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Ion Formation (ion + formation)
Selected AbstractsCatalytic cracking, dehydrogenation, and aromatization of isobutane over Ga/HZSM-5 and Zn/HZSM-5 at low pressuresINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2002Yanping Sun Isobutane cracking, dehydrogenation, and aromatization over Ga/HZSM-5 and Zn/HZSM-5 has been investigated in a Knudsen cell reactor and the kinetics of the primary reaction steps for isobutene and propene formation have been accurately determined. Although cracking is the dominant reaction channel, with propene and methane being primary products, methane formation is significantly less than propene formation. This indicates that a proportion of the cracking proceeds via Lewis acid attack at CC bonds, and not just via alkanium ion formation at Bronsted acid sites. This is particularly apparent over Zn/HZSM-5. Intrinsic rate constants for cracking, calculated from the rate of propene formation, are and for dehydrogenation, calculated from the rate of isobutene formation, are Large preexponential factors for cracking and dehydrogenation over Ga/HZSM-5 indicate that either the coverage of active sites is significantly less than the coverage of exposed sites or the intrinsic reaction step involves a large entropy change between reactant and transition state. For Zn/HZSM-5 the small preexponential factors suggest either small entropy changes during activation, perhaps initiated by Lewis acid sites, or a steady-state distribution of active and exposed sites is rapidly reached. Differences in intrinsic activation energies may reflect the ratio of Lewis and Bronsted acid sites on the respective catalyst surfaces. Aromatization is more prolific over Ga/HZSM-5 than over Zn/HZSM-5 under the low-pressure conditions. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 467,480, 2002 [source] Synthesis of 14C-labeled piperidines and application to synthesis of [14C]SCH 351125, a CCR5 receptor antagonistJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 7 2007Sumei Ren Abstract 1-Benzyl-4-hydroxy[2- 14C]piperidine, a useful intermediate in labeled compound synthesis, was prepared from [14C]formaldehyde in high yield. The distribution pattern of 14C in the product is consistent with a mechanism involving reversible iminium ion formation and rapid equilibration of the iminium ion through a cationic aza-Cope rearrangement. These steps precede the rate-determining intramolecular cyclization step. SCH 351125 is a potent, selective CCR5 receptor antagonist with potential as a treatment for HIV infection. [14C]SCH 351125, required for metabolism studies, was prepared from 1-benzyl-4-hydroxy[2- 14C]piperidine in six steps. [14C]SCH 351125 is a mixture of four atropisomers. Preparation of [14C]SCH 351125 besylate salt of the desired atropisomer pair is also described. Copyright © 2007 John Wiley & Sons, Ltd. [source] Direct analysis of lipids in mouse brain using electrospray droplet impact/SIMSJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 4 2010Daiki Asakawa Abstract Electrospray droplet impact (EDI)/secondary ion mass spectrometry (SIMS) is a new desorption/ionization technique for mass spectrometry in which highly charged water clusters produced from the atmospheric-pressure electrospray are accelerated in vacuum by 10 kV and impact the sample deposited on the metal substrate. EDI/SIMS was shown to enhance intact molecular ion formation dramatically compared to conventional SIMS. EDI/SIMS has been successfully applied to the analysis of mouse brain without any sample preparation. Five types of lipids, i.e. phosphatidylcholine (PC), phosphatidylserine, phosphatidylinositol (PI), galactocerebroside (GC) and sulfatide (ST), were readily detected from mouse brain section. In addition, by EDI/SIMS, six different regions of the mouse brain (cerebral cortex, corpus callosum, striatum, medulla oblongata, cerebellar cortex and cerebellar medulla) were examined. While GCs and STs were found to be rich in white matter, PIs were rich in gray matter. Copyright © 2010 John Wiley & Sons, Ltd. [source] Towards a universal product ion mass spectral library , reproducibility of product ion spectra across eleven different mass spectrometersRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2008Chris Hopley Product ion spectra produced by collision-induced dissociation (CID) in tandem mass spectrometry experiments can differ markedly between instruments. There have been a number of attempts to standardise the production of product ion spectra; however, a consensus on the most appropriate approach to the reproducible production of spectra has yet to be reached. We have previously reported the comparison of product ion spectra on a number of different types of instruments , a triple quadrupole, two ion traps and a Fourier transform ion cyclotron resonance mass spectrometer (Bristow AWT, Webb KS, Lubben AT, Halket JM. Rapid Commun. Mass Spectrom. 2004; 18: 1). The study showed that a high degree of reproducibility was achievable. The goal of this study was to improve the comparability and reproducibility of CID product ion mass spectra produced in different laboratories and using different instruments. This was carried out experimentally by defining a spectral calibration point on each mass spectrometer for product ion formation. The long-term goal is the development of a universal (instrument independent) product ion mass spectral library for the identification of unknowns. The spectra of 48 compounds have been recorded on eleven mass spectrometers: six ion traps, two triple quadrupoles, a hybrid triple quadrupole, and two quadrupole time-of-flight instruments. Initially, 4371 spectral comparisons were carried out using the data from eleven instruments and the degree of reproducibility was evaluated. A blind trial has also been carried out to assess the reproducibility of spectra obtained during LC/MS/MS. The results suggest a degree of reproducibility across all instrument types using the tuning point technique. The reproducibility of the product ion spectra is increased when comparing the tandem in time type instruments and the tandem in space instruments as two separate groups. This may allow the production of a more limited, yet useful, screening library for LC/MS/MS identification using instruments of the same type from different manufacturers. Copyright © 2008 John Wiley & Sons, Ltd. [source] Role of the support material on laser desorption/ionization mass spectraRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 7 2008A. Gruszecka We report the results of experimental studies on the effects of sample supports in laser desorption/ionization mass spectrometry (LDI-MS). LDI time-of-flight (TOF) mass spectra obtained for C60 and insulin samples deposited onto standard stainless steel substrate and/or onto some non-metallic materials (glass, scotch tape, floppy disc foil, Teflon foil, photocopy film), all recorded under identical, typical experimental conditions, have been compared with regard to their intensity and quality. The LDI investigations show that compared with stainless steel, glass and floppy disc foil sample supports boost (2,3.5 times) ion yields for C and C ions, respectively. The stainless steel and scotch tape sample supports are the best for the mass resolution of positive ions and the formation of (C60) (n,,,4) cluster ions, respectively. In the case of detection of insulin by matrix-assisted laser desorption/ionization (MALDI) we did not observe significant differences in sensitivity for the support materials tested. A mechanism of ion formation in the desorption plume is suggested. Copyright © 2008 John Wiley & Sons, Ltd. [source] Electron capture dissociation mass spectrometry of peptide cations containing a lysine homologue: a mobile proton model for explaining the observation of b-type product ionsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 21 2006Sunyoung Lee Eleven doubly protonated peptides with a residue homologous to lysine were investigated by electron capture dissociation mass spectrometry (ECD-MS). Lysine homologues provide the unique opportunity to examine the ECD fragmentation behavior by allowing us to vary the length of the lysine side chain, with minimal structural change. The lysine homologue has a primary amine side chain with a length that successively decreases by one methylene (CH2) unit from the CH2CH2CH2CH2NH2 of lysine and the accompanying decrease of its proton affinities: lysine (K), 1006.5(±7.2) kJ/mol; ornithine (K*), 1001.1(±6.6) kJ/mol; 2,4-diaminobutanoic acid (K**), 975.8(±7.4) kJ/mol; 2,3-diaminopropanoic acid (K***), 950.2(±7.2) kJ/mol. In general, the lysine-homologous peptides exhibited overall ECD fragmentation patterns similar to that of the lysine-containing peptides in terms of the locations, abundances, and ion types of products, such as yielding c+ and z+. ions as the dominant product ions. However, a close inspection of product ion mass spectra showed that ECD-MS for the alanine-rich peptides with an ornithinyl or 2,4-diaminobutanoyl residue gave rise to b ions, while the lysinyl-residue-containing peptides did not, in most cases, produce any b ions. The peptide selectivity in the generation of b+ ions could be understood from within the framework of the mobile proton model in ECD-MS, previously proposed by Cooper (Ref. 29). The exact mass analysis of the resultant b ions reveals that these b ions are not radical species but rather the cationic species with R-CO+ structure (or protonated oxozalone ion), that is, b+ ions. The absence of [M+2H]+. species in the ECD mass spectra and the selective b+ -ion formation are evidence that the peptides underwent H-atom loss upon electron capture, and then the resulting reduced species dissociated following typical MS/MS fragmentation pathways. This explanation was further supported by extensive b+ ions generated in the ECD of alanine-based peptides with extended conformations. Copyright © 2006 John Wiley & Sons, Ltd. [source] Phenol, chlorobenzene and chlorophenol isomers: resonant states and dissociative electron attachment,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 20 2003Roustem V. Khatymov This paper reports a study of resonant dissociative electron attachment (DEA) to the phenol, chlorobenzene, p- , m- , and o- chlorophenol molecules. On the basis of spectroscopic and thermochemical approaches the resonant states of the molecular negative ions (NIs) and the structures of some dissociative decay products are assigned. In the electron energy range up to 3,eV, DEA processes are determined by the two 2[,*]-shape resonances resulting mainly in formation of [MH], and/or Cl, ions. At higher electron energies the energy correlation between peaks in the negative ion effective yield curves and bands of UV spectra allowed identification of the core-excited resonances. The peculiarities of Cl, ion formation and the vibrational fine structure on the effective yield curves of the [MH], ions are discussed. The mass spectrometric procedures for measurement of relative cross sections for NI formation are described. Copyright © 2003 John Wiley & Sons, Ltd. [source] Secondary ion formation of low molecular weight organic dyes in time-of-flight static secondary ion mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 18 2003Jens Lenaerts Time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) was used to characterize thin layers of oxy- and thiocarbocyanine dyes on Ag and Si. Apart from adduct ions a variety of structural fragment ions were detected for which a fragmentation pattern is proposed. Peak assignments were confirmed by comparing spectra of dyes with very similar structures. All secondary ions were assigned with a mass accuracy better than 50,ppm. The intensity of molecular ions as well as fragment ions has been studied as a function of the type of organic dye, the substrate, the layer thickness and the type of primary ion. A large yield difference of two orders of magnitude was observed between the precursor ions of cationic carbocyanine dyes and the protonated molecules of the anionic dyes. Fragment ions, on the other hand, yielded similar intensities for both types of dye. As the dye layers deposited on an Ag substrate yielded higher secondary ion intensities than those deposited on a Si substrate, the Ag metal clearly acts as a promoting agent for secondary ion formation. The effect was more pronounced for precursor signals than for fragment ions. The promoting effect decreased as the deposited layer thickness of the organic dye layer was increased. Copyright © 2003 John Wiley & Sons, Ltd. [source] Application of sulfur as a matrix for laser desorption/ionization in the characterization of halogenated fullerenesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2002Alexey V. Streletskiy The application of sulfur as a matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis of highly chlorinated and fluorinated fullerenes is reported. Control over fluorofullerene fragmentation which resulted in the domination of the molecular peak C60F36, was achieved, with the optimal matrix-to-analyte ratio found to be 1000:1. We suggest the possible mechanism of the molecular ion formation according to the charge transfer between the sulfur anions and C60F36. For the first time the LDI and MALDI mass spectra of the highly chlorinated fullerene C60Clx(xmax,,,32) are presented. The formation of odd chlorine ions (positive and negative) is observed. We conclude that use of sulfur as a matrix leads to a significant decrease in fragmentation of the halogenated fullerenes. Copyright © 2001 John Wiley & Sons, Ltd. [source] The effect of alkylamine additives on the sensitivity of detection for paclitaxel and docetaxel and analysis in plasma of paclitaxel by liquid chromatography,tandem mass spectrometryBIOMEDICAL CHROMATOGRAPHY, Issue 8 2006Songmei Gao Abstract The formation of multiple molecular ions, especially due to sodium adduct ion formation, is commonly observed in electrospray mass spectrometry and may make reproducible and sensitive quantitation difficult. The objective of this work was to investigate the underlying mechanism involved in the suppression of multiple molecular ion formation and to improve the sensitivity of detection for the two anti-neoplastic agents paclitaxel and docetaxel. The results showed that alkylamine additives could significantly improve the detection of paclitaxel and docetaxel by suppression of multiple molecular ions through preferential formation of a predominant alkylamine adduct ion. Possible binding sites, binding interactions and binding competition were investigated for the sodium adduct and alkylamine adduct ions using various experimental techniques. The formation of a predominant amine adduct ion may be due to increased surface activity in the droplet. The optimal alkylamine for both analytes was octylamine, which increased peak heights of paclitaxel and docetaxel 4.8 and 3.7-fold (n = 3), respectively. The precision of the signals for the analytes was also improved 5.7-fold. A quantitative assay in plasma for paclitaxel was partially validated for the calibration range 1.0,1000 ng/mL (r = 0.9977) when using 0.05% octylamine as a reconstitution solution additive. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.5 and 0.9 ng/mL, respectively. Acceptable precision, accuracy, specificity and sample stability were demonstrated for this assay. This approach may prove useful for other analytes with similar binding sites. Copyright © 2005 John Wiley & Sons, Ltd. [source] | ||||||||||