X} = 2 Gy. Conclusions: These studies provide new information to quantify and assess uncertainties in the clinically relevant RBE values for carbon ion therapy based on biophysical mechanisms. We present results from

  11. The Effect of Stiffness Parameter on Mass Distribution in Heavy-Ion Induced Fission

    Science.gov (United States)

    Soheyli, Saeed; Khalil Khalili, Morteza; Ashrafi, Ghazaaleh

    2018-06-01

    The stiffness parameter of the composite system has been studied for several heavy-ion induced fission reactions without the contribution of non-compound nucleus fission events. In this research, determination of the stiffness parameter is based on the comparison between the experimental data on the mass widths of fission fragments and those predicted by the statistical model treatments at the saddle and scission points. Analysis of the results shows that for the induced fission reactions of different targets by the same projectile, the stiffness parameter of the composite system decreases with increasing the fissility parameter, as well as with increasing the mass number of the compound nucleus. This parameter also exhibits a similar behavior for the reactions of a given target induced by different projectiles. As expected, nearly same stiffness values are obtained for different reactions leading to the same compound nucleus.

  12. THE SMALL-SCALE PHYSICAL STRUCTURE AND FRAGMENTATION DIFFERENCE OF TWO EMBEDDED INTERMEDIATE-MASS PROTOSTARS IN ORION

    International Nuclear Information System (INIS)

    Van Kempen, T. A.; Longmore, S. N.; Johnstone, D.; Pillai, T.; Fuente, A.

    2012-01-01

    Intermediate-mass (IM) protostars, the bridge between the very common solar-like protostars and the more massive, but rarer, O and B stars, can only be studied at high physical spatial resolutions in a handful of clouds. In this paper, we present and analyze the continuum results from an observing campaign at the Submillimeter Array (SMA) targeting two well-studied IM protostars in Orion, NGC 2071 and L1641 S3 MMS 1. The extended SMA (eSMA) probes structure at angular resolutions up to 0.''2, revealing protostellar disks on scales of ∼200 AU. Continuum flux measurements on these scales indicate that a significant amount of mass, a few tens of M ☉ , is present. Envelope, stellar, and disk masses are derived using compact, extended, and eSMA configurations and compared against spectral energy distribution fitting models. We hypothesize that fragmentation into three components occurred within NGC 2071 at an early time, when the envelopes were less than 10% of their current masses, e.g., ☉ . No fragmentation occurred for L1641 S3 MMS 1. For NGC 2071, evidence is given that the bulk of the envelope material currently around each source was accreted after the initial fragmentation. In addition, about 30% of the total core mass is not yet associated to one of the three sources. A global accretion model is favored and a potential accretion history of NGC 2071 is presented. It is shown that the relatively low level of fragmentation in NGC 2071 was stifled compared to the expected fragmentation from a Jeans argument. Similarly, the lack of fragmentation in L1641 S3 MMS 1 is likely due to similar arguments.

  13. A comparison of flavonoid glycosides by electrospray tandem mass spectrometry

    Science.gov (United States)

    March, Raymond E.; Lewars, Errol G.; Stadey, Christopher J.; Miao, Xiu-Sheng; Zhao, Xiaoming; Metcalfe, Chris D.

    2006-01-01

    A comparison is presented of product ion mass spectra of protonated and deprotonated molecules of kaempferol-3-O-glucoside, quercitin-3-O-glucoside (isoquercitrin), quercitin-3-O-galactoside (hyperoin), apigenin-7-O-glucoside, luteolin-7-O-glucoside, genistein-7-O-glucoside, naringenin-7-O-glucoside (prunin), luteolin-4'-O-glucoside, luteolin-6-C-glucoside (homoorientin, known also as isoorientin), apigenin-8-C-glucoside (vitexin), and luteolin-8-C-glucoside (orientin) together with the product ion mass spectrum of deprotonated kaempferol-7-O-glucoside. All isomeric ions were distinguishable on the basis of their product ion mass spectra. For protonated 3-O-, 7-O-, and 4'-O-glycosides at a collision energy of 46-47 eV, homolytic cleavage of the O-glycosidic bond yielded aglycon Y+ ions, whereas in deprotonated 3-O-, 7-O-, and 4'-O-glycosides, heterolytic and homolytic cleavage of the O-glycosidic bond yielded radical aglycon (Y-H)- and aglycon (Y-) ions. In each case, fragmentation of either the glycan or the aglycon or both was observed. For 6-C- and 8-C-glycosides at a collision energy of 46-47 eV, fragmentation was restricted almost exclusively to the glycan. For luteolin-6-C-glucoside, the integrity of the aglycon structure is preserved at the expense of the glycan for which some 30 fragmentations were observed. Breakdown curves were determined as a function of collision energy for protonated and deprotonated luteolin-6-C-glucoside. An attempt has been made to rationalize the product ion mass spectra derived from C-O- and C-C-luteolin glucosides in terms of computed structures that indicate significant intramolecular hydrogen bonding and rotation of the B-ring to form a coplanar luteolin structure. It is proposed that protonated and deprotonated luteolin-6-C-glucoside may afford examples of cooperative interactive bonding that plays a major role in directing fragmentation.

  14. First in-situ measurements of a highly fragmented comet: ACE SWICS and WIND STICS measurements

    Science.gov (United States)

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

    2011-12-01

    While many of the characteristics of comets and their local plasma environment are obtained using remote sensing via spectroscopic methods, space-based mass spectrometers allow a unique opportunity to directly sample cometary material in situ. To date there have been only a handful of in-situ spacecraft encounters with comets, such as 1P/Halley, 103P/Hartley, 81P/Wild and others. Comet 73P/Schwassmann-Wachmann started to disintegrate in 1995, two major components B and C were recovered in 2001, and it burst into more than 36 pieces during its passage near the Earth in 2006. Serendipitously, some very distant fragmentation members, well-separated from the major identified fragments, passed between the Earth and Sun. Cometary pickup ions and possibly recombined solar wind minor ions convected past the Earth in late May 2006 and were observed by both the ACE/SWICS and WIND/STICS mass spectrometers, which are located in halo orbits around the Earth-Sun L1 Lagrange point. Most of these observations took place a few days after the main comet fragments passed through the ecliptic, when their orbits crossed the spacecraft-Sun line, suggesting additional pieces lagging far behind the main fragments. In this paper, we present the first in-situ observation of these pieces that passed very close to the spacecraft (<0.07AU) and conduct a comparative analysis of composition and characteristics of pick-up ions originating from a number of the cometary fragments. We find that the pick-up ion trail related to the comet fragments is much longer than expected. We constrain the C+/O+ and He+/He++ ratio and discuss the implications for the production rates of different fragments.

  15. A Ligand-observed Mass Spectrometry Approach Integrated into the Fragment Based Lead Discovery Pipeline

    Science.gov (United States)

    Chen, Xin; Qin, Shanshan; Chen, Shuai; Li, Jinlong; Li, Lixin; Wang, Zhongling; Wang, Quan; Lin, Jianping; Yang, Cheng; Shui, Wenqing

    2015-01-01

    In fragment-based lead discovery (FBLD), a cascade combining multiple orthogonal technologies is required for reliable detection and characterization of fragment binding to the target. Given the limitations of the mainstream screening techniques, we presented a ligand-observed mass spectrometry approach to expand the toolkits and increase the flexibility of building a FBLD pipeline especially for tough targets. In this study, this approach was integrated into a FBLD program targeting the HCV RNA polymerase NS5B. Our ligand-observed mass spectrometry analysis resulted in the discovery of 10 hits from a 384-member fragment library through two independent screens of complex cocktails and a follow-up validation assay. Moreover, this MS-based approach enabled quantitative measurement of weak binding affinities of fragments which was in general consistent with SPR analysis. Five out of the ten hits were then successfully translated to X-ray structures of fragment-bound complexes to lay a foundation for structure-based inhibitor design. With distinctive strengths in terms of high capacity and speed, minimal method development, easy sample preparation, low material consumption and quantitative capability, this MS-based assay is anticipated to be a valuable addition to the repertoire of current fragment screening techniques. PMID:25666181

  16. Asymmetric fission and evaporation of C60r+ (r = 2-4) fullerene ions in ion-C60 collisions: I. Proton results

    International Nuclear Information System (INIS)

    Rentenier, A; Bordenave-Montesquieu, A; Moretto-Capelle, P; Bordenave-Montesquieu, D

    2004-01-01

    A quantitative description of the asymmetric fission (AF) of C 60 r+ fullerene ions (r = 2-4), using a multistop coincidence technique between both fragment ions, is presented. Charged light fragment (LF) and heavy fragment (HF) size distributions are discussed together with the corresponding averaged sizes. Complete AF distributions are reported for the first time for C 60 2+ ions. Simple dependences of the more probable channels and averaged fragment sizes on the partner size are found and discussed. The LF ones are not very sensitive to the parent fullerene ion charge r and vary linearly with the HF size at least for the largest ones. On the other hand the HF ones present an oscillating dependence against the LF size, the odd-numbered LFs being correlated to a smaller HF size, and depend on r. In the comparison of branching ratios between AF and the competing pure neutral evaporation channel, some emphasis is given to the behaviour of the unimolecular processes with r which are compared with the evolution of the activation energies and fission barriers. From a close examination of the individual HF distributions the production mechanisms of odd-n fragments are discussed, and the most probable dissociation channels of even-numbered C n + excited carbon clusters identified. Finally, an analysis of the neutral channels is also presented for the first time, the total neutral mass N (in carbon units) being deduced from the mass conservation law. Surprising similarities between the charged LF- and N-distributions are found. AF processes are also identified where light neutrals and ions play a symmetrical role. These findings lead us to suggest that a concerted emission of ions and heavy neutrals is probably a fission mechanism to be considered to understand the AF process of the C 60 molecule in addition to the often assumed multistep fragmentation cascade scheme

  17. Studies of complex fragment emission in heavy ion reactions. Progress report, January 1, 1993 - September 1, 1995

    International Nuclear Information System (INIS)

    Charity, R.J.; Sobotka, L.G.

    1995-01-01

    This work involves the study of low and intermediate energy heavy-ion nuclear reactions. This work has two foci. First, the authors desired to learn about the properties of both nuclei and nuclear matter under abnormal conditions. Their efforts towards this end run abreast of those for their second focus which is the study of the relevant reaction mechanisms. The two objectives are inexorably linked because their experimental laboratory for studying nuclear properties is a dynamic one. Their task is to answer the questions of how nuclear and nuclear matter properties are reflected in the dynamics of the reactions. The second objective also has great intrinsic value in that they can anticipate improving upon their understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. The program has been: to study the dynamics of fusion reactions, specifically the dynamics of energy, mass, and angular momentum deposition. This work includes reactions near the Coulomb barrier, where fusion dominates the reaction cross section as well as higher energies where incomplete fusion reactions are the primary reactions. This includes the dynamics of fission, still the premier example of collective nuclear motion, as a function of excitation, spin, mass, and mass asymmetry. The authors push these kinds of studies into the intermediate energy domain, and where novel reaction scenarios are predicted. They have studied very central and peripheral collisions between very massive nuclei, and simplified projectile fragmentation reactions utilizing medium to light mass projectiles. The study of central collisions has shown us the importance of collective expansion. The study of peripheral collisions between very heavy nuclei has demonstrated the importance of dynamical production of fragments from the neck region

  18. 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.

    Science.gov (United States)

    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.

  19. Characterization of the surface organization of nanostructured hybrid organic-inorganic materials by time-of-flight secondary ion mass spectrometry

    Science.gov (United States)

    Cerveau; Corriu; Dabosi; Fischmeister-Lepeytre; Combarieu

    1999-01-01

    Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has been used to analyse the surface composition of organic-inorganic hybrid solids obtained by a sol-gel process. Gels of type O(1.5)Si-R-SiO(1. 5), obtained from bis-silylated precursors (R'O)(3)-R-Si(OR')(3) (R' = Me, Et and R = (-CH(2))(n)-, n = 1, 2, 6, 10, 12;--CH=CH-; (-CH(2))(3)NH(CH(2))(3)-; 1, 1'-ferrocenyl; (CH(2))(n)-Ph-(CH(2))(n)- with Ph = 1,4-phenylene and n = 0, 1, 2; Ph = 1,3,5-phenyl and n = 0) were analysed. The results were highly dependent on the nature of the organic group. When the organic group was small or 'rigid', the main peaks detected corresponded to SiOH and SiOR' residual groups. Fragment ions from the organic group were poorly detected in this case. When the organic group was larger and more 'flexible', characteristic mass fragment ions were detected at higher relative intensities, indicative of a different organization of the organic units in the solid. TOF-SIMS clearly showed the differences between the xerogels derived from mono- and bis-silylated organic precursors : the organic group is present at the surface of mono-silylated xerogels, whereas for bis-silylated ones, the organization is dependent on the length and the flexibility of the organic units. These TOF-SIMS results are in agreement with other features already reported. Copyright 1999 John Wiley & Sons, Ltd.

  20. Deeply inelastic collisions as a source of intermediate mass fragments at E/A = 27 MeV

    International Nuclear Information System (INIS)

    Borderie, B.; Montoya, M.; Rivet, M.F.; Jouan, D.; Cabot, C.; Fuchs, H.; Gardes, D.; Gauvin, H.; Jacquet, D.; Monnet, F.

    1988-01-01

    Intermediate-mass fragments detected in coincidence with heavy residues were measured in 40 Ar induced reactions on Ag at E/A = 27 MeV. From the observed characteristics, it is inferred that intermediate-mass fragments associated with the so-called intermediate-velocity source come mainly from deeply inelastic collisions occurring after or at the same time as preequilibrium particle emission. (orig.)

  1. Projectile fission of 238U relativistic ions in a Pb target and discovery of new fission fragments

    International Nuclear Information System (INIS)

    Bernas, M.; Donzaud, C.; Dessagne, Ph.; Miehe, Ch.; Hanelt, E.; Heinz, A.

    1994-01-01

    With the 238 U beam accelerated at relativistic energies by the heavy ion synchrotron (SIS) at GSI, fission was investigated using inverse kinematics. This geometry is well suited for analyzing fragments with the fragment separator. The fragments are identified by in flight measurements of their energy loss and time of flight signals. More than forty new isotopes have been discovered focusing on the light branch of fission products. (K.A.) 12 refs., 5 figs., 1 tab

  2. Matrix-assisted laser desorption/ionization mass spectrometry for the structural characterization of modified oligonucleotides

    International Nuclear Information System (INIS)

    Hurst, G.B.; Hettich, R.L.; Buchanan, M.V.; Stemmler, E.A.

    1993-01-01

    Matrix-assisted laser desorption ionization (MALDI) Fourier transform ion cyclotron resonance mass spectrometry (FTMS) and MALDI time-of-flight mass spectrometry (TOFMS) are being used to characterize conditions for the efficient desorption and ionization of normal and modified nucleic acid components. Basic and acidic matrix materials have been evaluated on the components. Basic and acidic matrix materials have been evaluated on the FTMS and TOFMS. Using MALDI-FTMS at 355 nm, less fragmentation has been observed using 2,5-dihydroxybenzoic acid, while more extensive fragmentation is observed for basic matrices, such as 1,5-diaminonaphthalene and 9-aminophenanthrene. Elevation of the cell pressure by the addition of Ar or CO 2 provides collisional cooling of desorbed ions, resulting in an enhancement of [M--H] - and structurally significant high-mass fragment ions. Using MALDI-TOFMS at 337 nm, fragmentation is significantly reduced relative to that observed on the FTMS, perhaps as a consequence of the longer times required for FTMS detection. On the FTMS and TOFMS, cluster ions have been observed in the negative ion mode when metal ions are present in the 2,5-dihydroxybenzoic acid matrix. Metal ion additions and clusters with matrix salts have also been observed for dinucleotides. Applications of MALDI-FTMS and MALDI-TOF to the detection of hydroxylated PAH nucleoside adducts are presented

  3. Neutron emission effects on final fragments mass and kinetic energy distribution from low energy fission of {sup 234}U

    Energy Technology Data Exchange (ETDEWEB)

    Montoya, M.; Rojas, J. [Instituto Peruano de Energia Nuclear, Av. Canada 1470, Lima 41 (Peru); Lobato, I. [Facultad de Ciencias, Universidad Nacional de Ingenieria, Av. Tupac Amaru 210, Apartado Postal 31-139, Lima (Peru)]. e-mail: mmontoya@ipen.gob.pe

    2008-07-01

    The standard deviation of the final kinetic energy distribution ({sigma}{sub e}) as a function of mass of final fragments (m) from low energy fission of {sup 234}U, measured with the Lohengrin spectrometer by Belhafaf et al., presents a peak around m = 109 and another around m = 122. The authors attribute the first peak to the evaporation of a large number of neutrons around the corresponding mass number, i.e. there is no peak on the standard deviation of the primary kinetic energy distribution ({sigma}{sub E}) as a function of primary fragment mass (A). The second peak is attributed to a real peak on {sigma}{sub E}(A). However, theoretical calculations related to primary distributions made by H.R. Faust and Z. Bao do not suggest any peak on {sigma}{sub E}(A). In order to clarify this apparent controversy, we have made a numerical experiment in which the masses and the kinetic energy of final fragments are calculated, assuming an initial distribution of the kinetic energy without structures on the standard deviation as function of fragment mass. As a result we obtain a pronounced peak on {sigma}{sub e} (m) curve around m = 109, a depletion from m = 121 to m = 129, and an small peak around m = 122, which is not as great as that measured by Belhafaf et al. Our simulation also reproduces the experimental results on the yield of the final mass Y(m), the average number of emitted neutrons as a function of the provisional mass (calculated from the values of the final kinetic energy of the complementary fragments) and the average value of fragment kinetic energy as a function of the final mass. From our results we conclude that there are no peaks on the {sigma}{sub E} (A) curve, and the observed peaks on {sigma}{sub e} (m) are due to the emitted neutron multiplicity and the variation of the average fragment kinetic energy as a function of primary fragment mass. (Author)

  4. Surface Ionization and Soft Landing Techniques in Mass Spectrometry

    International Nuclear Information System (INIS)

    Futrell, Jean H.; Laskin, Julia

    2010-01-01

    The advent of soft ionization techniques, notably electrospray and laser desorption ionization methods, has extended mass spectrometric methods to large molecules and molecular complexes. This both greatly expands applications of mass spectrometry and makes the activation and dissociation of complex ions an integral part of large molecule mass spectrometry. A corollary of the much greater number of internal degrees of freedom and high density of states associated with molecular complexity is that internal energies much higher than the dissociation energies for competing fragmentation processes are required for observable fragmentation in time scales sampled by mass spectrometers. This article describes the kinetics of surface-induced dissociation (SID), a particularly efficient activation method for complex ions. Two very important characteristics of SID are very rapid, sub-picosecond activation and precise control of ion internal energy by varying ion collision energy. The nature of the surface plays an important role in SID, determining both efficiency and mechanism of ion activation. Surface composition and morphology strongly influence the relative importance of competing reactions of SID, ion capture (soft-landing), surface reaction and neutralization. The important features of SID and ion soft-landing are described briefly in this review and more fully in the recommended reading list.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hunka Deborah Elaine; Austin, Daniel E.

    2005-07-01

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

  6. Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

    International Nuclear Information System (INIS)

    Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun; Fang, Hua; Zheng, Zhen-Yu; Gao, Xiang; Zhao, Yu-Fen; Wu, Zhen

    2015-01-01

    Highlights: • ESI-MS n , HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS n were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS 2 spectra of [M + Na] + ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C 3 H 7 PO 3 (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C 16 H 20 O 2 (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins

  7. Using positive-ion electrospray ionization mass spectrometry and H/D exchange study phosphoryl group transfer reactions involved in amino acid ester isopropyl phosphoramidates of Brefeldin A

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Mei-Juan; Zhang, He; Liao, Chao; Qiu, Ying-Kun [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Fang, Hua [The Third Institute of Oceanography of the State Oceanic Administration, Xiamen 361005 (China); Zheng, Zhen-Yu [College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Gao, Xiang [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); Zhao, Yu-Fen [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China); College of Chemistry and Chemical Engineering, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Wu, Zhen, E-mail: wuzhen@xmu.edu.cn [School of Pharmaceutical Sciences and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiang-An South Road, Xiamen 361102 (China)

    2015-01-01

    Highlights: • ESI-MS{sup n}, HRMS and H/D exchange were used. • The fragmentation pathways of NPAAE-BFA in ESI-MS{sup n} were described. • Fragment ions involved in phosphorus group’s rearrangement reactions were observed. • Two rearrangement mechanisms about phosphorylation–dephosphorylation were proposed. - Abstract: As mini-chemical models, amino acid ester isopropyl phosphoramidates of Brefeldin A (compounds 2a–2d) were synthesized and investigated by electrospray ionization tandem mass spectrometry in combination with H/D exchange. To further confirm the fragments’s structures, off-line Fourier transform resonance tandem mass spectrometry (FT-ICR-MS/MS) was also performed. The fragmentation rules of compounds 2a–2d have been summarized and the plausible schemes for the fragmentation pathways were proposed. In this study, one dephosphorylated ion and two phosphorylated ions were observed in ESI-MS{sup 2} spectra of [M + Na]{sup +} ions for compounds 2a–2d. The possible mechanisms about phosphorylation and dephosphorylation were proposed and confirmed by H/D exchange. For the “dephosphorylation” rearrangement, a nitrogen atom was migrated from the phosphoryl group to the carbon atom of Brefeldin A’s backbone with losing a molecule of C{sub 3}H{sub 7}PO{sub 3} (122 Da). For the “phosphorylation” rearrangement, an oxygen atom of one phosphoryl group attacked the sideward phosphorus atom to form a nine-member ring intermediate, then two steps of C-H covalent bond cleavage with consecutive migration of hydrogen atom to lose a molecule of C{sub 16}H{sub 20}O{sub 2} (244 Da). The two proposed rearrangement mechanisms about phosphoryl group transfer might be valuable for the structure analysis of other analogs and provide insights into elucidating the dynamic process of the phosphorylation–dephosphorylation of proteins.

  8. Turning an energy analyzer into a mass spectrometer and a charge sorter

    International Nuclear Information System (INIS)

    Lee, K.

    2004-01-01

    Full text:When a swarm of ions are accelerated by a pulsed electric field for a common duration before entering an electrostatically dispersive energy analyzer, they will be sorted according to their charge-to-mass ratio q/m. In other words, the apparent kinetic energy upon which an ion will be registered in an apparent 'energy' spectrum thus obtained is proportional to its q/m ratio. For ions of a fixed mass m, the apparent energy spectrum becomes a charge state distribution spectrum. For ions of a fixed charge q, the apparent energy spectrum becomes a mass spectrum. In essence, an energy analyzer becomes both a charge sorter and a mass spectrometer when operated in this mode. When this technique is brought to bear on the detection of photofragment ions, a distinct advantage emerges. Kinetic energy release distribution (KERD) of fragment ions conventionally is extracted from fitting of the ion time-of-flight profile to ion trajectory simulation results, as such a fair amount of uncertainty exists in the KERD thus obtained. With the current novel approach to mass spectrometry, the KERDs of photofragment ions can be obtained directly, and as a result, with a greater accuracy. This should advance the study of fragmentation dynamics considerably

  9. THE SMALL-SCALE PHYSICAL STRUCTURE AND FRAGMENTATION DIFFERENCE OF TWO EMBEDDED INTERMEDIATE-MASS PROTOSTARS IN ORION

    Energy Technology Data Exchange (ETDEWEB)

    Van Kempen, T. A. [Joint ALMA Offices, Alonso de Cordova 3107, Vitacura, Santiago (Chile); Longmore, S. N. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Johnstone, D. [National Research Council Canada, Herzberg Institute for Astronomy, 5071 West Saanich Road, Victoria, BC (Canada); Pillai, T. [Caltech, MC 249-17, 1200 East California Blvd, Pasadena, CA 91125 (United States); Fuente, A., E-mail: tkempen@alma.cl [Observatorio Astronomico Nacional (OAN), Apdo. 112, E-28803 Alcala de Henares, Madrid (Spain)

    2012-06-01

    Intermediate-mass (IM) protostars, the bridge between the very common solar-like protostars and the more massive, but rarer, O and B stars, can only be studied at high physical spatial resolutions in a handful of clouds. In this paper, we present and analyze the continuum results from an observing campaign at the Submillimeter Array (SMA) targeting two well-studied IM protostars in Orion, NGC 2071 and L1641 S3 MMS 1. The extended SMA (eSMA) probes structure at angular resolutions up to 0.''2, revealing protostellar disks on scales of {approx}200 AU. Continuum flux measurements on these scales indicate that a significant amount of mass, a few tens of M{sub Sun }, is present. Envelope, stellar, and disk masses are derived using compact, extended, and eSMA configurations and compared against spectral energy distribution fitting models. We hypothesize that fragmentation into three components occurred within NGC 2071 at an early time, when the envelopes were less than 10% of their current masses, e.g., <0.5 M{sub Sun }. No fragmentation occurred for L1641 S3 MMS 1. For NGC 2071, evidence is given that the bulk of the envelope material currently around each source was accreted after the initial fragmentation. In addition, about 30% of the total core mass is not yet associated to one of the three sources. A global accretion model is favored and a potential accretion history of NGC 2071 is presented. It is shown that the relatively low level of fragmentation in NGC 2071 was stifled compared to the expected fragmentation from a Jeans argument. Similarly, the lack of fragmentation in L1641 S3 MMS 1 is likely due to similar arguments.

  10. Studies of complex fragment emission in heavy ion reactions: Progress report, September 1, 1987--August 31, 1988

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1988-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this emission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of large fragment production in low energy reactions should go hand in hand with the study of energy, mass, and angular momentum transfer in incomplete fusion and non-compound reactions. This thread joins the apparently divergent subjects covered in this report

  11. SOFIA: An innovative setup to measure complete isotopic yield of fission fragments

    Directory of Open Access Journals (Sweden)

    Pellereau E.

    2013-12-01

    Full Text Available We performed an experiment dedicated to the accurate isotopic yield measurement of fission fragments over the whole range. SOFIA exploits the inverse kinematics technique: using heavy ion beams at relativistic energies, fission is induced by Coulomb excitation in a high-Z target. The fragments are emitted forward and both of them are identified in charge and mass. The setup will be presented, as well as preliminary spectra.

  12. Application of selected ion monitoring to the analysis of triacylglycerols in olive oil by high temperature-gas chromatography/mass spectrometry.

    Science.gov (United States)

    Ruiz-Samblás, C; González-Casado, A; Cuadros-Rodríguez, L; García, F P Rodríguez

    2010-06-30

    The analysis of the triacylglycerol (TAG) composition of oils is a very challenging task, since the TAGs have very similar physico-chemical properties. In this work, a high temperature-gas chromatographic method coupled to electron ionization-mass spectrometry (HT-GC/EI-MS), in the Selected Ion Monitoring (SIM) mode, method was developed for the analysis of TAGs in the olive oil; this is a method suitable for routine analysis. This method was developed using commercially available standard TAGs. The TAGs studied were separated according to their equivalent carbon number and degree of unsaturation. The peak assignment was carried out by locating the characteristic fragment ions having the same retention time on the SIM profile such as [RCO+74](+) and [RCO+128](+) ions, due to the fatty acyl residues on sn-1, sn-2 and sn-3 positions of the TAG molecule and the [M-OCOR](+) ions corresponding to the acyl ions. The developed method was very useful to eliminate the interferences that appeared in the mass spectrum since electron ionization can prevent satisfactory interpretation of spectra. Copyright 2010 Elsevier B.V. All rights reserved.

  13. Emission of H- fragments from collisions of OH+ ions with atoms and molecules

    International Nuclear Information System (INIS)

    Juhasz, Z.; Sulik, B.

    2010-01-01

    Compete text of publication follows. Detailed measurement of the kinematics of positive fragment ions from molecular collisions pro-vide useful information about the collision dynamics (see e.g. and references therein). In the present work, we turn our attention to negative fragments. Double differential emission spectra of negative charged particles have been measured in collisions of OH + ions with gas jets of Ar atoms and acetone (CH 3 -CO-CH 3 ) molecules at 7 keV impact energy. Among the emitted electrons, a relatively strong contribution of H - ions has been observed in both collision systems. According to a kinematic analysis, the observed H - ions were produced in close atom-atom collisions. For acetone, these ions originated from both the projectile and the target. The present ion impact energy range falls in the distal region of the Bragg peak. Therefore, a non negligible H - production in biological tissues could be relevant for ion therapy and for radiolysis in general. The present experiments were conducted at the 14.5 GHz Electron Cyclotron Resonance (ECR) ion source of the ARIBE facility, at the Grand Accelerateur National d'Ions Lourds (GANIL) in Caen, France. The molecular OH + ions were produced by introducing water vapor in the ECR plasma chamber. The extracted ions were collimated to a diameter of 2.5 mm before entering the collision chamber. In its center, the OH + projectiles crossed an effusive gas jet of either argon atoms or acetone molecules. In the collision area, the density of the gas target was typically of 10 13 cm -3 . The electrons and negative ions produced in the collision were detected by means of a single-stage spectrometer consisting of an electrostatic parallel-plate analyzer. Spectra taken at 30 deg observation angle are shown in Figure 1. Contributions from H - appear in clearly visible peaks. Kinematics shows that the peak at 410 eV in both panels is due emission of H - ions moving with nearly the projectile velocity. An H

  14. A generic approach for expanding homolog-targeted residue screening of sulfonamides using a fast matrix separation and class-specific fragmentation-dependent acquisition with a hybrid quadrupole-linear ion trap mass spectrometer

    International Nuclear Information System (INIS)

    Huang Chunlin; Guo Bin; Wang Xiaoying; Li Jie; Zhu Weitao; Chen Bo; Ouyang Shan; Yao Shouzhuo

    2012-01-01

    Highlights: ► Generic homolog-targeted screening approach for multi-residual sulfonamide analogs. ► Single-tube extraction/partitioning-multifunction adsorption cleanup for direct injection. ► Class-specific fragmentation for expanding coverage of N 4 -acetyl and N-OH metabolites. ► PreS–IDA–EPI in LC–QqLIT for simultaneous screening and confirmation of real samples. - Abstract: A generic and efficient homolog-targeted approach was used to expand screening and detection of target class of sulfonamides and structural analogs, based on a fast single-tube extraction/partitioning-multifunction adsorption cleanup (SEP/MAC) for class-specific fragmentation-dependent acquisition with a liquid chromatography–hybrid triple-quadrupole linear ion trap mass spectrometer (LC–QqLIT). By combining the two-stage process conducted in a single tube as one-pot protocol, the straightforward SEP/MAC procedure was optimized to offer clean extracts with reasonable recovery (71–109% with RSDs 4 -acetyl and hydroxylamine metabolites plus their possible dimers. Moreover, the PreS-triggered automatically enhanced product ion spectral acquisition enabled simultaneous screening, profiling and confirmation of an unlimited number of analytes belonging to the sulfonamide class within a single analysis. The validation and application results of the generic SEP/MAC-based LC–QqLIT strategy consistently demonstrated favorable performances with acceptable accuracy (67–116%), precision (RSDs −1 ) to meet the acceptance criteria for all the sulfonamide–tissue combinations. Thus, the integration of the matrix-independent SEP/MAC procedure and the multiparameter matching algorithm with the unit-resolution LC–QqLIT instrument can serve as a valuable semi-targeted discovery strategy for rapid screening and reliable quantitative/confirmatory analysis of real samples.

  15. Binding energies of cluster ions

    International Nuclear Information System (INIS)

    Parajuli, R.; Matt, S.; Scheier, P.; Echt, O.; Stamatovic, A.; Maerk, T.D.

    2002-01-01

    The binding energy of charged clusters may be measured by analyzing the kinetic energy released in the metastable decay of mass selected parent ions. Using finite heat bath theory to determine the binding energies of argon, neon, krypton, oxygen and nitrogen from their respective average kinetic energy released were carried out. A high-resolution double focussing two-sector mass spectrometer of reversed Nier-Johnson type geometry was used. MIKE ( mass-analysed ion kinetic energy) were measured to investigate decay reactions of mass-selected ions. For the inert gases neon (Ne n + ), argon (Ar n + ) and krypton (Kr n + ), it is found that the binding energies initially decrease with increasing size n and then level off at a value above the enthalpy of vaporization of the condensed phase. Oxygen cluster ions shown a characteristic dependence on cluster size (U-shape) indicating a change in the metastable fragmentation mechanism when going from the dimer to the decamer ion. (nevyjel)

  16. THE DYNAMICAL EVOLUTION OF LOW-MASS HYDROGEN-BURNING STARS, BROWN DWARFS, AND PLANETARY-MASS OBJECTS FORMED THROUGH DISK FRAGMENTATION

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yun; Kouwenhoven, M. B. N. [Department of Astronomy, School of Physics, Peking University, Yiheyuan Lu 5, Haidian Qu, Beijing 100871 (China); Stamatellos, D. [Jeremiah Horrocks Institute for Mathematics, Physics and Astronomy, University of Central Lancashire, Preston, PR1 2HE (United Kingdom); Goodwin, S. P., E-mail: yunli@pku.edu.cn [Department of Physics and Astronomy, The University of Sheffield, Hicks Building, Hounsfield Road, Sheffield S3 7RH (United Kingdom)

    2015-06-01

    Theory and simulations suggest that it is possible to form low-mass hydrogen-burning stars, brown dwarfs (BDs), and planetary-mass objects (PMOs) via disk fragmentation. As disk fragmentation results in the formation of several bodies at comparable distances to the host star, their orbits are generally unstable. Here, we study the dynamical evolution of these objects. We set up the initial conditions based on the outcomes of the smoothed-particle hydrodynamics simulations of Stamatellos and Whitworth, and for comparison we also study the evolution of systems resulting from lower-mass fragmenting disks. We refer to these two sets of simulations as set 1 and set 2, respectively. At 10 Myr, approximately half of the host stars have one companion left, and approximately 22% (set 1) to 9.8% (set 2) of the host stars are single. Systems with multiple secondaries in relatively stable configurations are common (about 30% and 44%, respectively). The majority of the companions are ejected within 1 Myr with velocities mostly below 5 km s{sup −1}, with some runaway escapers with velocities over 30 km s{sup −1}. Roughly 6% (set 1) and 2% (set 2) of the companions pair up into very low-mass binary systems, resulting in respective binary fractions of 3.2% and 1.2%. The majority of these pairs escape as very low-mass binaries, while others remain bound to the host star in hierarchical configurations (often with retrograde inner orbits). Physical collisions with the host star (0.43 and 0.18 events per host star for set 1 and set 2, respectively) and between companions (0.08 and 0.04 events per host star for set 1 and set 2, respectively) are relatively common and their frequency increases with increasing disk mass. Our study predicts observable properties of very low-mass binaries, low-mass hierarchical systems, the BD desert, and free-floating BDs and PMOs in and near young stellar groupings, which can be used to distinguish between different formation scenarios of very low-mass

  17. DNA double-strand breaks in mammalian cells exposed to γ-rays and very heavy ions. Fragment-size distributions determined by pulsed-field gel electrophoresis

    International Nuclear Information System (INIS)

    Kraxenberger, F.; Friedl, A.A.; Eckardt-Schupp, F.; Weber, K.J.; Flentje, M.; Quicken, P.; Kellerer, A.M.; Ludwig-Maximilians University, Munich

    1998-01-01

    The spatial distribution of DNA double-strand breaks (DSB) was assessed after treatment of mammalian cells (V79) with densely ionizing radiation. Cells were exposed to beams of heavy charged particles (calcium ions: 6.9 MeV/u, 2.1.10 3 keV/μm; uranium ions: 9.0 MeV/u, 1.4.10 4 keV/μm) at the linear accelerator UNILAC of GSI, Darmstadt. DNA was isolated in agarose plugs and subjected to pulsed-field gel electrophoresis under conditions that separated DNA fragments of size 50 kbp to 5 Mbp. The measured fragment distributions were compared to those obtained after γ-irradiation and were analyzed by means of a convolution and a deconvolution technique. In contrast to the finding for γ-radiation, the distributions produced by heavy ions do not correspond to the random breakage model. Their marked overdispersion and the observed excess of short fragments reflect spatial clustering of DSB that extends over large regions of the DNA, up to several mega base pairs (Mbp). At fluences of 0.75 and 1.5/μm 2 , calcium ions produce nearly the same shape of fragment spectrum, merely with a difference in the amount of DNA entering the gel; this suggests that the DNA is fragmented by individual calcium ions. At a fluence of 0.8/μm 2 uranium ions produce a profile that is shifted to smaller fragment sizes in comparison to the profile obtained at a fluence of 0.4/μm 2 ; this suggests cumulative action of two separate ions in the formation of fragments. These observations are not consistent with the expectation that the uranium ions, with their much larger LET, should be more likely to produce single particle action than the calcium ions. However, a consideration of the greater lateral extension of the tracks of the faster uranium ions explains the observed differences; it suggests that the DNA is closely coiled so that even DNA locations several Mbp apart are usually not separated by less than 0.1 or 0.2 μm. (orig.)

  18. Peptide Peak Detection for Low Resolution MALDI-TOF Mass Spectrometry.

    Science.gov (United States)

    Yao, Jingwen; Utsunomiya, Shin-Ichi; Kajihara, Shigeki; Tabata, Tsuyoshi; Aoshima, Ken; Oda, Yoshiya; Tanaka, Koichi

    2014-01-01

    A new peak detection method has been developed for rapid selection of peptide and its fragment ion peaks for protein identification using tandem mass spectrometry. The algorithm applies classification of peak intensities present in the defined mass range to determine the noise level. A threshold is then given to select ion peaks according to the determined noise level in each mass range. This algorithm was initially designed for the peak detection of low resolution peptide mass spectra, such as matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) mass spectra. But it can also be applied to other type of mass spectra. This method has demonstrated obtaining a good rate of number of real ions to noises for even poorly fragmented peptide spectra. The effect of using peak lists generated from this method produces improved protein scores in database search results. The reliability of the protein identifications is increased by finding more peptide identifications. This software tool is freely available at the Mass++ home page (http://www.first-ms3d.jp/english/achievement/software/).

  19. Mass spectra of liquid crystals. III.Phenylpyrimidine derivatives

    NARCIS (Netherlands)

    Leclercq, P.A.; Bogaert, van den H.M.

    1991-01-01

    The 70 eV electron impact mass spectra of 34 1-phenyl-2,5-pyrimidine derivatives are presented. Based on the observed mass shifts by the various substituents, the nature of the main fragment ions is rationalized.

  20. Measurements of isomers at the FRS ion catcher

    Energy Technology Data Exchange (ETDEWEB)

    Hornung, Christine [Justus-Liebig Universitaet Giessen (Germany); Collaboration: FRS Ion Catcher-Collaboration

    2016-07-01

    Projectile fragmentation and fission reactions at in-flight facilities are important production mechanisms to access short-lived exotic nuclei. It is a challenge to describe the angular momentum distribution after the collision of relativistic nuclei. This can be experimentally accessed by measuring the population of isomeric states. Isomeric ratios and excitation energies of isomers of short-lived exotic nuclei can be determined at the FRS Ion Catcher at GSI. At the FRS, projectile and fission fragments are produced at relativistic energies, separated in-flight and range-focused. They are slowed down and thermalized in a cryogenic stopping cell. In a multi-purpose RFQ beamline alpha spectroscopy can be performed. Alternatively the ions can be transported to a multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS), where masses of the ground and isomeric states can be measured simultaneously with high resolving power. The MR-TOF-MS can also be used to spatially separate the ions in order to provide isomerically clean ion beams. During a recent experiment isomer-to-ground state ratios and excitation energies of uranium projectile and fission fragments produced at 1 GeV/u were measured. The ratios, measured with the MR-TOF-MS, were verified by alpha spectroscopy. Furthermore the ratios were compared to calculations based on an abrasion-ablation model of fragmentation.

  1. Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    Farnsworth, Paul B.; Spencer, Ross L.

    2017-08-01

    Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

  2. Radio-frequency ion deflector for mass separation

    Energy Technology Data Exchange (ETDEWEB)

    Schlösser, Magnus, E-mail: magnus.schloesser@googlemail.com; Rudnev, Vitaly; Ureña, Ángel González, E-mail: laseres@pluri.ucm.es [Unidad de Láseres y Haces Moleculares, Instituto Plurisdisciplinar, Universidad Complutense de Madrid, Madrid 28040 (Spain)

    2015-10-15

    Electrostatic cylindrical deflectors act as energy analyzer for ion beams. In this article, we present that by imposing of a radio-frequency modulation on the deflecting electric field, the ion transmission becomes mass dependent. By the choice of the appropriate frequency, amplitude, and phase, the deflector can be used as mass filter. The basic concept of the new instrument as well as simple mathematic relations are described. These calculations and further numerical simulations show that a mass sensitivity is achievable. Furthermore, we demonstrate the proof-of-principle in experimental measurements, compare the results to those of from a 1 m linear time-of-flight spectrometer, and comment on the mass resolution of the method. Finally, some potential applications are indicated.

  3. Mass spectrometer with two ion sources

    International Nuclear Information System (INIS)

    Glickman, L.G.; Mit', A.G.

    2002-01-01

    Static mass spectrometer with mid-plane near which ions are moving is considered in this article. Two ion sources are used, their exit slits are perpendicular to the mid-plane. The simple method of the replacement of source is offered. Two concave two-electrode transaxial mirrors with two-plate electrodes are used for this aim. The mid-plane of these mirrors coincides with the mid-plane of the device. The exit slit of each source is located in the principal plane of the object space. The principal planes of the image space of the both mirrors coincide. The images of the exit slits of the sources are in these planes and coincide too. We used the mirrors making stigmatic images with the magnification one to one, in which the dispersion on energy and spherical aberrations of the second order are equal to zero. These images are the objects on which the ion-optical system of the mass spectrometer is tuned. When you choose one from two ion sources it is enough to switch the corresponding mirror

  4. Effects of Neutron Emission on Fragment Mass and Kinetic Energy Distribution from Thermal Neutron-Induced Fission of 235U

    International Nuclear Information System (INIS)

    Montoya, M.; Rojas, J.; Saetone, E.

    2007-01-01

    The mass and kinetic energy distribution of nuclear fragments from thermal neutron-induced fission of 235 U(n th ,f) have been studied using a Monte-Carlo simulation. Besides reproducing the pronounced broadening in the standard deviation of the kinetic energy at the final fragment mass number around m = 109, our simulation also produces a second broadening around m = 125. These results are in good agreement with the experimental data obtained by Belhafaf et al. and other results on yield of mass. We conclude that the obtained results are a consequence of the characteristics of the neutron emission, the sharp variation in the primary fragment kinetic energy and mass yield curves. We show that because neutron emission is hazardous to make any conclusion on primary quantities distribution of fragments from experimental results on final quantities distributions

  5. Screening and identification of steroidal saponins from Anemarrhena asphodeloides employing UPLC tandem triple quadrupole linear ion trap mass spectrometry.

    Science.gov (United States)

    Xia, Yong-Gang; Guo, Xin-Dong; Liang, Jun; Yang, Bing-You; Kuang, Hai-Xue

    2017-09-01

    This study presents a practical and valid strategy for the screening and structural characterization of Anemarrhena asphodeloides Bge steroidal saponins (SSs) using ultra-high performance liquid chromatography coupled with triple quadrupole linear ion trap mass spectrometry. The whole analytical protocols integrate four-step procedures in the positive mode: (1) rational deduction of mass fragmentation pathways of A. asphodeloides SSs; (2) untargeted screening of potential A. asphodeloides SSs by multiple-ion monitoring-information-dependent-acquiring-enhanced product ion (MIM-IDA-EPI) scan through reverse phase liquid chromatography; (3) comprehensive construction of an ammoniated precursor ion database by combining untargeted MIM-IDA-EPI scans and data literature; and (4) structural interpretation of targeted A. asphodeloides SSs using MIM-IDA-EPI and multiple reaction monitoring (MRM)-IDA-EPI with an energy-resolved technique. The protocols were used to analyze SSs in A. asphodeloides; of the 87 detected SSs that were unambiguously characterized or tentatively identified, 19 compounds were the first to be reported from A. asphodeloides and 13 ones were characterized as potential new compounds. Accuracy of the analytical procedure was demonstrated by structural identification of three SSs by NMR spectroscopy. The proposed schemes hold an excellent promise in the structural prediction and interpretation of complex SSs from plant medicines by mass spectrometry. Copyright © 2017 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

    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.

  7. Monte Carlo simulation for fragment mass and kinetic energy distributions from the neutron-induced fission of 235U

    International Nuclear Information System (INIS)

    Montoya, M.; Rojas, J.; Saettone, E.

    2007-01-01

    The mass and kinetic energy distribution of nuclear fragments from the thermal neutron-induced fission of 235 U have been studied using a Monte Carlo simulation. Besides reproducing the pronounced broadening on the standard deviation of the final fragment kinetic energy distribution (σ e (m)) around the mass number m = 109, our simulation also produces a second broadening around m = 125 that is in agreement with the experimental data obtained by Belhafaf et al. These results are a consequence of the characteristics of the neutron emission, the variation in the primary fragment mean kinetic energy, and the yield as a function of the mass. (Author)

  8. A Microchannel Inlet to Reduce High-Velocity Impact Fragmentation of Molecules in Orbital and Fly-by Mass Spectrometers

    Science.gov (United States)

    Turner, Brandon; Anupriya, Anupriya; Sevy, Eric; Austin, Daniel E.

    2017-10-01

    Closed source neutral mass spectrometers are often used on flyby missions to characterize the molecular components of planetary exospheres. In a typical closed source, neutrals are thermalized as they deflect off the walls within a spherical antechamber prior to ionization and mass analysis. However, the high kinetic energy of each molecule as it impacts the chamber can lead to fragmentation before the ionization region is reached. Due to this fragmentation, the original composition of the molecule can be altered, leading to ambiguous identification.Even knowing the fragmentation pathways that occur may not allow deconvolution of data to give the correct composition. Only stable, volatile fragments will be observed in the subsequent mass spectrometer and different organic compounds likely give similar fragmentation products. Simply detecting these products will not lead to unambiguous identication of the precursor molecules. Here, we present a hardware solution to this problem—an inlet that reduces the fragmentation of molecules that impact at high velocities.We present a microchannel inlet that reduces the impact fragmentation by allowing the molecules to dissipate kinetic energy faster than their respective dissociation lifetimes. Preliminary calculations indicate that impact-induced fragmentation will be reduced up to three orders of magnitude compared with conventional closed sources by using this inlet. The benefits of such an inlet apply to any orbital or flyby velocity. The microchannel inlet enables detection of semi-volatile molecules that were previously undetectable due to impact fragmentation.

  9. U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

    Science.gov (United States)

    Bischoff, J.L.; Wooden, J.; Murphy, F.; Williams, Ross W.

    2005-01-01

    We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ???60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few ??m deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems. Copyright ?? 2005 Elsevier Ltd.

  10. The effects of electron transfer on the energy loss of slow He2+, C2+, and C4+ ions penetrating a graphene fragment

    International Nuclear Information System (INIS)

    Mao, Fei; Zhang, Chao; Gao, Cong-Zhang; Dai, Jinxia; Zhang, Feng-Shou

    2014-01-01

    Electronic energy loss in the collision processes of slow ions with a graphene fragment is investigated by combining ab initio time-dependent density functional theory calculations for electrons with molecular dynamics simulations for ions in real time and real space. We study the electronic energy loss of slow He 2+ , C 2+ , and C 4+ ions penetrating the graphene fragment as a function of the ion velocity, and establish the velocity-proportional energy loss for low-charged ions down to 0.1 a.u. One mechanism clarified in the simulations for electron transfer is polarization capture, which is effective for bare ions at low velocities. The other one is resonance capture, by which the incident ion can capture electrons from the graphene fragment to its electron affinity levels, which have the same, or nearly the same, energy as those of the electron donor levels. The results demonstrate that the nonlinear behavior of energy loss of C 4+ is attributed to the large number of electrons captured by this multi-charged ion during the collision. (paper)

  11. Ion deposition by inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Hu, K.; Houk, R.S.

    1996-01-01

    An atmospheric pressure inductively coupled plasma (ICP) is used with a quadrupole mass spectrometer (MS) for ion deposition. The deposited element is introduced as a nebulized aqueous solution. Modifications to the ICP-MS device allow generation and deposition of a mass-resolved beam of 165 Ho + at 5x10 12 ions s -1 . The ICP is a universal, multielement ion source that can potentially be used for applications such as deposition of mixtures of widely varying stoichiometry or of alternating layers of different elements. copyright 1996 American Vacuum Society

  12. Recent ion optics and mass spectrometers

    International Nuclear Information System (INIS)

    Matsuda, Hisashi

    1976-01-01

    The establishment of the third order approximation method for computing the orbit of the ion optical system for mass spectrometers and the completion of its computer program are reported. A feature of this orbit computation is in that the effect of the fringing field can be considered with the accuracy of third order approximation. Several new ion optical systems for mass spectrometers have been proposed by using such orbit computing programs. Brief explanation and the description on the future prospect and problems are made on the following items: the vertual image double focusing mass spectrometer, the second order double focusing mass spectrometer, the E x B superposed field mass spectrometer, and the apparatus with a cylindrical electric field and Q-lens. In the E x B superposed field with Matsuda plates, if the magnetic field is generated by an electromagnet instead of a permanent magnet, the dispersion of mass and energy can be changed at will. The Matsuda plates are known as the auxiliary electrodes positioned at the top and bottom of a cylindrical capacitor. Utilizing those characteristics, a zoom spectrometer can be made, with which only a necessary part of mass spectra can be investigated in detail, but the whole spectra are investigated roughly. In addition, the distribution of energy can be investigated simultaneously after the separation of ionic mass similarly to the parabola apparatus. (Iwakiri, K.)

  13. Electrostatic ion trap and Fourier transform measurements for high-resolution mass spectrometry

    International Nuclear Information System (INIS)

    Bhushan, K. G.; Gadkari, S. C.; Yakhmi, J. V.; Sahni, V. C.

    2007-01-01

    We report on the development of an electrostatic ion trap for high-resolution mass spectrometry. The trap works on purely electrostatic fields and hence trapping and storing of ions is not mass restrictive, unlike other techniques based on Penning, Paul, or radio frequency quadrupole ion traps. It allows simultaneous trapping and studying of multiple mass species over a large mass range. Mass spectra were recorded in ''dispersive'' and ''self-bunching'' modes of ions. Storage lifetimes of about 100 ms and mass resolving power of about 20 000 could be achieved from the fifth harmonic Fourier transform spectrum of Xe ions recorded in the self-bunching mode

  14. Fragmentation of the C60 molecule in collision with light ions studied by a multi-correlation technique. Cross-sections, electron spectroscopy

    International Nuclear Information System (INIS)

    Rentenier, A.

    2004-04-01

    A quantitative study of the C60 fullerenes fragmentation in collision with light ions (H n + with n=1,2,3, He q+ with q=1,2) in the velocity range 0,1 - 2,3 u.a.) is presented. The multi-correlation technique, developed between fragment ions and electrons with well defined energy, has enlightened some of the dependences and properties of fragmentation mechanisms (cross sections, electron spectroscopy, size distributions, kinetic energy of fragment ions, Campi's scatter plot, activation energies). The deposited energy hence appeared as an important parameter. Cross sections have been measured, for the first time, for all the collisional processes. Ionisation and capture only depends on the collision velocity. On the other hand, scaling laws with the deposited energy have been observed for the cross sections of multifragmentation, which depends on the collision energy and the nature of the projectile. The deposited energy has also been found as an essential parameter to understand the evolution of the charged fragment size distributions. The electron spectroscopy, achieved at an emission angle of 35 degrees, showed spectra peaked at important energies (from 5 to 20 eV). The spectra shape depends on the collision velocity. A first theoretical analysis points out the link between the observed energy distribution and the presence of a centrifugal potential barrier. Finally, correlation experiments between produced ions and electron energy reveal that electron energy increases with internal energy. (author)

  15. Radiocarbon detection by ion charge exchange mass spectrometry

    International Nuclear Information System (INIS)

    Hotchkis, Michael; Wei, Tao

    2007-01-01

    A method for detection of radiocarbon at low levels is described and the results of tests are presented. We refer to this method as ion charge exchange mass spectrometry (ICE-MS). The ICE-MS instrument is a two stage mass spectrometer. In the first stage, molecular interferences which would otherwise affect radiocarbon detection at mass 14 are eliminated by producing high charge state ions directly in the ion source (charge state ≥2). 14 N interference is eliminated in the second stage by converting the beam to negative ions in a charge exchange cell. The beam is mass-analysed at each stage. We have built a test apparatus consisting of an electron cyclotron resonance ion source and a pair of analysing magnets with a charge exchange cell in between, followed by an electrostatic analyser to improve the signal to background ratio. With this apparatus we have measured charge exchange probabilities for (C n+ → C - ) from 4.5 to 40.5 keV (n = 1-3). We have studied the sources of background including assessment of limits for nitrogen interference by searching for negative ions from charge exchange of 14 N ions. Our system has been used to detect 14 C in enriched samples of CO 2 gas with 14 C/ 12 C isotopic ratio down to the 10 -9 level. Combined with a measured sample consumption rate of 4 ng/s, this corresponds to a capability to detect transient signals containing only a few μBq of 14 C activity, such as may be obtained from chromatographic separation. The method will require further development to match the sensitivity of AMS with a gas ion source; however, even in its present state its sensitivity is well suited to tracer studies in biomedical research and drug development

  16. Cells exposed to a huntingtin fragment containing an expanded polyglutamine tract show no sign of ion channel formation: results arguing against the ion channel hypothesis

    DEFF Research Database (Denmark)

    Nørremølle, Anne; Grunnet, Morten; Hasholt, Lis

    2003-01-01

    Ion channels formed by expanded polyglutamine tracts have been proposed to play an important role in the pathological processes leading to neurodegeneration in Huntington's disease and other CAG repeat diseases. We tested the capacity of a huntingtin fragment containing an expanded polyglutamine...... in the currents recorded in any of the two expression systems, indicating no changes in ion channel activity. The results therefore argue against the proposed hypothesis of expanded polyglutamines forming ion channels....

  17. Studies of complex fragment emission in heavy ion reactions: Progress report, September 1, 1986 through August 31, 1987

    International Nuclear Information System (INIS)

    Sobotka, L.G.

    1987-01-01

    The production of large fragments, fragments with mass between light particles and fission fragments, in intermediate and high energy nuclear reactions has fostered the proposal of a number of novel reaction mechanisms. These include liquid-vapor equilibrium and nuclear shattering. Temporarily left in the wake of these exciting proposed mechanisms was the old standard, statistical decay of compound nuclei. To be sure, the standard treatment of compound nucleus decay did not deal with large fragment production. However, this omission was not due to any fundamental deficiency of statistical models, but rather an uncertainty concerning exactly how to splice large fragment emission into statistical models. A large portion of our program deals with this problem. Specifically, by studying the yields of large fragments produced in sufficiently low energy reactions we are attempting to deduce the asymmetry and l-wave dependence of large fragment emission from compound nuclear intermediates. This, however, is only half of the problem. Since the novel mechanisms proposed for large fragment emission were spawned by intermediate and high energy reaction data, we must also realize the relevance of the compound nucleus mechanisms at high energies. It is not unreasonable to suspect that compound nucleus-like objects are formed with less than complete momentum transfer and perhaps less than complete mass transfer. Therefore the study of large fragment production in low energy reactions should go hand in hand with the study of energy, mass, and angular momentum transfer in non-compound reactions. This thread joins the apparently divergent subjects covered in this report. 39 refs., 24 figs., 2 tabs

  18. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim

    2013-10-01

    Rationale Polycyclic aromatic sulfur heterocycles (PASHs) are detrimental species for refining processes in petroleum industry. Current mass spectrometric Methods that determine their composition are often preceded by derivatization and dopant addition approaches. Different ionization Methods have different impact on the molecular assignment of complex PASHs. The analysis of such species under atmospheric pressure chemical ionization (APCI) is still considered limited due to uncontrolled ion generation with low- and high-mass PASHs. Methods The ionization behavior of a model mixture of five selected PASH standards was investigated using an APCI source with nitrogen as the reagent gas. A complex thiophenic fraction was separated from a vacuum gas oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same ionization pattern was observed for the real thiophenic sample. It was found that S1 class species were the major sulfur-containing species found in the VGO sample. These species indicated the presence of alkylated benzothiophenic (BT), dibenzothiophenic (DBT) and benzonaphthothiophenic (BNT) series that were detected by APCI-FTICR MS. CONCLUSIONS This study provides an established APCI-FTICR MS method for the analysis of complex PASHs. PASHs were detected without using any derivatization and without fragmentation. The method can be used for the analysis of S-containing crude oil samples. © 2013 John Wiley & Sons, Ltd.

  19. Fragmentation and lateral scattering of 120 and 200 MeV/u {sup 4}He ions in water targets

    Energy Technology Data Exchange (ETDEWEB)

    Rovituso, Marta

    2016-06-02

    Along with an increased popularity of heavy ions in cancer therapy, {sup 4}He ions have regained the interest of the medical community as a compromise between protons and {sup 12}C ions. Although 2054 patients have been treated with {sup 4}He beams at Lawrence Berkeley Laboratory (LBL) (Berkeley CA, US) between 1975 and 1992, a comprehensive database of biological and physics measurements in the therapeutic energy range is still missing. One of the first steps necessary for introducing {sup 4}He ions in particle therapy, is the development of a dedicated treatment planning system, for which basic physics information such as the characterization of the beam lateral scattering and fragmentation cross sections describing the loss of primary particles and the build up of secondary fragments are required. Examination of data found in the literature reveals a gap in the therapeutic energy range. These measurements are essential for benchmarking not only the new model developed for the in-house treatment planning code TRiP98 (Treatment Planning for Particles), but also for already existing beam algorithms and for Monte Carlo codes like Geant4 and Fluka. The aim of this work is to provide fragmentation cross sections of {sup 4}He ions in the therapeutic energy range. The experimental data presented here were measured at Heidelberg Ion Beam Therapy Center (HIT) (Heidelberg, Germany) using 120 MeV/u and 200 MeV/u {sup 4}He beams. The attenuation of 200 MeV/u {sup 4}He beam in water was studied together with the build up of the secondary fragments produced by nuclear fragmentation processes. Target thicknesses between 1 and 25 cm H{sub 2}O were chosen to investigate nuclear fragmentation also beyond the maximum penetration depth of the {sup 4}He ions. The mixed radiation field produced by the interaction of 120 and 200 {sup 4}He ions with water targets (4.28 and 13.96 cm thick, respectively) has also been investigated in this work by measuring double differential cross

  20. Computational analyses of spectral trees from electrospray multi-stage mass spectrometry to aid metabolite identification.

    Science.gov (United States)

    Cao, Mingshu; Fraser, Karl; Rasmussen, Susanne

    2013-10-31

    Mass spectrometry coupled with chromatography has become the major technical platform in metabolomics. Aided by peak detection algorithms, the detected signals are characterized by mass-over-charge ratio (m/z) and retention time. Chemical identities often remain elusive for the majority of the signals. Multi-stage mass spectrometry based on electrospray ionization (ESI) allows collision-induced dissociation (CID) fragmentation of selected precursor ions. These fragment ions can assist in structural inference for metabolites of low molecular weight. Computational investigations of fragmentation spectra have increasingly received attention in metabolomics and various public databases house such data. We have developed an R package "iontree" that can capture, store and analyze MS2 and MS3 mass spectral data from high throughput metabolomics experiments. The package includes functions for ion tree construction, an algorithm (distMS2) for MS2 spectral comparison, and tools for building platform-independent ion tree (MS2/MS3) libraries. We have demonstrated the utilization of the package for the systematic analysis and annotation of fragmentation spectra collected in various metabolomics platforms, including direct infusion mass spectrometry, and liquid chromatography coupled with either low resolution or high resolution mass spectrometry. Assisted by the developed computational tools, we have demonstrated that spectral trees can provide informative evidence complementary to retention time and accurate mass to aid with annotating unknown peaks. These experimental spectral trees once subjected to a quality control process, can be used for querying public MS2 databases or de novo interpretation. The putatively annotated spectral trees can be readily incorporated into reference libraries for routine identification of metabolites.

  1. Fragmentation Pathways of Lithiated Hexose Monosaccharides

    Science.gov (United States)

    Abutokaikah, Maha T.; Frye, Joseph W.; Tschampel, John; Rabus, Jordan M.; Bythell, Benjamin J.

    2018-05-01

    We characterize the primary fragmentation reactions of three isomeric lithiated D-hexose sugars (glucose, galactose, and mannose) utilizing tandem mass spectrometry, regiospecific labeling, and theory. We provide evidence that these three isomers populate similar fragmentation pathways to produce the abundant cross-ring cleavage peaks (0,2A1 and 0,3A1). These pathways are highly consistent with the prior literature (Hofmeister et al. J. Am. Chem. Soc. 113, 5964-5970, 1991, Bythell et al. J. Am. Soc. Mass Spectrom. 28, 688-703, 2017, Rabus et al. Phys. Chem. Chem. Phys. 19, 25643-25652, 2017) and the present labeling data. However, the structure-specific energetics and rate-determining steps of these reactions differ as a function of precursor sugar and anomeric configuration. The lowest energy water loss pathways involve loss of the anomeric oxygen to furnish B1 ions. For glucose and galactose, the lithiated α-anomers generate ketone structures at C2 in a concerted reaction involving a 1,2-migration of the C2-H to the anomeric carbon (C1). In contrast, the β-anomers are predicted to form 1,3-anhydroglucose/galactose B1 ion structures. Initiation of the water loss reactions from each anomeric configuration requires distinct reactive conformers, resulting in different product ion structures. Inversion of the stereochemistry at C2 has marked consequences. Both lithiated mannose forms expel water to form 1,2-anhydromannose B1 ions with the newly formed epoxide group above the ring. Additionally, provided water loss is not instantaneous, the α-anomer can also isomerize to generate a ketone structure at C2 in a concerted reaction involving a 1,2-migration of the C2-H to C1. This product is indistinguishable to that from α-glucose. The energetics and interplay of these pathways are discussed. [Figure not available: see fulltext.

  2. Gas-phase ion-molecule reactions and high-pressure mass spectrometer, 1

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo

    1977-01-01

    The reasons for the fact that the research in gas-phase ion-molecule reactions, to which wide interest is shown, have greatly contributed to the physical and chemical fields are that, first it is essential in understanding general phenomena concerning ions, second, it can furnish many unique informations in the dynamics of chemical reactions, and third, usefulness of '' chemical ionization'' methods has been established as its application to chemical analysis. In this review, the history and trend of studies and equipments in gas-phase ion-molecule reactions are surveyed. The survey includes the chemical ionization mass spectrometer for simultaneously measuring the positive and negative ions utilizing a quadrupole mass spectrometer presented by Hunt and others, flowing afterglow method derived from the flowing method which traces neutral chemical species mainly optically, ion cyclotron resonance mass spectrometer, trapped ion mass spectrometer and others. Number of reports referred to ion-molecule reactions issued during the last one year well exceeds the total number of reports concerning mass spectrometers presented before 1955. This truly shows how active the research and development are in this field. (Wakatsuki, Y.)

  3. Search for ternary fragmentation in the reaction 856 MeV 98Mo + 51V: Kinematic probing of intermediate-mass-fragment emissions

    International Nuclear Information System (INIS)

    Vardaci, Emanuele; Kaplan, Morton; Parker, Winifred E.; Moses, David J.; Boger, J.T.; Gilfoyle, G.T.; McMahan, M.A.; Montoya, M.

    2000-05-01

    A new technique has been applied to coincidence measurements between fission fragments (FF) and intermediate mass fragments (IMF) emitted from the composite system 149 65 Tb at an excitation energy of 224 MeV. The method permits simultaneous observation of IMF emissions along and normal to the FF separation axes. For the integrated total of 0.10 +-0.02 IMF emitted per fission, we find no significant correlation with FF direction, suggesting that IMFs associated with fission reactions are predominantly emitted from the system prior to fission

  4. An ion cooling and state characterization apparatus for studies of molecular ion dissociative interactions

    International Nuclear Information System (INIS)

    Deng, Shihu; Vane, C R; Bannister, M E; Havener, C C; Meyer, F W; Krause, H F; Hettich, R L; Goeringer, D E; Van Berkel, G J

    2009-01-01

    An experimental capability is being developed at the Oak Ridge National Laboratory Multi-Charged Ion Research Facility (ORNL MIRF) to enable stored cooling and state characterization of molecular ions of essentially any mass. Ions selected from a variety of available sources are injected from the side into a 1.5 meter long electrostatic mirror trap, where excited internal states are cooled by radiative cooling. An electron beam target located near the middle of the ion-trap region, coupled with neutral fragment imaging detector systems at each end of the trap, permits state-specific studies of electron-molecular ion dissociation.

  5. Procedure and apparatus for controlling the ion energy in a mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Fies, W J; Reeher, J R; Story, M S; Smith, R D

    1977-03-03

    The invention relates to a process and apparatus for adjusting the energy of ions of different masses in a mass spectrometer. Specifically, it concerns a mass spectrometer having a gas inlet and ionisation space. A multipole mass filter includes several electrodes. A focusing system connects the ionisation space and the mass filter. Provision is made for applying to the electrodes a mass adjusting voltage combining a high frequency voltage and a d.c. voltage of increasing amplitude, so that the ions of a pre-determined mass can be selected. This system also includes a device connected to the electrodes, sensitive to the mass adjusting voltage and enabling the energy of the ions to be adjusted to that of the selected ions, depending on the mass of the ions, by modifying the difference in potential between the ionisation volume and the mean potential of the electrodes .

  6. A compact time-of-flight mass spectrometer for ion source characterization

    International Nuclear Information System (INIS)

    Chen, L.; Wan, X.; Jin, D. Z.; Tan, X. H.; Huang, Z. X.; Tan, G. B.

    2015-01-01

    A compact time-of-flight mass spectrometer with overall dimension of about 413 × 250 × 414 mm based on orthogonal injection and angle reflection has been developed for ion source characterization. Configuration and principle of the time-of-flight mass spectrometer are introduced in this paper. The mass resolution is optimized to be about 1690 (FWHM), and the ion energy detection range is tested to be between about 3 and 163 eV with the help of electron impact ion source. High mass resolution and compact configuration make this spectrometer useful to provide a valuable diagnostic for ion spectra fundamental research and study the mass to charge composition of plasma with wide range of parameters

  7. Characterization of cationic glycoporphyrins by electrospray tandem mass spectrometry.

    Science.gov (United States)

    Silva, Eduarda M P; Serra, Vanda Vaz; Ribeiro, Anderson O; Tomé, João P C; Domingues, Pedro; Faustino, M Amparo F; Neves, M Graça P M S; Tomé, Augusto C; Cavaleiro, José A S; Ferrer-Correia, António J; Iamamoto, Yassuko; Domingues, M Rosário M

    2006-01-01

    Novel cationic porphyrin derivatives having a galactose or a bis(isopropylidene)galactose unit linked directly to a pyridine or to an aminophenyl group were characterized by electrospray tandem mass spectrometry (ESI-MS/MS). The electrospray mass spectra (ESI-MS) show the M(+) ions, since these porphyrins are already monocharged in solution. The fragmentation of these ions under ESI-MS/MS conditions was studied and it was found that elimination of the sugar residue as a radical (-163 or -243 Da) is a common fragmentation pathway. Loss of the sugar unit as a neutral fragment (-162 or -242 Da) and cross-ring fragmentations typical of glyco-derivatives are also observed for the pyridinium glycoporphyrins, but they are absent in the case of ammonium glycoporphyrins. The cationic beta-pyridiniumvinyl porphyrins show an atypical fragmentation due to the cleavage of the C(5)-C(6) bond of the sugar unit. Overall, the different patterns of fragmentation observed in the ESI-MS/MS spectra of the sugar pyridinium porphyrins and of the sugar ammonium phenyl porphyrins can give important information about the type of spacer between the porphyrin and the sugar unit. Copyright (c) 2006 John Wiley & Sons, Ltd.

  8. Characterization of nitrated sugar alcohols by atmospheric-pressure chemical-ionization mass spectrometry.

    Science.gov (United States)

    Ostrinskaya, Alla; Kelley, Jude A; Kunz, Roderick R

    2017-02-28

    The nitrated sugar alcohols mannitol hexanitrate (MHN), sorbitol hexanitrate (SHN) and xylitol pentanitrate (XPN) are in the same class of compounds as the powerful military-grade explosive pentaerythritol tetranitrate (PETN) and the homemade explosive erythritol tetranitrate (ETN) but, unlike for PETN and ETN, ways to detect MHN, SHN and XPN by mass spectrometry (MS) have not been fully investigated. Atmospheric-pressure chemical-ionization mass spectrometry (APCI-MS) was used to detect ions characteristic of nitrated sugar alcohols. APCI time-of-flight mass spectrometry (APCI-TOF MS) and collision-induced dissociation tandem mass spectrometry (CID MS/MS) were used for confirmation of each ion assignment. In addition, the use of the chemical ionization reagent dichloromethane was investigated to improve sensitivity and selectivity for detection of MHN, SHN and XPN. All the nitrated sugar alcohols studied followed similar fragmentation pathways in the APCI source. MHN, SHN and XPN were detectable as fragment ions formed by the loss of NO 2 , HNO 2 , NO 3 , and CH 2 NO 2 groups, and in the presence of dichloromethane chlorinated adduct ions were observed. It was determined that in MS/MS mode, chlorinated adducts of MHN and SHN had the lowest limits of detection (LODs), while for XPN the lowest LOD was for the [XPN-NO 2 ] - fragment ion. Partially nitrated analogs of each of the three compounds were also present in the starting materials, and ions attributable to these compounds versus those formed from in-source fragmentation of MHN, SHN, and XPN were distinguished and assigned using liquid chromatography APCI-MS and ESI-MS. The APCI-MS technique provides a selective and sensitive method for the detection of nitrated sugar alcohols. The methods disclosed here will benefit the area of explosives trace detection for counterterrorism and forensics. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  9. Comparison of secondary ion emission induced in silicon oxide by MeV and KeV ion bombardment

    International Nuclear Information System (INIS)

    Allali, H.; Nsouli, B.; Thomas, J.P.; Szymczak, W.; Wittmaack, K.

    1993-09-01

    The surface and near-surface composition of SiO 2 layers, has been investigated by negative secondary ion emission mass spectrometry (SIMS) using MeV and KeV ion bombardment in combination with time-of-flight (TOF) mass analysis. The spectra recorded in the mass range 0-100 u are dominated by surface impurities, notably hydrocarbons and silicon polyanions incorporating H and OH entities. The characteristic (fragmentation) patterns are quite different for light and high-velocity ion impact. In high-velocity TOF-SIMS analysis of P-doped layers, prepared by chemical vapour deposition (CVD), the mass lines at 63 and 79 u are very prominent and appear to correlate with the phosphorus concentration (PO 2 and PO 3 , respectively). It is shown, however, that for unambiguous P analysis one has to use dynamic SIMS or high mass resolution. (author) 11 refs., 5 figs

  10. Dynamic Secondary Ion Mass Spectrometry | Materials Science | NREL

    Science.gov (United States)

    Ion Mass Spectrometry (SIMS) uses a continuous, focused beam of primary ions to remove material from the surface of a sample by sputtering. The fraction of sputtered material that is ionized is extracted Identifies all elements or isotopes present in a material, from hydrogen to uranium. Different primary-ion

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

    Science.gov (United States)

    Rannulu, Nalaka S.; Cole, Richard B.

    2012-09-01

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

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

    NARCIS (Netherlands)

    Lou, X.; Li, B.; de Waal, B.F.M.; Schill, J.; Baker, M.B.; Bovee, R.A.A.; van Dongen, J.L.J.; Milroy, L.G.; 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

  13. Mass Spectrometric Study of Some Fluoroquinolone Drugs Using Electron Ionization and Chemical Ionization Techniques in Combination With Semi-Empirical Calculations

    International Nuclear Information System (INIS)

    Abd EL Kareem, M.S.M.

    2013-01-01

    A mass spectrometer of the type QMS (SSQ710) is used to record the electron ionization mass spectra of some 6-fluoroquinolones molecules, namely: Norfloxacin, Pefloxacin, Ciprofloxacin and Levofloxacin.While the chemical ionization mass spectra of these compounds are recorded using Thermo Finnigan TRACE DSQ GC/MS system.In EI mass spectra, the relative intensities for the molecular ions [M] +. of the studied compounds and the prominent fragment ions are reported and discussed. Furthermore, fragmentation patterns for the four compounds have been suggested and discussed and the most important fragmentation processes such as [M-CO 2 ] +. , [M-C 2 H 4 N] + and [M-CO 2 -C 2 H 4 N] + are investigated.On the other hand, the chemical ionization (CI) mass spectra of the compounds have been recorded using methane as the reagent gas. These spectra are discussed in terms of the structure of the compounds, with particular reference to their conventional electron ionization mass spectra. The protonated molecules [M + H] + are more relatively intense than [M] +. ions in the recorded EI mass spectra indicating higher stability in the case of [M + H] + .Also, fragmentation patterns for the four compounds have been suggested and discussed (using chemical ionization technique) and the most important fragmentation processes such as [MH-CO 2 ] +. , [MH-C 2 H 4 N] + and [MH-H 2 O] + are investigated.

  14. Monte Carlo simulation for fragment mass and kinetic energy distributions from the neutron-induced fission of {sup 235}U

    Energy Technology Data Exchange (ETDEWEB)

    Montoya, M.; Rojas, J. [Instituto Peruano de Energia Nuclear, Av. Canada 1470, Lima 41 (Peru); Saettone, E. [Facultad de Ciencias, Universidad Nacional de lngenieria, Av. Tupac Amaru 210, Apartado 31-139, Lima (Peru)

    2007-07-01

    The mass and kinetic energy distribution of nuclear fragments from the thermal neutron-induced fission of {sup 235}U have been studied using a Monte Carlo simulation. Besides reproducing the pronounced broadening on the standard deviation of the final fragment kinetic energy distribution ({sigma}{sub e}(m)) around the mass number m = 109, our simulation also produces a second broadening around m = 125 that is in agreement with the experimental data obtained by Belhafaf et al. These results are a consequence of the characteristics of the neutron emission, the variation in the primary fragment mean kinetic energy, and the yield as a function of the mass. (Author)

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

    Science.gov (United States)

    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.

  16. Effect of ion and ion-beam mass ratio on the formation of ion-acoustic solitons in magnetized plasma in the presence of electron inertia

    International Nuclear Information System (INIS)

    Kalita, B. C.; Barman, S. N.

    2009-01-01

    The propagation of ion-acoustic solitary waves in magnetized plasma with cold ions and ion-beams together with electron inertia has been investigated theoretically through the Korteweg-de Vries equation. Subject to the drift velocity of the ion beam, the existence of compressive solitons is found to become extinct as α (=cold ion mass/ion-beam mass) tends to 0.01 when γ=0.985 (γ is the beam velocity/phase velocity). Interestingly, a transitional direction of propagation of solitary waves has been unearthed for change over, from compressive solitons to rarefactive solitons based on α and σ υ (=cosine of the angle θ made by the wave propagation direction ξ with the direction of the magnetic field) for fixed Q(=electron mass/ion mass). Further, the direction of propagation of ion-acoustic waves is found to be the deterministic factor to admit compressive or rarefactive solitons subject to beam outsource.

  17. Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams.

    Science.gov (United States)

    Shon, Hyun Kyong; Yoon, Sohee; Moon, Jeong Hee; Lee, Tae Geol

    2016-06-09

    The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration.

  18. Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic-ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Schmarr, Hans-Georg [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)], E-mail: hans-georg.schmarr@dlr.rlp.de; Potouridis, Theodoros; Ganss, Sebastian; Sang, Wei; Koepp, Benedikt; Bokuz, Ursula; Fischer, Ulrich [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)

    2008-06-09

    An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC-ITMS). Selecting specific fragment ions within the electron ionization (EI{sup +}) mass spectra of these oxime derivatives as precursor ions for MS-MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, (E)-2-alkenals, (E,E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI{sup +} mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.

  19. Ion beam properties after mass filtering with a linear radiofrequency quadrupole

    International Nuclear Information System (INIS)

    Ferrer, R.; Kwiatkowski, A.A.; Bollen, G.; Lincoln, D.L.; Morrissey, D.J.; Pang, G.K.; Ringle, R.; Savory, J.; Schwarz, S.

    2014-01-01

    The properties of ion beams passing through a linear radiofrequency quadrupole mass filter were investigated with special attention to their dependence on the mass resolving power. Experimentally, an increase of the transverse emittance was observed as the mass-to-charge selectivity of the mass filter was raised. The experimental behavior was confirmed by beam transport simulations. -- Highlights: • The ion-optical properties of a Quadrupole Mass Filter (QMF) are presented. • Measured beam emittances follow a trend to larger values for smaller A/Q ratios and increasing mass resolution. • The experimental behavior was confirmed by beam transport simulations. • The use of a QMF for mass filtering comes at the cost of emittance growth of the ion beam

  20. Fast atom bombardment tandem mass spectrometry of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    van Breeman, R.B. [Univ. of Illinois, Chicago, IL (United States); Schmitz, H.H.; Schwartz, S.J. [North Carolina State Univ., Raleigh, NC (United States)

    1995-02-01

    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 carotenes 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.

  1. IN SITU PLASMA MEASUREMENTS OF FRAGMENTED COMET 73P SCHWASSMANN–WACHMANN 3

    International Nuclear Information System (INIS)

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

    2015-01-01

    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

  2. In Situ Plasma Measurements of Fragmented Comet 73P Schwassmann-Wachmann 3

    Science.gov (United States)

    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.

  3. IN SITU PLASMA MEASUREMENTS OF FRAGMENTED COMET 73P SCHWASSMANN–WACHMANN 3

    Energy Technology Data Exchange (ETDEWEB)

    Gilbert, J. A.; Lepri, S. T.; Combi, M.; Zurbuchen, T. H. [University of Michigan, Ann Arbor, MI 48109 (United States); Rubin, M., E-mail: jagi@umich.edu [Universität Bern, Bern (Switzerland)

    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 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{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.

  4. Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

    Science.gov (United States)

    Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

    2006-02-01

    Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

  5. Microscope mode secondary ion mass spectrometry imaging with a Timepix detector.

    NARCIS (Netherlands)

    Kiss, A.; Jungmann, JH; Smith, D.F.; Heeren, R.M.A.

    2013-01-01

    In-vacuum active pixel detectors enable high sensitivity, highly parallel time- and space-resolved detection of ions from complex surfaces. For the first time, a Timepix detector assembly was combined with a secondary ion mass spectrometer for microscope mode secondary ion mass spectrometry (SIMS)

  6. [Screening and confirmation of 24 hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    Science.gov (United States)

    Li, Zhaoyong; Wang, Fengmei; Niu, Zengyuan; Luo, Xin; Zhang, Gang; Chen, Junhui

    2014-05-01

    A method of ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was established to screen and confirm 24 hormones in cosmetics. Various cosmetic samples were extracted with methanol. The extract was loaded onto a Waters ACQUITY UPLC BEH C18 column (50 mm x 2.1 mm, 1.7 microm) using a gradient elution of acetonitrile/water containing 0.1% (v/v) formic acid for the separation. The accurate mass of quasi-molecular ion was acquired by full scanning of electrostatic field orbitrap. The rapid screening was carried out by the accurate mass of quasi-molecular ion. The confirmation analysis for targeted compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode. Under the optimal conditions, the 24 hormones were routinely detected with mass accuracy error below 3 x 10(-6) (3 ppm), and good linearities were obtained in their respective linear ranges with correlation coefficients higher than 0.99. The LODs (S/N = 3) of the 24 compounds were hormones in 50 cosmetic samples. The results demonstrate that the method is a useful tool for the rapid screening and identification of the hormones in cosmetics.

  7. Formation and fragmentation of radical peptide anions: insights from vacuum ultra violet spectroscopy.

    Science.gov (United States)

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2012-02-01

    We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS(3) scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M-2H](2-)) non-radical ions and open-shell ([M-3H](2-•)) radical ions. These latter ions are generated by electron photodetachment from [M-3H](3-) precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides. © American Society for Mass Spectrometry, 2011

  8. Fragmentation Pathways of Trifluoroacetyl Derivatives of Methamphetamine, Amphetamine, and Methylenedioxyphenylalkylamine Designer Drugs by Gas Chromatography/Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Takeshi Kumazawa

    2011-01-01

    Full Text Available Methamphetamine (MA, amphetamine (AM, and the methylenedioxyphenylalkylamine designer drugs, such as 3,4-methylenedioxymethamphetamine (MDMA, 3,4-methylenedioxyethylamphetamine (MDEA, N-methyl-1-(3,4-methylenedioxyphenyl-2-butanamine (MBDB, 3,4-methylenedioxyamphetamine (MDA, and 3,4-(methylenedioxyphenyl-2-butanamine (BDB, are widely abused as psychedelics. In this paper, these compounds were derivatized with trifluoroacetic (TFA anhydride and analyzed by gas chromatography/mass spectrometry using electron ionization in positive mode. Gas chromatographic separation for TFA derivatives of all compounds was successfully resolved using an Equity-5 fused silica capillary column with a poly (5% diphenyl-95% dimethylsiloxane stationary phase. Base peaks or prominent peaks of MA, AM, MDMA, MDEA, MBDB, MDA, and BDB appeared at m/z 154, 140, 154, 168, 168, 135, and 135, respectively. These occurred due to α-cleavage from the amide nitrogen, splitting into the TFA imine species and benzyl or methylenedioxybenzyl cations. Further prominent fragment ions at m/z 118 for MA and AM, m/z 162 for MDMA, MDEA, and MDA, and m/z 176 for MBDB and BDB were produced by cleavage of the phenylpropane or methylenedioxypropane hydrocarbon radical cation via a hydrogen rearrangement. These fragmentation pathways for the TFA derivatives of all the compounds are summarized and illustrated in this paper.

  9. Macroscopic model description of heavy-ion induced complex-fragment emission

    International Nuclear Information System (INIS)

    Carjan, N.

    1988-01-01

    The Yukawa-plus-exponential finite-range model and the standard liquid-drop model are shortly reviewed and compared. The dependence of the barrier heights and of the saddle-point shapes on mass-asymmetry and on angular momentum is studied for the compound nuclei 110 Sn, 149 Tb and 194 Hg. The predicted asymmetric-fission barriers, charge yields and total kinetic energies are compared with experimental data obtained from the deexcitation of compound nuclei by complex-fragment emission

  10. Online quench-flow electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for elucidating kinetic and chemical enzymatic reaction mechanisms.

    Science.gov (United States)

    Clarke, David J; Stokes, Adam A; Langridge-Smith, Pat; Mackay, C Logan

    2010-03-01

    We have developed an automated quench-flow microreactor which interfaces directly to an electrospray ionization (ESI) mass spectrometer. We have used this device in conjunction with ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to demonstrate the potential of this approach for studying the mechanistic details of enzyme reactions. For the model system chosen to test this device, namely, the pre-steady-state hydrolysis of p-nitrophenyl acetate by the enzyme chymotrypsin, the kinetic parameters obtained are in good agreement with those in the literature. To our knowledge, this is the first reported use of online quench-flow coupled with FTICR MS. Furthermore, we have exploited the power of FTICR MS to interrogate the quenched covalently bound enzyme intermediate using top-down fragmentation. The accurate mass capabilities of FTICR MS permitted the nature of the intermediate to be assigned with high confidence. Electron capture dissociation (ECD) fragmentation allowed us to locate the intermediate to a five amino acid section of the protein--which includes the known catalytic residue, Ser(195). This experimental approach, which uniquely can provide both kinetic and chemical details of enzyme mechanisms, is a potentially powerful tool for studies of enzyme catalysis.

  11. Action spectroscopy of SrCl{sup +} using an integrated ion trap time-of-flight mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Puri, Prateek, E-mail: teek24@ucla.edu; Schowalter, Steven J.; Hudson, Eric R. [Department of Physics and Astronomy, University of California, Los Angeles, California 90095 (United States); Kotochigova, Svetlana; Petrov, Alexander [Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States)

    2014-07-07

    The photodissociation cross-section of SrCl{sup +} is measured in the spectral range of 36 000–46 000 cm{sup −1} using a modular time-of-flight mass spectrometer (TOF-MS). By irradiating a sample of trapped SrCl{sup +} molecular ions with a pulsed dye laser, X{sup 1}Σ{sup +} state molecular ions are electronically excited to the repulsive wall of the A{sup 1}Π state, resulting in dissociation. Using the TOF-MS, the product fragments are detected and the photodissociation cross-section is determined for a broad range of photon energies. Detailed ab initio calculations of the SrCl{sup +} molecular potentials and spectroscopic constants are also performed and are found to be in good agreement with experiment. The spectroscopic constants for SrCl{sup +} are also compared to those of another alkaline earth halogen, BaCl{sup +}, in order to highlight structural differences between the two molecular ions. This work represents the first spectroscopy and ab initio calculations of SrCl{sup +}.

  12. Asymmetric fission and evaporation of C{sub 60}{sup r+} (r = 2-4) fullerene ions in ion-C{sub 60} collisions: I. Proton results

    Energy Technology Data Exchange (ETDEWEB)

    Rentenier, A; Bordenave-Montesquieu, A; Moretto-Capelle, P; Bordenave-Montesquieu, D [LCAR-IRSAMC, UMR 5589 Universite Paul Sabatier-CNRS, 118 rte de Narbonne, 31062 Toulouse Cedex (France)

    2004-06-28

    A quantitative description of the asymmetric fission (AF) of C{sub 60}{sup r+} fullerene ions (r = 2-4), using a multistop coincidence technique between both fragment ions, is presented. Charged light fragment (LF) and heavy fragment (HF) size distributions are discussed together with the corresponding averaged sizes. Complete AF distributions are reported for the first time for C{sub 60}{sup 2+} ions. Simple dependences of the more probable channels and averaged fragment sizes on the partner size are found and discussed. The LF ones are not very sensitive to the parent fullerene ion charge r and vary linearly with the HF size at least for the largest ones. On the other hand the HF ones present an oscillating dependence against the LF size, the odd-numbered LFs being correlated to a smaller HF size, and depend on r. In the comparison of branching ratios between AF and the competing pure neutral evaporation channel, some emphasis is given to the behaviour of the unimolecular processes with r which are compared with the evolution of the activation energies and fission barriers. From a close examination of the individual HF distributions the production mechanisms of odd-n fragments are discussed, and the most probable dissociation channels of even-numbered C{sub n}{sup +} excited carbon clusters identified. Finally, an analysis of the neutral channels is also presented for the first time, the total neutral mass N (in carbon units) being deduced from the mass conservation law. Surprising similarities between the charged LF- and N-distributions are found. AF processes are also identified where light neutrals and ions play a symmetrical role. These findings lead us to suggest that a concerted emission of ions and heavy neutrals is probably a fission mechanism to be considered to understand the AF process of the C{sub 60} molecule in addition to the often assumed multistep fragmentation cascade scheme.

  13. Studies of complex fragment emission in heavy ion reactions

    International Nuclear Information System (INIS)

    Charity, R.J.; Sobotka, L.G.

    1992-01-01

    Our work involves the study of intermediate energy heavy-ion nuclear reactions. This work has two foci. On the one hand, we desire to learn about the properties of nuclear matter under abnormal conditions, in this energy domain, predominately low densities. This purpose runs abreast of the second, which is the study of the relevant reaction mechanisms. The two objectives are inexorably linked because our experimental laboratory for studying nuclear matter properties is a dynamic one. We are forced to ask how nuclear matter properties, such as phase transitions, are reflected in the dynamics of the reactions. It may be that irrefutable information about nuclear matter will not be extracted from the reaction work. Nevertheless, we are compelled to undertake this effort not only because it is the only game in town and as yet we do not know that information cannot be extracted, but also because of our second objective. The process leads to an understanding of the reaction mechanism themselves and therefore to the response characteristics of finite, perhaps non-equilibrium, strongly interacting systems. Our program has been: To study energy, mass, and angular momentum deposition by studying incomplete fusion reactions. To gain confidence that we understand how highly excited systems decompose by studying all emissions from the highly excited systems. To push these kinds of studies into the intermediate energy domain, with excitation function studies. And attempt to learn about the dynamics of the decays using particle-particle correlations. In the last effort, we have decided to focus on simple systems, where we believe, definitive statements are possible. These avenues of research share a common theme, large complex fragment production

  14. Fission fragment mass distribution in the 13C+182W and 176Yb reactions

    International Nuclear Information System (INIS)

    Ramachandran, K.; Hinde, D.J.; Dasgupta, M.; Williams, E.; Wakhle, A.; Luong, D.H.; Evers, M.; Carter, I.P.; Das, S.

    2014-01-01

    Fission fragment mass distributions have been measured for many systems and found to be asymmetric in the fission of nuclei with nucleon number A in the range 228-258 and proton number Z in the range 90-100. For lighter systems, it has been observed that fission fragment mass distributions are usually symmetric. At high excitation energies the shell effects are expected to vanish and the nuclei are expected to behave like a charged liquid drop; hence, only symmetric fission is expected for all the nuclei. Even after much experimental and theoretical work in this field, the rate of damping of shell effects with excitation energy is not well known. This abstract reports our measurements with 13 C beams on 182 W and 176 Yb targets

  15. Proton Transfer Time-of-Flight Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Watson, Thomas B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2016-03-01

    The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H3O+), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-charge ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.

  16. Implementation of dipolar direct current (DDC) collision-induced dissociation in storage and transmission modes on a quadrupole/time-of-flight tandem mass spectrometer.

    Science.gov (United States)

    Webb, Ian K; Londry, Frank A; McLuckey, Scott A

    2011-09-15

    Means for effecting dipolar direct current collision-induced dissociation (DDC CID) on a quadrupole/time-of-flight in a mass spectrometer have been implemented for the broadband dissociation of a wide range of analyte ions. The DDC fragmentation method in electrodynamic storage and transmission devices provides a means for inducing fragmentation of ions over a large mass-to-charge range simultaneously. It can be effected within an ion storage step in a quadrupole collision cell that is operated as a linear ion trap or as ions are continuously transmitted through the collision cell. A DDC potential is applied across one pair of rods in the quadrupole collision cell of a QqTOF hybrid mass spectrometer to effect fragmentation. In this study, ions derived from a small drug molecule, a model peptide, a small protein, and an oligonucleotide were subjected to the DDC CID method in either an ion trapping or an ion transmission mode (or both). Several key experimental parameters that affect DDC CID results, such as time, voltage, low mass cutoff, and bath gas pressure, are illustrated with protonated leucine enkephalin. The DDC CID dissociation method gives a readily tunable, broadband tool for probing the primary structures of a wide range of analyte ions. The method provides an alternative to the narrow resonance conditions of conventional ion trap CID and it can access more extensive sequential fragmentation, depending upon conditions. The DDC CID approach constitutes a collision analog to infrared multiphoton dissociation (IRMPD). Copyright © 2011 John Wiley & Sons, Ltd.

  17. Ion beam alignment in the MSX-4 mass spectrometer

    International Nuclear Information System (INIS)

    Busygin, A.I.; Nevzorov, A.A.; Ul'masbaev, B.Sh.

    1977-01-01

    A method for electrically adjusting an ion beam in an MSKh-4 mass-spectrometer has been developed. The adjusting system consists of two deflecting plates fastened to the frame of the ion source. By adjusting the potential difference at the plates in the range 0-150 v, one can increase the intensity of the mass-spectrum by a factor of 3 to 5

  18. Light fragment formation at intermediate energies

    International Nuclear Information System (INIS)

    Boal, D.H.

    1982-03-01

    This paper concerns itself mainly with the production of energetic protons and light fragments at wide angles. The experiments point to nucleon emission in proton-induced reactions as involving a mechanism in which the observed nucleon is directly knocked out of the nucleus. A similar feature seems to be required to explain (p,F) and (e,F) reactions: an energetic nucleon is produced in one scattering of the projectile, and the struck nucleon subsequently loses some of its energy as it traverses the remaining part of the nucleus, gathering up other nucleons as it goes, to become a fragment. This is what one might call the extreme snowball model, and a more accurate description probably involves multiple scattering of the projectile in addition to the extreme snowball contribution. This will be particularly true for fragments in the mass 6 to 9 region. This scenario also appears to apply to deuteron-induced fragment production. However, for alpha-induced reactions it would appear that the nucleons forming a fragment can originate from collisions involving different incident nucleons in the projectile. For heavy ions, this effect is even stronger, and the snowball contribution is greatly reduced compared to that of the traditional coalescence model

  19. Application of ion mobility-mass spectrometry to microRNA analysis.

    Science.gov (United States)

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

    2013-03-01

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

  20. Simulation of a relativistic heavy ions beam transport in the matter: contribution of the fragmentation process and biological implications; Simulation du transport d`un faisceau d`ions lourds relativistes dans la matiere: contribution du processus de fragmentation et implication sur le plan biologique

    Energy Technology Data Exchange (ETDEWEB)

    Ibnouzahir, M

    1995-03-01

    The study of relativistic heavy ion collisions permit an approach of the properties of dense and not hadronic matter, and an analysis of the reaction mechanisms. Such studies are also interesting on the biological point of view, since there exist now well defined projects concerning the radiotherapy with high LET particles as neutrons, protons, heavy ions. It is thus necessary to have a good understanding of the processes which occur in the propagation of a relativistic heavy ion beam (E{>=} 100 A.MeV) in matter. We have elaborated a three dimensional transport code, using a Monte Carlo method, in order to describe the propagation of Ne and Ar ions in water. Violent nuclear collisions giving fragmentation process have been taken into account by use of the FREESCO program. We have tested the validity of our transport model and we show an important change of the energy deposition at the vicinity of the Bragg peak; such a distortion, due mainly to fragmentation reactions, is of a great interest for biological applications. (author).

  1. Combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for qualitative analysis of drugs.

    Science.gov (United States)

    Pavlic, Marion; Libiseller, Kathrin; Oberacher, Herbert

    2006-09-01

    The potential of the combined use of ESI-QqTOF-MS and ESI-QqTOF-MS/MS with mass-spectral library search for the identification of therapeutic and illicit drugs has been evaluated. Reserpine was used for standardizing experimental conditions and for characterization of the performance of the applied mass spectrometric system. Experiments revealed that because of the mass accuracy, the stability of calibration, and the reproducibility of fragmentation, the QqTOF mass spectrometer is an appropriate platform for establishment of a tandem-mass-spectral library. Three-hundred and nineteen substances were used as reference samples to build the spectral library. For each reference compound, product-ion spectra were acquired at ten different collision-energy values between 5 eV and 50 eV. For identification of unknown compounds, a library search algorithm was developed. The closeness of matching between a measured product-ion spectrum and a spectrum stored in the library was characterized by a value called "match probability", which took into account the number of matched fragment ions, the number of fragment ions observed in the two spectra, and the sum of the intensity differences calculated for matching fragments. A large value for the match probability indicated a close match between the measured and the reference spectrum. A unique feature of the library search algorithm-an implemented spectral purification option-enables characterization of multi-contributor fragment-ion spectra. With the aid of this software feature, substances comprising only 1.0% of the total amount of binary mixtures were unequivocally assigned, in addition to the isobaric main contributors. The spectral library was successfully applied to the characterization of 39 forensic casework samples.

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

    Science.gov (United States)

    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.

  3. Centrifugal Fragmentation of a Dinuclear System in the Process of Its Evolution to the Compound Nucleus

    CERN Document Server

    Volkov, V V

    2005-01-01

    The physical content of centrifugal fragmentation is discussed. It is a specific nuclear process which is realized in the evolution of a dinuclear system into a compound nucleus at large angular momenta and large mass asymmetry of the system. The dinuclear system concept which describes the process of the compound nucleus formation in heavy ion reactions predicts the possibility of centrifugal fragmentation. Experimental data giving evidence of the realization of this nuclear process are given. A possible scheme of the centrifugal fragmentation model is discussed.

  4. Centrifugal fragmentation of a dinuclear system in the process of its evolution to the compound nucleus

    International Nuclear Information System (INIS)

    Volkov, V.V.

    2005-01-01

    The physical content of centrifugal fragmentation is discussed. It is a specific nuclear process which is realized in the evolution of a dinuclear system into a compound nucleus at large angular momenta and large mass asymmetry of the system. The dinuclear system concept which describes the process of the compound nucleus formation in heavy ion reactions predicts the possibility of centrifugal fragmentation. Experimental data giving evidence of the realization of this nuclear process are given. A possible scheme of the centrifugal fragmentation model is discussed

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

    Science.gov (United States)

    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.

  6. Hyperthermal surface ionization mass spectrometry of organic molecules: monoterpenes

    International Nuclear Information System (INIS)

    Kishi, Hiroshi; Fujii, Toshihiro.

    1997-01-01

    This paper describes an experimental study on the influence of kinetic energy of fast monoterpene molecules on the surface ionization efficiency and on the mass spectral patterns, using rhenium oxide (ReO 2 ) surface. Molecular kinetic energy, given to the molecules through the acceleration in the seeded supersonic molecular beam, ranged from 1 to 10 eV. Hyperthermal surface ionization mass spectra (HSIMS) were taken for various incident kinetic energies and surface temperatures. The observed mass spectra were interpreted in a purely empirical way, by means of evidence from the previous investigations, and they were compared with conventional EI techniques and with the thermal energy surface ionization technique (SIOMS; Surface Ionization Organic Mass Spectrometry). Ionization efficiency (β) was also studied. Under hyperthermal surface ionization (HSI) conditions, many kinds of fragment ions, including quite abundant odd electron ions (OE +· ) are observed. HSIMS patterns of monoterpenes are different among 6-isomers, contrary to those of SIOMS and EIMS, where very similar patterns for isomers are observed. HSIMS patterns are strongly dependent on the molecular kinetic energies. The surface temperature does not affect much the spectral patterns, but it controls the total amount of ion formation. We conclude from these mass spectral findings, HSI-mechanism contains an impulsive process of ion formation, followed by the fragmentation process as a results of the internal energies acquired through the collision processes. (author)

  7. Charmed-meson fragmentation functions with finite-mass corrections and their application in various processes

    Energy Technology Data Exchange (ETDEWEB)

    Kneesch, Torben

    2010-12-15

    We have calculated the single-inclusive production cross section of massive quarks in electron-positron-annihilation with next-to-leading order QCD corrections. With these results we have extracted fragmentation functions for the fragmentation from partons into D{sup 0}, D{sup +} and D{sup *} mesons, where we have used experimental data from the B factories Belle and CLEO and from the ALEPH and OPAL experiments at the LEP collider. In our analysis we have included the masses of c and b quarks and of the D mesons and tested the evolution of fragmentation functions with a global fit spanning the B factories' center-of-mass energy of {radical}(s)=10.5 GeV to LEP's run at the Z boson resonance at M{sub Z}. We have applied this fragmentation functions in deep inelastic scattering for comparisons with HERA data using parton cross sections from the literature available in program form. We have then modified this cross section to calculate predictions for deep inelastic two-photon-scattering. By applying the Weizsaecker-Williams spectrum on the real photon we have calculated predictions for LEP1, LEP2 and the future ILC experiments. For ILC we have also included a beamstrahlung spectrum. Finally we have calculated production cross sections for the planned e{gamma} mode of the ILC with the help of a Compton spectrum. (orig.)

  8. Fragment emission in reactions of 18.5-GeV 12C ions with complex nuclei

    International Nuclear Information System (INIS)

    Porile, N.T.; Cole, G.D.

    1982-01-01

    The emission of fragments ranging from 24 Na to 52 Mn in reactions of 18.5 GeV 12 C ions with Cu, Ag, Gd, Ta, Au, and U targets has been studied by means of activation techniques. The experiments involved determination of the fragment production cross sections and thick-target recoil properties. The latter were used to obtain mean fragment kinetic energies and values of β/sub parallel to/, the forward velocity component of the struck nucleus (in units of c). The results are compared with similar data for incident protons of the same total kinetic energy. The data may be used to assess the importance of central collisions in fragment production. Such collisions lead to the near total destruction of both interacting nuclei and the resulting fragments are emitted by a system of intermediate rapidity. In such a process, the factorization hypothesis, which has been shown to be valid for target and projectile fragmentation reactions, should not be obeyed. A test for factorization is performed by means of a relation which states that the ratio of the cross sections for producing fragment /sup A/Z in 12 C reactions to that for producing the same fragment in proton reactions with the same target is unity, provided both cross sections are reduced by the values of the corresponding total reaction cross sections sigma/sub R/, and evaluated for the same total kinetic energy of the projectile. The results of this comparison for the targets studied are presented and discussed

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

    Science.gov (United States)

    Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan; Junninen, Heikki; Massoli, Paola; Lambe, Andrew T.; Kimmel, Joel R.; Cubison, Michael J.; Graf, Stephan; Lin, Ying-Hsuan; Budisulistiorini, Sri H.; Zhang, Haofei; Surratt, Jason D.; Knochenmuss, Richard; Jayne, John T.; Worsnop, Douglas R.; Jimenez, Jose-Luis; Canagaratna, Manjula R.

    2016-07-01

    Measurement techniques that provide molecular-level information are needed to elucidate the multiphase processes that produce secondary organic aerosol (SOA) species in the atmosphere. Here we demonstrate the application of ion mobility spectrometry-mass spectrometry (IMS-MS) to the simultaneous characterization of the elemental composition and molecular structures of organic species in the gas and particulate phases. Molecular ions of gas-phase organic species are measured online with IMS-MS after ionization with a custom-built nitrate chemical ionization (CI) source. This CI-IMS-MS technique is used to obtain time-resolved measurements (5 min) of highly oxidized organic molecules during the 2013 Southern Oxidant and Aerosol Study (SOAS) ambient field campaign in the forested SE US. The ambient IMS-MS signals are consistent with laboratory IMS-MS spectra obtained from single-component carboxylic acids and multicomponent mixtures of isoprene and monoterpene oxidation products. Mass-mobility correlations in the 2-D IMS-MS space provide a means of identifying ions with similar molecular structures within complex mass spectra and are used to separate and identify monoterpene oxidation products in the ambient data that are produced from different chemical pathways. Water-soluble organic carbon (WSOC) constituents of fine aerosol particles that are not resolvable with standard analytical separation methods, such as liquid chromatography (LC), are shown to be separable with IMS-MS coupled to an electrospray ionization (ESI) source. The capability to use ion mobility to differentiate between isomers is demonstrated for organosulfates derived from the reactive uptake of isomers of isoprene epoxydiols (IEPOX) onto wet acidic sulfate aerosol. Controlled fragmentation of precursor ions by collisionally induced dissociation (CID) in the transfer region between the IMS and the MS is used to validate MS peak assignments, elucidate structures of oligomers, and confirm the

  10. Food contaminant analysis at ultra-high mass resolution: application of hybrid linear ion trap - orbitrap mass spectrometry for the determination of the polyether toxins, azaspiracids, in shellfish.

    LENUS (Irish Health Repository)

    2010-10-30

    The biotoxins, azaspiracids (AZAs), from marine phytoplankton accumulate in shellfish and affect human health by causing severe gastrointestinal disturbance, diarrhea, nausea and vomiting. Specific and sensitive methods have been developed and validated for the determination of the most commonly occurring azaspiracid analogs. An LTQ Orbitrap mass spectrometer is a hybrid instrument that combines linear ion trap (LIT) mass spectrometry (MS) with high-resolution Fourier transform (FT) MS and this was exploited to perform simultaneous ultra-high-resolution full-scan MS analysis and collision-induced dissociation (CID) tandem mass spectrometry (MS\\/MS). Using the highest mass resolution setting (100,000 FWHM) in full-scan mode, the methodology was validated for the determination of six AZAs in mussel (Mytilus galloprovincialis) tissue extracts. Ultra-high mass resolution, together with a narrow mass tolerance window of ±2 mDa, dramatically improved detection sensitivity. In addition to employing chromatographic resolution to distinguish between the isomeric azaspiracid analogs, AZA1\\/AZA6 and AZA4\\/AZA5, higher energy collisionally induced dissociation (HCD) fragmentation on selected precursor ions were performed in parallel with full-scan FTMS. Using HCD MS\\/MS, most precursor and product ion masses were determined within 1 ppm of the theoretical m\\/z values throughout the mass spectral range and this enhanced the reliability of analyte identity.For the analysis of mussels (M. galloprovincialis), the method limit of quantitation (LOQ) was 0.010 µg\\/g using full-scan FTMS and this was comparable with the LOQ (0.007 µg\\/g) using CID MS\\/MS. The repeatability data were; intra-day RSD% (1.8-4.4%; n = 6) and inter-day RSD% (4.7-8.6%; n = 3). Application of these methods to the analysis of mussels (M. edulis) that were naturally contaminated with azaspiracids, using high-resolution full-scan Orbitrap MS and low-resolution CID MS\\/MS, produced

  11. Sulphur-containing compounds in the essential oil of Ferula alliacea roots and their mass spectral fragmentation patterns.

    Science.gov (United States)

    Kasaian, Jamal; Asili, Javad; Iranshahi, Mehrdad

    2016-10-01

    Context GC-MS analysis is the best way to characterize volatile sulphur-containing compounds. Ferula (Apiaceae) is a genus of perennial herbs. Due to the occurrence of essential oils or oleoresins in the Ferula species, these plants usually possess strong aromatic scent. Terpenoid compounds were the most abundant constituents of Ferula oils, however, in some of Ferula species, the essential oils were dominated by volatile sulphur-containing compounds. Objectives Ferula alliacea Boiss. is considered one of the sources of the oleo-gum-resin asafoetida. In this study, we analyzed the hydrodistilled essential oil from its dried roots and provide new data about retention indices and mass fragmentation patterns of some volatile sulphur-containing compounds that are useful for future studies on this class of compounds. Materials and methods The roots of F. alliacea were collected during the flowering stage of plant, from Bezgh, Kashmar to Neishabour road, Khorasan-Razavi province, Iran, in June 2012. The oil was obtained by hydrodistillation using a Clevenger apparatus and analyzed by GC-MS. Results This is the first report on phytochemical analysis of F. alliacea roots. Seventy-six components, representing 99.5% of the oil, were characterized. The major components were 10-epi-γ-eudesmol (22.3%), valerianol (12.5%), hinesol (8.3%), guaiol (7.3%) and Z-propenyl-sec-butyl trisulphide (6.5%). Predominant mass fragment ions of the identified sulphur-containing compounds are explained in this paper. Conclusion The volatile oil of F. alliacea mostly contains oxygenated sesquiterpenes, however, its odour was dominated by sulphur-containing compounds. The most abundant sulphur-containing compound includes Z-propenyl-sec-butyl trisulphide (6.5%).

  12. Observed mass distribution of spontaneous fission fragments from samples of lime - an SSNTD study

    CERN Document Server

    Paul, D; Ghose, D; Sastri, R C

    1999-01-01

    SSNTD is one of the most commonly used detectors in the studies involving nuclear phenomena. The ease of registration of the presence of alpha particles and fission fragments has made it particularly suitable in studies where stable long exposures are needed to extract reliable information. Studies on the presence of alpha emitting nuclides in the environment assume importance since they are found to be carcinogenic. Lime samples from Silchar in Assam of Eastern India have shown the presence of spontaneous fission fragments besides alphas. In the present study we look at the ratio of the average mass distribution of these fission fragments, that gives us an indication of the presence of the traces of transuranic elements.

  13. Laser-induced-fluorescence studies of fragment ions: CH+ and CD+

    International Nuclear Information System (INIS)

    O'Keefe, A.

    1981-08-01

    The dynamics of ion-molecule interactions within a mass selective rf quadrupole ion trap are studied for several ion-molecule systems. Laser induced fluorescence is used as a probe of the internal energy distributions of molecular ions under collision free conditions and under controlled collision conditions. The effects of collisions at near thermal energies (0.3 to 0.5 eV) are easily understood in terms of processes such as charge transfer and other energy transfer mechanisms. The A 1 PI - X 1 Σ + system of CH + and CD + has been examined under collision free conditions. The ions were produced from methane through electron impact ionization/dissociation. The observed energy distributions reflect the dynamical partitioning of dissociation exothermicity, excepting short lived electronic states. Many new transitions belonging to this electronic system have been observed and a reliable vibrational frequency for the X 1 Σ + state has been obtained. The radiative lifetimes of CH + and CD + A 1 PI(v = 0) states have been measured and a revised oscillator strength for the A-X transition has been derived from this data

  14. Low mass dilepton production in heavy ion collisions

    International Nuclear Information System (INIS)

    Pisutova, N.; Pisut, J.

    1988-01-01

    The total transverse energy dependence of low mass dilepton (and single low p T photon) production was demonstrated to be a signature of the onset of the evidence of plasma formation in heavy ion collisions. Cross-sections are presented for low mass dilepton production in proton-nucleus and heavy ion collisions which represent lower bounds for the ''collectivization'' and the thermalization of matter produced in the collision. Higher cross-section are a signature of the onset of the formation of thermalized matter. (author). 4 figs., 11 refs

  15. First signal from a broadband cryogenic preamplifier cooled by circulating liquid nitrogen in a 7 T Fourier transform ion cyclotron resonance mass spectrometer.

    Science.gov (United States)

    Choi, Myoung Choul; Lee, Jeong Min; Lee, Se Gyu; Choi, Sang Hwan; Choi, Yeon Suk; Lee, Kyung Jae; Kim, SeungYong; Kim, Hyun Sik; Stahl, Stefan

    2012-12-18

    Despite the outstanding performance of Fourier transform ion cyclotron/mass spectrometry (FTICR/MS), the complexity of the cellular proteome or natural compounds presents considerable challenges. Sensitivity is a key performance parameter of a FTICR mass spectrometer. By improving this parameter, the dynamic range of the instrument can be increased to improve the detection signal of low-abundance compounds or fragment ion peaks. In order to improve sensitivity, a cryogenic detection system was developed by the KBSI (Korean Basic Science Institute) in collaboration with Stahl-Electronics (Mettenheim, Germany). A simple, efficient liquid circulation cooling system was designed and a cryogenic preamplifier implemented inside a FTICR mass spectrometer. This cooling system circulates a cryoliquid from a Dewar to the "liquid circulation unit" through a CF flange to cool a copper block and a cryopreamplifier; the cooling medium is subsequently exhausted into the air. The cryopreamplifier can be operated over a very wide temperature range, from room temperature to low temperature environments (4.2 K). First, ion signals detected by the cryopreamplifier using a circulating liquid nitrogen cooling system were observed and showed a signal-to-noise ratio (S/N) about 130% better than that obtained at room temperature.

  16. Simulation of a relativistic heavy ions beam transport in the matter: contribution of the fragmentation process and biological implications

    International Nuclear Information System (INIS)

    Ibnouzahir, M.

    1995-03-01

    The study of relativistic heavy ion collisions permit an approach of the properties of dense and not hadronic matter, and an analysis of the reaction mechanisms. Such studies are also interesting on the biological point of view, since there exist now well defined projects concerning the radiotherapy with high LET particles as neutrons, protons, heavy ions. It is thus necessary to have a good understanding of the processes which occur in the propagation of a relativistic heavy ion beam (E≥ 100 A.MeV) in matter. We have elaborated a three dimensional transport code, using a Monte Carlo method, in order to describe the propagation of Ne and Ar ions in water. Violent nuclear collisions giving fragmentation process have been taken into account by use of the FREESCO program. We have tested the validity of our transport model and we show an important change of the energy deposition at the vicinity of the Bragg peak; such a distortion, due mainly to fragmentation reactions, is of a great interest for biological applications. (author)

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  18. Evidence of site-specific fragmentation on thioacetic acid, CH3C(O)SH, irradiated with synchrotron radiation around the S 2p and O 1s regions.

    Science.gov (United States)

    Erben, Mauricio F; Geronés, Mariana; Romano, Rosana M; Della Védova, Carlos O

    2006-01-26

    Site-specific fragmentations following S 2p and O 1s photoexcitation of thioacetic acid, CH3C(O)SH, have been studied by means of synchrotron radiation. Total ion yield (TIY) spectra were measured and multicoincidence techniques, which include photoelectron-photoion coincidence (PEPICO) and photoelectron-photoion-photoion coincidence (PEPIPICO) time-of-flight mass spectrometry, were applied. The equivalent-core approximation was employed in order to estimate ionization transition values, and the observed peaks were tentatively assigned. A site-specific fragmentation is moderately observed by comparing the mass spectra collected at resonant energies around the inner and shallow inner shell S 2p and O 1s ionization edges. Beside H+ ion, the most abundant ions observed at the S 2p edge excitation were CH3CO+, SH+, S+, and CH3+. At the O 1s region the large CH3CO+ fragment was depressed, and small CHx+ (x = 0, 1, 2, 3), S+, and SH+ fragments were dominant. The dissociation dynamic for the main ion-pair production has been discussed. Two- and three-body dissociation channels have been observed in the PEPIPICO spectra, and the dissociation mechanisms were proposed.

  19. Synthesis and Electrospray Ionization Mass Spectra of N-(1,3,2-Dioxaphosphorinan-2-ylmethyl)thiophosphoramidates

    Institute of Scientific and Technical Information of China (English)

    MIAO,Zhi-Wei; FU,Cui-Rong; WANG,Bin; CUI,Zhan-Wei; ZHANG,Jian-Feng; CHEN,Ru-Yu

    2007-01-01

    N-(1,3,2-Dioxaphosphorinan-2-ylmethyl) thiophosphoramidates were synthesized and determined by NMR spectra and positive ion electrospray ionization mass spectrometry (ESI-MS) in conjunction with tandem mass spectrometry (MS/MS). The fragmentation pathways were investigated. The results show that these characteristic ions in ESI mass spectra are useful in the structural determination of N-(1,3,2-dioxaphosphorinan-2-ylmethyl)thiophosphoramidates.

  20. Application of High-Performance Liquid Chromatography Coupled with Linear Ion Trap Quadrupole Orbitrap Mass Spectrometry for Qualitative and Quantitative Assessment of Shejin-Liyan Granule Supplements

    OpenAIRE

    Jifeng Gu; Weijun Wu; Mengwei Huang; Fen Long; Xinhua Liu; Yizhun Zhu

    2018-01-01

    A method for high-performance liquid chromatography coupled with linear ion trap quadrupole Orbitrap high-resolution mass spectrometry (HPLC-LTQ-Orbitrap MS) was developed and validated for the qualitative and quantitative assessment of Shejin-liyan Granule. According to the fragmentation mechanism and high-resolution MS data, 54 compounds, including fourteen isoflavones, eleven ligands, eight flavonoids, six physalins, six organic acids, four triterpenoid saponins, two xanthones, two alkaloi...

  1. Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

    Science.gov (United States)

    Kaufmann, A; Walker, S; Mol, G

    2016-04-15

    Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  2. Development of portable mass spectrometer with electron cyclotron resonance ion source for detection of chemical warfare agents in air.

    Science.gov (United States)

    Urabe, Tatsuya; Takahashi, Kazuya; Kitagawa, Michiko; Sato, Takafumi; Kondo, Tomohide; Enomoto, Shuichi; Kidera, Masanori; Seto, Yasuo

    2014-01-01

    A portable mass spectrometer with an electron cyclotron resonance ion source (miniECRIS-MS) was developed. It was used for in situ monitoring of trace amounts of chemical warfare agents (CWAs) in atmospheric air. Instrumental construction and parameters were optimized to realize a fast response, high sensitivity, and a small body size. Three types of CWAs, i.e., phosgene, mustard gas, and hydrogen cyanide were examined to check if the mass spectrometer was able to detect characteristic elements and atomic groups. From the results, it was found that CWAs were effectively ionized in the miniECRIS-MS, and their specific signals could be discerned over the background signals of air. In phosgene, the signals of the 35Cl+ and 37Cl+ ions were clearly observed with high dose-response relationships in the parts-per-billion level, which could lead to the quantitative on-site analysis of CWAs. A parts-per-million level of mustard gas, which was far lower than its lethal dosage (LCt50), was successfully detected with a high signal-stability of the plasma ion source. It was also found that the chemical forms of CWAs ionized in the plasma, i.e., monoatomic ions, fragment ions, and molecular ions, could be detected, thereby enabling the effective identification of the target CWAs. Despite the disadvantages associated with miniaturization, the overall performance (sensitivity and response time) of the miniECRIS-MS in detecting CWAs exceeded those of sector-type ECRIS-MS, showing its potential for on-site detection in the future. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Kinetics of fragmentation-annihilation processes

    OpenAIRE

    Filipe, JAN; Rodgers, GJ

    1996-01-01

    We investigate the kinetics of systems in which particles of one species undergo binary fragmentation and pair annihilation. In the latter, nonlinear process, fragments react at collision to produce an inert species, causing loss of mass. We analyze these systems in the reaction-limited regime by solving a continuous model within the mean-field approximation. The rate of fragmentation for a particle of mass x to break into fragments of masses y and x-y has the form x(lambda-1) (lambda > 0), a...

  4. Fragmentation Pathways of Trifluoroacetyl Derivatives of Methamphetamine, Amphetamine, and Methylenedioxyphenyl alkylamine Designer Drugs by Gas Chromatography/Mass Spectrometry

    International Nuclear Information System (INIS)

    Kumazawa, T.; Xiao-Pen, L.; Sato, K.

    2011-01-01

    Methamphetamine (MA), amphetamine (AM), and the methylenedioxyphenyl alkylamine designer drugs, such as 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxy ethylamphetamine (MDEA), N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine (MBDB), 3,4-methylenedioxyamphetamine (MDA), and 3,4-(methylenedioxyphenyl)-2-butanamine (BDB), are widely abused as psychedelics. In this paper, these compounds were derivatized with trifluoroacetic (TFA) anhydride and analyzed by gas chromatography/mass spectrometry using electron ionization in positive mode. Gas chromatographic separation for TFA derivatives of all compounds was successfully resolved using an Equity-5 fused silica capillary column with a poly (5% diphenyl-95% dimethylsiloxane) stationary phase. Base peaks or prominent peaks of MA, AM, MDMA, MDEA, MBDB, MDA, and BDB appeared at m/z 154, 140, 154, 168, 168, 135, and 135, respectively. These occurred due to a-cleavage from the amide nitrogen, splitting into the TFA imine species and benzyl or methylenedioxybenzyl cations. Further prominent fragment ions at m/z 118 for MA and AM, m/z 162 for MDMA, MDEA, and MDA, and m/z 176 for MBDB and BDB were produced by cleavage of the phenylpropane or methylenedioxy propane hydrocarbon radical cation via a hydrogen rearrangement. These fragmentation pathways for the TFA derivatives of all the compounds are summarized and illustrated in this paper.

  5. Fourier Transfrom Ion Cyclotron Resonance Mass Spectrometry at High Magnetic Field

    Science.gov (United States)

    Marshall, Alan G.

    1998-03-01

    At high magnetic field (9.4 tesla at NHMFL), Fourier transform ion cyclotron resonance mass spectrometry performance improves dramatically: mass resolving power, axialization efficiency, and scan speed (each proportional to B), maximum ion mass, dynamic range, ion trapping period, kinetic energy, and electron self-cooling rate for sympathetic cooling (each proportional to B^2), and ion coalescence tendency (proportional 1/B^2). These advantages may apply singly (e.g., unit mass resolution for proteins of >100,000 Da), or compound (e.g., 10-fold improvement in S/N ratio for 9.4 T vs. 6 T at the same resolving power). Examples range from direct determination of molecular formulas of diesel fuel components by accurate mass measurement (=B10.1 ppm) to protein structure and dynamics probed by H/D exchange. This work was supported by N.S.F. (CHE-93-22824; CHE-94-13008), N.I.H. (GM-31683), Florida State University, and the National High Magnetic Field Laboratory in Tallahassee, FL.

  6. Accurate mass analysis of ethanesulfonic acid degradates of acetochlor and alachlor using high-performance liquid chromatography and time-of-flight mass spectrometry

    Science.gov (United States)

    Thurman, E.M.; Ferrer, I.; Parry, R.

    2002-01-01

    Degradates of acetochlor and alachlor (ethanesulfonic acids, ESAs) were analyzed in both standards and in a groundwater sample using high-performance liquid chromatography-time-of-flight mass spectrometry with electrospray ionization. The negative pseudomolecular ion of the secondary amide of acetochlor ESA and alachlor ESA gave average masses of 256.0750??0.0049 amu and 270.0786??0.0064 amu respectively. Acetochlor and alachlor ESA gave similar masses of 314.1098??0.0061 amu and 314.1153??0.0048 amu; however, they could not be distinguished by accurate mass because they have the same empirical formula. On the other hand, they may be distinguished using positive-ion electrospray because of different fragmentation spectra, which did not occur using negative-ion electrospray.

  7. Nuclear fragmentation energy and momentum transfer distributions in relativistic heavy-ion collisions

    Science.gov (United States)

    Khandelwal, Govind S.; Khan, Ferdous

    1989-01-01

    An optical model description of energy and momentum transfer in relativistic heavy-ion collisions, based upon composite particle multiple scattering theory, is presented. Transverse and longitudinal momentum transfers to the projectile are shown to arise from the real and absorptive part of the optical potential, respectively. Comparisons of fragment momentum distribution observables with experiments are made and trends outlined based on our knowledge of the underlying nucleon-nucleon interaction. Corrections to the above calculations are discussed. Finally, use of the model as a tool for estimating collision impact parameters is indicated.

  8. High-precision spectrometer for studies of ion-induced and spontaneous fission dynamics

    International Nuclear Information System (INIS)

    Batenkov, O.; Elmgren, K.; Majorov, M.; Blomgren, J.; Conde, H.; Hultqvist, S.; Olsson, N.; Rahm, J.; Ramstroem, E.; Smirnov, S.; Veshikov, A.

    1997-01-01

    A spectrometer has been designed and built to investigate the dynamics of spontaneous and ion-induced fission processes. It consists of 8 neutron detectors surrounding a low mass scattering chamber containing the fissionable targets and two fission fragment telescopes. The spectrometer measures neutron spectra, and energy and angular correlations of neutrons, as well as kinetic energy, mass, and relative angle of fission fragments. A 252 Cf fission reference source is used for calibration. (orig.)

  9. Quantification of steroid conjugates using fast atom bombardment mass spectrometry

    International Nuclear Information System (INIS)

    Gaskell, S.J.

    1990-01-01

    Fast atom bombardment/mass spectrometry or liquid secondary ion mass spectrometry provides the capability for direct analysis of steroid conjugates (sulfates, glucuronides) without prior hydrolysis or derivatization. During the analysis of biologic extracts, limitations on the sensitivity of detection arise from the presence of co-extracted material which may suppress or obscure the analyte signal. A procedure is described for the quantitative determination of dehydroepiandrosterone sulfate in serum which achieved selective isolation of the analyte using immunoadsorption extraction and highly specific detection using tandem mass spectrometry. A stable isotope-labeled analog [( 2H2]dehydroepiandrosterone sulfate) was used as internal standard. Fast atom bombardment of dehydroepiandrosterone sulfate yielded abundant [M-H]- ions that fragmented following collisional activation to give HSO4-; m/z 97. During fast atom bombardment/tandem mass spectrometry of serum extracts, a scan of precursor ions fragmenting to give m/z 97 detected dehydroepiandrosterone sulfate and the [2H2]-labeled analog with a selectivity markedly superior to that observed using conventional mass spectrometry detection. Satisfactory agreement was observed between quantitative data obtained in this way and data obtained by gas chromatography/mass spectrometry of the heptafluorobutyrates of dehydroepiandrosterone sulfate and [2H2]dehydroepiandrosterone sulfate obtained by direct derivatization. 21 refs

  10. Nuclear fragmentation reactions in extended media studied with Geant4 toolkit

    Energy Technology Data Exchange (ETDEWEB)

    Pshenichnov, Igor, E-mail: pshenich@fias.uni-frankfurt.d [Frankfurt Institute for Advanced Studies, J.-W. Goethe University, 60438 Frankfurt am Main (Germany); Institute for Nuclear Research, Russian Academy of Science, 117312 Moscow (Russian Federation); Botvina, Alexander [Frankfurt Institute for Advanced Studies, J.-W. Goethe University, 60438 Frankfurt am Main (Germany); Institute for Nuclear Research, Russian Academy of Science, 117312 Moscow (Russian Federation); Mishustin, Igor [Frankfurt Institute for Advanced Studies, J.-W. Goethe University, 60438 Frankfurt am Main (Germany); Kurchatov Institute, Russian Research Center, 123182 Moscow (Russian Federation); Greiner, Walter [Frankfurt Institute for Advanced Studies, J.-W. Goethe University, 60438 Frankfurt am Main (Germany)

    2010-03-15

    It is well-known from numerous experiments that nuclear multifragmentation is a dominating mechanism for production of intermediate mass fragments in nucleus-nucleus collisions at energies above 100AMeV. In this paper we investigate the validity and performance of the Fermi break-up model and the statistical multifragmentation model implemented as parts of the Geant4 toolkit. We study the impact of violent nuclear disintegration reactions on the depth-dose profiles and yields of secondary fragments for beams of light and medium-weight nuclei propagating in extended media. Implications for ion-beam cancer therapy and shielding from cosmic radiation are discussed.

  11. Nuclear fragmentation reactions in extended media studied with Geant4 toolkit

    International Nuclear Information System (INIS)

    Pshenichnov, Igor; Botvina, Alexander; Mishustin, Igor; Greiner, Walter

    2010-01-01

    It is well-known from numerous experiments that nuclear multifragmentation is a dominating mechanism for production of intermediate mass fragments in nucleus-nucleus collisions at energies above 100AMeV. In this paper we investigate the validity and performance of the Fermi break-up model and the statistical multifragmentation model implemented as parts of the Geant4 toolkit. We study the impact of violent nuclear disintegration reactions on the depth-dose profiles and yields of secondary fragments for beams of light and medium-weight nuclei propagating in extended media. Implications for ion-beam cancer therapy and shielding from cosmic radiation are discussed.

  12. Quantitative analysis of modified proteins and their positional isomers by tandem mass spectrometry: human histone H4.

    Science.gov (United States)

    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 fragment ions, with intact protein ions created by electrospray greatly easing many of the systematic biases that more strongly affect small peptides (e.g., differences in ionization efficiency and ion m/z values). The ion fragmentation methods validated here are directly extensible to intact human proteins to derive quantitative information on the highly related and often isomeric protein forms created by combinatorial arrays of posttranslational modifications.

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

    Science.gov (United States)

    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

  14. Characterization of hydrophobic peptides in the presence of detergent by photoionization mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Aïcha Bagag

    Full Text Available 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.

  15. Comparison of Se and Te clusters produced by ion bombardment

    Directory of Open Access Journals (Sweden)

    Trzyna Małgorzata

    2017-01-01

    Full Text Available Nanostructures based on tellurium and selenium are materials used as components for the manufacturing topological insulators. Therefore it is crucial to precisely characterize these materials. In this work the emission of selenium and tellurium cluster ions, sputtered by Bi+ primary ion guns, was investigated by using Time-of-Flight Secondary Ion Mass Spectrometry (TOF SIMS. It has been found that BixTex and BixSex clusters appear in addition to Sex and Tex clusters in the mass range up to ~ 1300 m/z. Local maxima or minima (magic numbers are observed in the ion intensity versus a number of atoms per cluster for both positive and negative ions spectra for all types of clusters and primary ions used. These extrema can be attributed to different yield and stability of certain clusters but also to fragmentation of high-mass clusters.

  16. Comparison of Se and Te clusters produced by ion bombardment

    Science.gov (United States)

    Trzyna, Małgorzata

    2017-01-01

    Nanostructures based on tellurium and selenium are materials used as components for the manufacturing topological insulators. Therefore it is crucial to precisely characterize these materials. In this work the emission of selenium and tellurium cluster ions, sputtered by Bi+ primary ion guns, was investigated by using Time-of-Flight Secondary Ion Mass Spectrometry (TOF SIMS). It has been found that BixTex and BixSex clusters appear in addition to Sex and Tex clusters in the mass range up to 1300 m/z. Local maxima or minima (magic numbers) are observed in the ion intensity versus a number of atoms per cluster for both positive and negative ions spectra for all types of clusters and primary ions used. These extrema can be attributed to different yield and stability of certain clusters but also to fragmentation of high-mass clusters.

  17. A high-resolution mass spectrometer to measure atmospheric ion composition

    Directory of Open Access Journals (Sweden)

    H. Junninen

    2010-08-01

    Full Text Available In this paper we present recent achievements on developing and testing a tool to detect the composition of ambient ions in the mass/charge range up to 2000 Th. The instrument is an Atmospheric Pressure Interface Time-of-Flight Mass Spectrometer (APi-TOF, Tofwerk AG. Its mass accuracy is better than 0.002%, and the mass resolving power is 3000 Th/Th. In the data analysis, a new efficient Matlab based set of programs (tofTools were developed, tested and used. The APi-TOF was tested both in laboratory conditions and applied to outdoor air sampling in Helsinki at the SMEAR III station. Transmission efficiency calibrations showed a throughput of 0.1–0.5% in the range 100–1300 Th for positive ions, and linearity over 3 orders of magnitude in concentration was determined. In the laboratory tests the APi-TOF detected sulphuric acid-ammonia clusters in high concentration from a nebulised sample illustrating the potential of the instrument in revealing the role of sulphuric acid clusters in atmospheric new particle formation. The APi-TOF features a high enough accuracy, resolution and sensitivity for the determination of the composition of atmospheric small ions although the total concentration of those ions is typically only 400–2000 cm−3. The atmospheric ions were identified based on their exact masses, utilizing Kendrick analysis and correlograms as well as narrowing down the potential candidates based on their proton affinities as well isotopic patterns. In Helsinki during day-time the main negative ambient small ions were inorganic acids and their clusters. The positive ions were more complex, the main compounds were (polyalkyl pyridines and – amines. The APi-TOF provides a near universal interface for atmospheric pressure sampling, and this key feature will be utilized in future laboratory and field studies.

  18. Direct trace analysis of metals and alloys in a quadrupole ion-trap mass spectrometer

    CERN Document Server

    Song, K S; Yang, M; Cha, H K; Lee, J M; Lee, G H

    1999-01-01

    An ion-trap mass spectrometer adopting a quadrupole ion-trap and laser ablation/ionization method was constructed. The developed system was tested for composition analysis of some metals (Cu, stainless), and alloys (hastalloy C, mumetal) by mass spectrometry. Samples were analyzed by using laser ablation from a sample probe tip followed by a mass analysis with the quadrupole ion-trap. The quadrupole ion-trap was modified to enable laser ablation by a XeCl excimer laser pulse that passed radially through the ring electrode. A mass scan of the produced ions was performed in the mass selective instability mode wherein trapped ions were successively detected by increasing the rf voltage through the ring electrode. Factors affecting the mass resolution, such as pressure of buffer gas and ablation laser power, are discussed.

  19. A comparative study of carbocyanine dyes measured with TOF-SIMS and other mass spectrometric techniques

    International Nuclear Information System (INIS)

    Adriaensen, L.; Vangaever, F.; Gijbels, R.

    2004-01-01

    A series of cationic, zwitterionic and anionic carbocyanine dyes have been measured with TOF-SIMS under Ga + bombardment. In contrast to the cationic dyes, which give very intense molecular ion and characteristic fragment signals in the positive mode, the anionic dyes produce only a few fragment signals of low intensity. Even in the negative mode no molecular ions of the anionic dyes are seen in the recorded spectra. Actually, none of the studied molecules produces negative SIMS spectra containing molecular information. A comparative study was made between TOF-SIMS and other mass spectrometric techniques, namely, fast atom bombardment (FAB), electro spray ionization (ESI) and matrix assisted laser desorption ionization (MALDI). The measurements show that MALDI, ESI as well as FAB all give rise to spectra containing molecular ion signals, either in the positive, in the negative or in both modes. Unlike with TOF-SIMS, this observation also applies to the anionic dyes. Characteristic fragments of the dyes are present in all the recorded spectra. However, TOF-SIMS appears to induce more fragment ions in comparison with the other techniques. ESI, for instance, produces hardly any molecular fragments. Finally, the kind of fragment ions recorded depends upon the technique used, though some signals are produced by various techniques. For these carbocyanine dyes there is no clear correlation between the mass spectra obtained with TOF-SIMS and spectra obtained with the other techniques. This points to different desorption/ionization mechanisms, and makes it difficult, in practice, to make predictions on the feasibility of TOF-SIMS, starting from results of the other MS techniques

  20. Surface-Induced Dissociation of Protein Complexes in a Hybrid Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Jing; Zhou, Mowei; Gilbert, Joshua D.; Wolff, Jeremy J.; Somogyi, Árpád; Pedder, Randall E.; Quintyn, Royston S.; Morrison, Lindsay J.; Easterling, Michael L.; Paša-Tolić, Ljiljana; Wysocki, Vicki H.

    2017-01-03

    Mass spectrometry continues to develop as a valuable tool in the analysis of proteins and protein complexes. In protein complex mass spectrometry studies, surface-induced dissociation (SID) has been successfully applied in quadrupole time-of-flight (Q-TOF) instruments. SID provides structural information on non-covalent protein complexes that is complementary to other techniques. However, the mass resolution of Q-TOF instruments can limit the information that can be obtained for protein complexes by SID. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolution and ultrahigh mass accuracy measurements. In this study, an SID device was designed and successfully installed in a hybrid FT-ICR instrument in place of the standard gas collision cell. The SID-FT-ICR platform has been tested with several protein complex systems (homooligomers, a heterooligomer, and a protein-ligand complex, ranging from 53 kDa to 85 kDa), and the results are consistent with data previously acquired on Q-TOF platforms, matching predictions from known protein interface information. SID fragments with the same m/z but different charge states are well-resolved based on distinct spacing between adjacent isotope peaks, and the addition of metal cations and ligands can also be isotopically resolved with the ultrahigh mass resolution available in FT-ICR.

  1. Collision induced dissociation of protonated N-nitrosodimethylamine by ion trap mass spectrometry: Ultimate carcinogens in gas phase

    Science.gov (United States)

    Kulikova, Natalia; Baker, Michael; Gabryelski, Wojciech

    2009-12-01

    Collision induced dissociation of protonated N-nitrosodimethylamine (NDMA) and isotopically labeled N-nitrosodimethyl-d6-amine (NDMA-d6) was investigated by sequential ion trap mass spectrometry to establish mechanisms of gas phase reactions leading to intriguing products of this potent carcinogen. The fragmentation of (NDMA + H+) occurs via two dissociation pathways. In the alkylation pathway, homolytic cleavage of the N-O bond of N-dimethyl, N'-hydroxydiazenium ion generates N-dimethyldiazenium distonic ion which reacts further by a CH3 radical loss to form methanediazonium ion. Both methanediazonium ion and its precursor are involved in ion/molecule reactions. Methanediazonium ion showed to be capable of methylating water and methanol molecules in the gas phase of the ion trap and N-dimethyldiazenium distonic ion showed to abstract a hydrogen atom from a solvent molecule. In the denitrosation pathway, a tautomerization of N-dimethyl, N'-hydroxydiazenium ion to N-nitrosodimethylammonium intermediate ion results in radical cleavage of the N-N bond of the intermediate ion to form N-dimethylaminium radical cation which reacts further through [alpha]-cleavage to generate N-methylmethylenimmonium ion. Although the reactions of NDMA in the gas phase are different to those for enzymatic conversion of NDMA in biological systems, each activation method generates the same products. We will show that collision induced dissociation of N-nitrosodiethylamine (NDEA) and N-nitrosodipropylamine (NDPA) is also a feasible approach to gain information on formation, stability, and reactivity of alkylating agents originating from NDEA and NDPA. Investigating such biologically relevant, but highly reactive intermediates in the condensed phase is hampered by the short life-times of these transient species.

  2. Mass-spectrometric investigation of rare earth acetylacetonates dipivaloylmethanates and their adducts

    International Nuclear Information System (INIS)

    Gavrishzhuk, E.M.; Dzyubenko, N.G.; Martynenko, L.I.

    1985-01-01

    Peculiarities of fragmentation of molecular ions of rare earth acetylacetonates and dipivaloylmethanates under mass-spectrometric investigation of these compounds as well as their adducts with o-phenanthroline, α,α'-dipyridyl, triphenylphosphine oxide are considered in the given review. Similar data for identical derivants of some transitions metals are presented. Data on potentials of appearance and dissociation energy of basic ions in mass-spectra of the studied β-diketonates are analyzed

  3. Theory of peak coalescence in Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Boldin, Ivan A; Nikolaev, Eugene N

    2009-10-01

    Peak coalescence, i.e. the merging of two close peaks in a Fourier transform ion cyclotron resonance (FTICR) mass spectrum at a high number of ions, plays an important role in various FTICR experiments. In order to describe the coalescence phenomenon we would like to propose a new theory of motion for ion clouds with close mass-to-charge ratios, driven by a uniform magnetic field and Coulomb interactions between the clouds. We describe the motion of the ion clouds in terms of their averaged drift motion in crossed magnetic and electric fields. The ion clouds are considered to be of constant size and their motion is studied in two dimensions. The theory deals with the first-order approximation of the equations of motion in relation to dm/m, where dm is the mass difference and m is the mass of a single ion. The analysis was done for an arbitrary inter-cloud interaction potential, which makes it possible to analyze finite-size ion clouds of any shape. The final analytical expression for the condition of the onset of coalescence is found for the case of uniformly charged spheres. An algorithm for finding this condition for an arbitrary interaction potential is proposed. The critical number of ions for the peak coalescence to take place is shown to depend quadratically on the magnetic field strength and to be proportional to the cyclotron radius and inversely proportional to the ion masses. Copyright (c) 2009 John Wiley & Sons, Ltd.

  4. Time-of-flight secondary ion mass spectrometry with energetic cluster ion impact ionization for highly sensitive chemical structure characterization

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, K., E-mail: k.hirata@aist.go.jp [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K.; Narumi, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)

    2013-11-01

    Energetic cluster ions with energies of the order of sub MeV or greater were applied to time-of-flight (TOF) secondary ion (SI) mass spectrometry. This gave various advantages including enhancement of SIs required for chemical structure characterization and prevention of charging effects in SI mass spectra for organic targets. We report some characteristic features of TOF SI mass spectrometry using energetic cluster ion impact ionization and discuss two future applications of it.

  5. Ion mobility analyzer - quadrupole mass spectrometer system design

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  6. Ion mobility analyzer - quadrupole mass spectrometer system design

    Energy Technology Data Exchange (ETDEWEB)

    Cuna, C; Leuca, M; Lupsa, N; Mirel, V; Cuna, Stela; Cosma, V; Tusa, Florina [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Bocos-Bintintan, V, E-mail: cornel.cuna@itim-cj.r [Babes-Bolyai University, Faculty of Environmental Sciences, 3 Fantanele, 400294 Cluj Napoca (Romania)

    2009-08-01

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

  7. Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework.

    Science.gov (United States)

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

    2013-08-01

    The electron-impact (EI) mass spectra of a series of O-alkyl methylphosphonothionocyanidates were studied for Chemical Weapons Convention (CWC) purposes. General EI fragmentation pathways were constructed and discussed, and collision-induced dissociation studies of the major EI ions were performed to confirm proposed fragment structures by analyzing fragment ions of deuterated analogs and by use of density functional theory (DFT) calculations. Thiono-thiolo rearrangement, McLafferty-type rearrangement, and a previously unknown intramolecular electrophilic aromatic substitution reaction were observed and confirmed. The study also focused on differentiation of isomeric compounds. Retention indices for all compounds, and an electrophilicity index for several compounds, are reported and interpreted.

  8. Towards Liquid Chromatography Time-Scale Peptide Sequencing and Characterization of Post-Translational Modifications in the Negative-Ion Mode Using Electron Detachment Dissociation Tandem Mass Spectrometry

    DEFF Research Database (Denmark)

    Kjeldsen, Frank; Hørning, Ole B; Jensen, Søren S

    2008-01-01

    Electron detachment dissociation (EDD) of peptide poly-anions is gentle towards post-translational modifications (PTMs) and produces predictable and interpretable fragment ion types (a., x ions). However, EDD is considered an inefficient fragmentation technique and has not yet been implemented...... coverage and extended PTM characterization the new regime of EDD in combination with other ion-electron fragmentation techniques in the positive-ion mode is a step towards a more comprehensive strategy of analysis in proteome research....

  9. Secondary emission from a CuBe target due to bombardment with parent and fragment ions of ammonia and phosphine

    International Nuclear Information System (INIS)

    Maerk, T.D.

    1977-01-01

    The secondary electron emission of the first dynode of a CuBe alloy sixteen dynode electron multiplier has been studied in the course of electron impact ionization studies of ammonia and phosphine. Relative secondary electron emission coefficients have been obtained for the singly and doubly charged parent and fragment ions of ammonia, ammonia-d 3 , phosphine and phosphine-d 3 for kinetic energies of 5,25 and 10,5 keV. It has been found, that in general deuterated ions have smaller γ coefficients, that ammonia ions have larger γ coefficients than corresponding phosphine ions, and that the γ coefficients increase with the complexity of the ion under study. (Auth.)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2018-05-01

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

  12. High mass accuracy and high mass resolving power FT-ICR secondary ion mass spectrometry for biological tissue imaging

    NARCIS (Netherlands)

    Smith, D.F.; Kiss, A.; Leach, F.E.; Robinson, E.W.; Paša-Tolić, L.; Heeren, R.M.A.

    2013-01-01

    Biological tissue imaging by secondary ion mass spectrometry has seen rapid development with the commercial availability of polyatomic primary ion sources. Endogenous lipids and other small bio-molecules can now be routinely mapped on the sub-micrometer scale. Such experiments are typically

  13. Chemical characterization of microparticles by laser ablation in an ion trap mass spectrometer

    International Nuclear Information System (INIS)

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

    1991-01-01

    We are developing a new technique for the chemical characterization of microparticles based upon the use of electrodynamic traps. The electrodynamic trap has achieved widespread use in the mass spectrometry community in the form of the ion trap mass spectrometer or quadrupole ion trap. Small macroscopic particles can be confined or levitated within the electrode structure of a three-dimensional quadrupole electrodynamic trap in the same way as fundamental charges or molecular ions by using a combination of ac and dc potentials. Our concept is to use the same electrode structure to perform both microparticle levitation and ion trapping/mass analysis. The microparticle will first be trapped and spatially stabilized within the trap for characterization by optical probes, i.e., absorption, fluorescence, or Raman spectroscopy. After the particle has been optically characterized, it is further characterized using mass spectrometry. Ions are generated from the particle surface using laser ablation or desorption. The characteristics of the applied voltages are changed to trap the ions formed by the laser with the ions subsequently mass analyzed. The work described in this paper focuses on the ability to perform laser desorption experiments on microparticles contained within the ion trap

  14. Depth profiling of residual activity of ^{237}U fragments as a range verification technique for ^{238}U primary ion beam

    Directory of Open Access Journals (Sweden)

    I. Strašík

    2012-07-01

    Full Text Available Experimental and simulation data concerning fragmentation of ^{238}U ion beam in aluminum, copper, and stainless-steel targets with the initial energy 500 and 950  MeV/u are collected in the paper. A range-verification technique based on depth profiling of residual activity is presented. The irradiated targets were constructed in the stacked-foil geometry and analyzed using gamma-ray spectroscopy. One of the purposes of these experiments was depth profiling of residual activity of induced nuclides and projectile fragments. Among the projectile fragments, special attention is paid to the ^{237}U isotope that has a range very close to the range of the primary ^{238}U ions. Therefore, the depth profiling of the ^{237}U isotope can be utilized for experimental verification of the ^{238}U primary-beam range, which is demonstrated and discussed in the paper. The experimental data are compared with computer simulations by FLUKA, SRIM, and ATIMA, as well as with complementary experiments.

  15. Fragmentation of copper current collectors in Li-ion batteries during spherical indentation

    International Nuclear Information System (INIS)

    Wang, Hsin; Watkins, Thomas R.; Simunovic, Srdjan; Bingham, Philip R.; Allu, Srikanth; Turner, John A.

    2017-01-01

    Large, areal, brittle fracture of copper current collector foils was observed by 3D x-ray computed tomography (XCT) of a spherically indented Li-ion cell. This fracture was hidden and non-catastrophic to a degree because the graphite layers deformed plastically, and held the materials together so that the cracks in the foils could not be seen under optical and electron microscopy. 3D XCT on the indented cell showed “mud cracks” within the copper layer. The cracking of copper foils could not be immediately confirmed when the cell was opened for post-mortem examination. However, an X-ray radiograph on a single foil of the Cu anode showed clearly that the copper foil had broken into multiple pieces similar to the brittle cracking of a ceramic under indentation. This new failure mode of anodes on Li-ion cell has very important implications on the behavior of Li-ion cells under mechanical abuse conditions. Furthermore, the fragmentation of current collectors in the anode must be taken into consideration for the electrochemical responses which may lead to capacity loss and affect thermal runaway behavior of the cells.

  16. Time evolution of the mass exchange in grazing heavy-ion collisions

    International Nuclear Information System (INIS)

    Bastrukov, S.I.; Deak, F.; Kiss, A.; Seres, Z.

    1989-10-01

    On the basis of a macroscopical approach to the description of two interpenetrating quantum objects, the equations of two-fluid hydrodynamics for the cohesion stage of deeply inelastic heavy-ion collisions are formulated. The elasticity of the ions is analyzed in peripheral mass exchange reactions at intermediate energies. The system of closed equations of Newtonian mechanics, which simultaneously describes the motion of the ions along classical trajectories as well as the mass time evolution during the interaction period are derived and solved. The role of mass exchange in the friction force is discussed. (author) 22 refs.; 2 figs

  17. Ultra High-Mass Resolution Paper Spray by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Kevin D. Quinn

    2012-01-01

    Full Text Available Paper Spray Ionization is an atmospheric pressure ionization technique that utilizes an offline electro-osmotic flow to generate ions off a paper medium. This technique can be performed on a Bruker SolariX Fourier transform ion cyclotron resonance mass spectrometer by modifying the existing nanospray source. High-resolution paper spray spectra were obtained for both organic and biological samples to demonstrate the benefit of linking the technique with a high-resolution mass analyzer. Error values in the range 0.23 to 2.14 ppm were obtained for calf lung surfactant extract with broadband mass resolving power (m/Δm50% above 60,000 utilizing an external calibration standard.

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

    Science.gov (United States)

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

    2016-03-01

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

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

    Science.gov (United States)

    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.

  20. Dissociation mechanism of HNIW ions investigated by chemical ionization and electron impact mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rongjie; Xiao, Hemiao [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

    2006-04-15

    Chemical Ionization (CI) with Collision-Induced Dissociation (CID) spectroscopy and Electron Impacting (EI) with metastable Mass analyzed Ion Kinetic Energy (MIKE) spectroscopy have been applied to study ionic dissociations of Hexanitrohexaazaisowurtzitane (HNIW). Similarities and differences between EI/MIKE and CI/CID mass spectra of HNIW were analyzed. In EI mass spectra, the ions [HNIW-n NO{sub 2}]{sup +} (n=2-5), such as the ion at m/z 347, were less frequent (1-2% relative abundance), but in CI mass spectra, these ions were very abundant. For some ions of large molar mass from HNIW, their dissociations pathways from parent ions to daughter ions were built according to CID and MIKE spectra. Molecular ions of HNIW with a protonated nitro group at five-member ring seem more stable than at six-member ring. The HNIW ions losing five of six nitro groups are very stable based on CID spectra, which agrees with some research results for thermal decomposition of HNIW in literature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  1. Achieving high baryon densities in the fragmentation regions in heavy ion collisions at top RHIC energy

    International Nuclear Information System (INIS)

    Li, Ming; Kapusta, Joseph I.

    2017-01-01

    Heavy ion collisions at extremely high energy, such as the top energy at RHIC, exhibit the property of transparency where there is a clear separation between the almost net-baryon-free central rapidity region and the net-baryon-rich fragmentation region. We calculate the net-baryon rapidity loss and the nuclear excitation energy using the energy-momentum tensor obtained from the McLerran-Venugopalan model. Nuclear compression during the collision is further estimated using a simple space-time picture. The results show that extremely high baryon densities, about twenty times larger than the normal nuclear density, can be achieved in the fragmentation regions. (paper)

  2. A Variety of Activation Methods Employed in 'Activated-Ion' Electron Capture Dissociation Mass Spectrometry: A Test against Bovine Ubiquitin 7+ Ions

    International Nuclear Information System (INIS)

    Oh, Han Bin; McLafferty, Fred W.

    2006-01-01

    Fragmentation efficiencies of various 'activated-ion' electron capture dissociation (AI-ECD) methods are compared for a model system of bovine ubiquitin 7+ cations. In AI-ECD studies, sufficient internal energy was given to protein cations prior to ECD application using IR laser radiation, collisions, blackbody radiation, or in-beam collisions, in turn. The added energy was utilized in increasing the population of the precursor ions with less intra-molecular noncovalent bonds or enhancing thermal fluctuations of the protein cations. Removal of noncovalent bonds resulted in extended structures, which are ECD friendly. Under their best conditions, a variety of activation methods showed a similar effectiveness in ECD fragmentation. In terms of the number of fragmented inter-residue bonds, IR laser/blackbody infrared radiation and 'in-beam' activation were almost equally efficient with ∼70% sequence coverage, while collisions were less productive. In particular, 'in-beam' activation showed an excellent effectiveness in characterizing a pre-fractionated single kind of protein species. However, its inherent procedure did not allow for isolation of the protein cations of interest

  3. Direct chemical-analysis of uv laser-ablation products of organic polymers by using selective ion monitoring mode in gas-chromatography mass-spectrometry

    Science.gov (United States)

    Cho, Yirang; Lee, H.W.; Fountain, S.T.; Lubman, D.M.

    1994-01-01

    Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the laser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in analyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.

  4. Fragmentation of dimethyl ether in femtosecond intense field

    Science.gov (United States)

    Zhu, Jingyi; Guo, Wei; Wang, Yanqiu; Wang, Li

    2006-08-01

    The fragmentation of dimethyl ether (DME) in intense femtosecond laser field has been studied at 810, 405 and 270 nm with intensities up to 2.48 × 10 15, 3.86 × 10 15 and 1.62 × 10 14 W/cm 2, respectively. At 405 nm, DME is possibly firstly ionized by multiphoton absorption, and then parent ion DME + dissociates into fragments via filed-induced dissociation. For 810 and 270 nm laser fields, DME firstly dissociates into CH 3O and CH 3 fragments and then these neutral fragments are ionized by field tunneling. Another possible way for DME to dissociate at 810 and 270 nm is that DME is ionized by intense field ejection of inner valance electron and then the excited DME + dissociates into fragment ions. Ultrafast rearrangement of DME or DME + in intense field may be responsible to the unpredictable fragment ions, CHO+/C2H5+andH2+.

  5. Optimizing recoil-isomer tagging with the Argonne fragment mass analyzer

    International Nuclear Information System (INIS)

    Garnsworthy, A.B.; Lister, C.J.; Regan, P.H.; Blank, B.B.; Cullen, I.J.; Gros, S.; Henderson, D.J.; Jones, G.A.; Liu, Z.; Seweryniak, D.; Shumard, B.R.; Thompson, N.J.; Williams, S.J.; Zhu, S.

    2008-01-01

    A new focal plane detector arrangement for the Fragment Mass Analyzer (FMA) has been built and tested at Argonne National Laboratory. This set-up is particularly sensitive for performing Recoil-Isomer Tagging on nuclei with isomeric states with lifetimes in the microsecond range. Recoiling nuclei from fusion-evaporation reactions at the target position are dispersed by their ratio of mass to charge (A/q) by the FMA and stopped in low pressure gas (air) at the focal plane. Subsequent gamma decays from isomeric states in the reaction products are observed using Ge detectors. A constant gas flow through the focal plane chamber efficiently removes longer-lived beta-decaying species from sight of the detectors. This set-up has been commissioned successfully with the microsecond isomer in 80 Rb, populated via the 52 Cr( 32 S, 3pn) reaction at 135 MeV

  6. Strategy to improve the quantitative LC-MS analysis of molecular ions resistant to gas-phase collision induced dissociation: application to disulfide-rich cyclic peptides.

    Science.gov (United States)

    Ciccimaro, Eugene; Ranasinghe, Asoka; D'Arienzo, Celia; Xu, Carrie; Onorato, Joelle; Drexler, Dieter M; Josephs, Jonathan L; Poss, Michael; Olah, Timothy

    2014-12-02

    Due to observed collision induced dissociation (CID) fragmentation inefficiency, developing sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) assays for CID resistant compounds is especially challenging. As an alternative to traditional LC-MS/MS, we present here a methodology that preserves the intact analyte ion for quantification by selectively filtering ions while reducing chemical noise. Utilizing a quadrupole-Orbitrap MS, the target ion is selectively isolated while interfering matrix components undergo MS/MS fragmentation by CID, allowing noise-free detection of the analyte's surviving molecular ion. In this manner, CID affords additional selectivity during high resolution accurate mass analysis by elimination of isobaric interferences, a fundamentally different concept than the traditional approach of monitoring a target analyte's unique fragment following CID. This survivor-selected ion monitoring (survivor-SIM) approach has allowed sensitive and specific detection of disulfide-rich cyclic peptides extracted from plasma.

  7. Time-of-flight mass spectrographs—From ions to neutral atoms

    Science.gov (United States)

    Möbius, E.; Galvin, A. B.; Kistler, L. M.; Kucharek, H.; Popecki, M. A.

    2016-12-01

    After their introduction to space physics in the mid 1980s time-of-flight (TOF) spectrographs have become a main staple in spaceborne mass spectrometry. They have largely replaced magnetic spectrometers, except when extremely high mass resolution is required to identify complex molecules, for example, in the vicinity of comets or in planetary atmospheres. In combination with electrostatic analyzers and often solid state detectors, TOF spectrographs have become key instruments to diagnose space plasma velocity distributions, mass, and ionic charge composition. With a variety of implementation schemes that also include isochronous electric field configurations, TOF spectrographs can respond to diverse science requirements. This includes a wide range in mass resolution to allow the separation of medium heavy isotopes or to simply provide distributions of the major species, such as H, He, and O, to obtain information on source tracers or mass fluxes. With a top-hat analyzer at the front end, or in combination with deflectors for three-axis stabilized spacecraft, the distribution function of ions can be obtained with good time resolution. Most recently, the reach of TOF ion mass spectrographs has been extended to include energetic neutral atoms. After selecting the arrival direction with mechanical collimation, followed by conversion to ions, adapted TOF sensors form a new branch of the spectrograph family tree. We review the requirements, challenges, and implementation schemes for ion and neutral atom spectrographs, including potential directions for the future, while largely avoiding overlap with complementary contributions in this special issue.

  8. Statistical and off-equilibrium production of fragments in heavy ion collisions at intermediate energies; Production statistique et hors-equilibre de fragments dans les collisions d`ions lourdes aux energies intermediaires

    Energy Technology Data Exchange (ETDEWEB)

    Bocage, Frederic [Lab. de Physique Corpusculaire, Caen Univ., 14 - Caen (France)

    1998-12-15

    The study of reaction products, fragments and light charged particles, emitted during heavy-ion collisions at intermediate energies has shown the dominant binary dissipative character of the reaction, which is persisting for almost all impact parameters. However, in comparison with this purely binary process, an excess of nuclear matter is observed in-between the quasi-projectile and the quasi-target. To understand the mechanisms producing such an excess, this work studies more precisely the breakup in two fragments of the quasi-projectile formed in Xe+Sn, from 25 to 50 MeV/u, and Gd+C and Gd+U at 36 MeV/u. The data were obtained during the first INDRA experiment at GANIL. The angular distributions of the two fragments show the competition between statistical fission and non-equilibrated breakup of the quasi-projectile. In the second case, the two fragments are aligned along the separation axis of the two primary partners. The comparison of the fission directions and probabilities with statistical models allows us to measure the fission time, as well as the angular momentum, temperature and size of the fissioning residue. The relative velocities are compatible with Coulomb and thermal effects in the case of statistical fission and are found much higher for the breakup of a non-equilibrated quasi-projectile, which indicates that the projectile was deformed during interaction with the target. Such deformations should be compared with dynamical calculations in order to constrain the viscosity of nuclear matter and the parameters of the nucleon-nucleon interaction, (author) 148 refs., 77 figs., 11 tabs.

  9. Infrared laser dissociation of single megadalton polymer ions in a gated electrostatic ion trap: the added value of statistical analysis of individual events.

    Science.gov (United States)

    Halim, Mohammad A; Clavier, Christian; Dagany, Xavier; Kerleroux, Michel; Dugourd, Philippe; Dunbar, Robert C; Antoine, Rodolphe

    2018-05-07

    In this study, we report the unimolecular dissociation mechanism of megadalton SO 3 -containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polymer cations and anions with the aid of infrared multiphoton dissociation coupled to charge detection ion trap mass spectrometry. A gated electrostatic ion trap ("Benner trap") is used to store and detect single gaseous polymer ions generated by positive and negative polarity in an electrospray ionization source. The trapped ions are then fragmented due to the sequential absorption of multiple infrared photons produced from a continuous-wave CO 2 laser. Several fragmentation pathways having distinct signatures are observed. Highly charged parent ions characteristically adopt a distinctive "stair-case" pattern (assigned to the "fission" process) whereas low charge species take on a "funnel like" shape (assigned to the "evaporation" process). Also, the log-log plot of the dissociation rate constants as a function of laser intensity between PAMPS positive and negative ions is significantly different.

  10. Analytical Core Mass Function (CMF) from Filaments: Under Which Circumstances Can Filament Fragmentation Reproduce the CMF?

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yueh-Ning; Hennebelle, Patrick [IRFU, CEA, Université Paris-Saclay, F-91191 Gif-sur-Yvette (France); Chabrier, Gilles, E-mail: yueh-ning.lee@cea.fr [École normale supérieure de Lyon, CRAL, UMR CNRS 5574, Université de Lyon, F-69364 Lyon Cedex 07 (France)

    2017-10-01

    Observations suggest that star formation in filamentary molecular clouds occurs in a two-step process, with the formation of filaments preceding that of prestellar cores and stars. Here, we apply the gravoturbulent fragmentation theory of Hennebelle and Chabrier to a filamentary environment, taking into account magnetic support. We discuss the induced geometrical effect on the cores, with a transition from 3D geometry at small scales to 1D at large ones. The model predicts the fragmentation behavior of a filament for a given mass per unit length (MpL) and level of magnetization. This core mass function (CMF) for individual filaments is then convolved with the distribution of filaments to obtain the final system CMF. The model yields two major results. (i) The filamentary geometry naturally induces a hierarchical fragmentation process, first into groups of cores, separated by a length equal to a few filament Jeans lengths, i.e., a few times the filament width. These groups then fragment into individual cores. (ii) Non-magnetized filaments with high MpL are found to fragment excessively, at odds with observations. This is resolved by taking into account the magnetic field (treated simply as additional pressure support). The present theory suggests two complementary modes of star formation: although small (spherical or filamentary) structures will collapse directly into prestellar cores, according to the standard Hennebelle–Chabrier theory, the large (filamentary) ones, the dominant population according to observations, will follow the aforedescribed two-step process.

  11. Gas-phase behaviour of Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands by electrospray ionization mass spectrometry: fragmentation pathways and energetics.

    Science.gov (United States)

    Madeira, Paulo J Amorim; Morais, Tânia S; Silva, Tiago J L; Florindo, Pedro; Garcia, M Helena

    2012-08-15

    The gas-phase behaviour of six Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands, compounds with antitumor activities against several cancer lines, was studied. This was performed with the intent of establishing fragmentation pathways and to determine the Ru-L(N) and Ru-L(P) ligand bond dissociation energies. Such knowledge can be an important tool for the postulation of the mechanisms of action of these anticancer drugs. Two types of instruments equipped with electrospray ionisation were used (ion trap and a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer). The dissociation energies were determined using energy-variable collision-induced dissociation measurements in the ion trap. The FTICR instrument was used to perform MS(n) experiments on one of the compounds and to obtain accurate mass measurements. Theoretical calculations were performed at the density functional theory (DFT) level using two different functionals (B3LYP and M06L) to estimate the dissociation energies of the complexes under study. The influence of the L(N) on the bond dissociation energy (D) of RuCp compounds with different nitrogen ligands was studied. The lability order of L(N) was: imidazole<1-butylimidazole<5-phenyl-1H-tetrazole<1-benzylimidazole. Both the functionals used gave the following ligand lability order: imidazole<1-benzylimidazole<5-phenyl-1H-tetrazole<1-butylimidazole. It is clear that there is an inversion between 1-benzylimidazole and 1-butylimidazole for the experimental and theoretical lability orders. The M06L functional afforded values of D closer to the experimental values. The type of phosphane (L(P) ) influenced the dissociation energies, with values of D being higher for Ru-L(N) with 1-butylimidazole when the phosphane was 1,2-bis(diphenylphosphino)ethane. The Ru-L(P) bond dissociation energy for triphenylphosphane was independent of the type of complex. The D values of Ru-L(N) and Ru-L(P) were determined for all six compounds and

  12. Ionic fragmentation of the isoprene molecule in the VUV energy range (12 to 310 eV)

    Energy Technology Data Exchange (ETDEWEB)

    Bernini, R.B., E-mail: rafael.bernini@ifrj.edu.br [Instituto Federal de Ciência e Tecnologia do Rio de Janeiro (IFRJ), 25050-100 Duque de Caxias, RJ (Brazil); Coutinho, L.H. [Instituto de Física, Universidade Federal do Rio De Janeiro (UFRJ), 21941-972 Rio de Janeiro, RJ (Brazil); Nunez, C.V. [Laboratório de Bioprospecção e Biotecnologia, Coordenação de Tecnologia e Inovação, Instituto Nacional de Pesquisas da Amazônia (INPA), 69060-001 Manaus, AM (Brazil); Castilho, R.B. de [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal do Amazonas (UFAM), 69077-000 Manaus, AM (Brazil); Souza, G.G.B. de [Instituto de Química, Universidade Federal do Rio de Janeiro (UFRJ), 21949-900 Rio de Janeiro, RJ (Brazil)

    2015-07-15

    Highlights: • Ionic fragmentation of isoprene following valence-shell and C 1s excitation. • Experimental observation of single and double ionization processes. • Large increase in fragmentation following core excitation. • Similar dissociation pattern bellow (270 eV) and above (310 eV) core edge. • Stable molecular ion observed at all photon energies. - Abstract: Isoprene, C{sub 5}H{sub 8}, is a biogenic volatile compound emitted from plants and animals, playing an important role in atmospheric chemistry. In this work, we have studied the ionic fragmentation of the isoprene molecule induced by high energy photons (synchrotron radiation), both at the valence (12.0, 14.0, 16.0, 18.0, and 21.0 eV) and carbon 1s edge (270 and 310 eV, respectively, below and above edge) energies. The ionic fragments were mass-analyzed using a Wiley–McLaren time-of-flight spectrometer (TOF) and single (PEPICO) and double ionization coincidence (PEPIPICO) spectra were obtained. As expected, the fragmentation degree increases with increasing energy. Below and above the carbon 1s edge, the fragmentation patterns are quite similar, and basically the same fragments are observed as compared to the spectra following valence-shell ionization. Stable doubly-charged ions were not observed. A PEPIPICO spectrum has shown that the main dissociation route for doubly-ionized species corresponds to the [CH{sub 3}]{sup +}/[C{sub 4}H{sub 2–5}]{sup +} ion pair. Intense fragmentation of the isoprene molecule has been observed following valence shell and core electron ionization. The observance of basically the same fragments when moving from valence to inner-shell suggests that basically the same fragmentation routes are present in both cases. All doubly (or multiply)-charged cations are unstable, at least on a microsecond scale.

  13. On spallation and fragmentation of heavy ions at intermediate energies

    International Nuclear Information System (INIS)

    Musulmanbekov, G.; Al-Haidary, A.

    2002-01-01

    A new code for simulation of spallation and (multi)fragmentation of nuclei in proton and nucleus induced collisions at intermediate and high energies is developed. The code is a combination of modified intranuclear cascade model with traditional fission - evaporation part and multifragmentation part based on lattice representation of nuclear structure and percolation approach. The production of s-wave resonances and formation time concept included into standard intranuclear cascade code provides correct calculation of excitation energy of residues. This modified cascade code served as a bridge between low and high energy model descriptions of nucleus-nucleus collisions. A good agreement with experiments has been obtained for multiparticle production at intermediate and relatively high energies. Nuclear structure of colliding nuclei is represented as face centered cubic lattice. This representation, being isomorphic to the shell model of nuclear structure, allows to apply percolation approach for nuclear fragmentation. The offered percolation model includes both site and bond percolation. Broken sites represent holes left by nucleons knocked out at cascade state. Therefore, in the first cascade stage mutual rescattering of the colliding nuclei results in knocking some nucleons out of them. After this fast stage paltrily destruct and excited residues remain. On the second stage residual nuclei either evaporate nucleons and light nuclei up to alpha-particles or fragment into pieces with intermediate masses. The choice depends on residue's destruction degree. At low excitation energy and small destruction of the residue the evaporation and fission mechanisms are preferable. The more excitation energy and destruction the more probability of (multi)fragmentation process. Moreover, the more destruction degree of the residual the more the site percolation probability. It is concluded, that at low and intermediate excitation energies the fragmentation of nuclei is slow

  14. Universality of projectile fragmentation model

    International Nuclear Information System (INIS)

    Chaudhuri, G.; Mallik, S.; Das Gupta, S.

    2012-01-01

    Presently projectile fragmentation reaction is an important area of research as it is used for the production of radioactive ion beams. In this work, the recently developed projectile fragmentation model with an universal temperature profile is used for studying the charge distributions of different projectile fragmentation reactions with different projectile target combinations at different incident energies. The model for projectile fragmentation consists of three stages: (i) abrasion, (ii) multifragmentation and (iii) evaporation