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Low Collision Energy (low + collision_energy)
Selected AbstractsReactions of BBrn+ (n = 0,2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion,surface scatteringJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 7 2001Nathan Wade Abstract Ion,surface reactions involving BBrn+ (n = 0,2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B+ ion yield BF2+ at threshold energy with the simpler product ion BF+· appearing at higher collision energies and remaining of lower abundance than BF2+ at all energies examined. In addition, the reactively sputtered ion CF+ accompanies the formation of BF2+ at low collision energies. These results stand in contrast with previous data on the ion,surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF2+ being the thermodynamically favored product. The fact that the abundance of BF2+ is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum,surface interface, one which involves interaction of the B+ ion simultaneously with two fluorine atoms. By contrast with the reaction of B+, the odd-electron species BBr+· reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF+. Corresponding gas-phase ion,molecule experiments involving B+ and BBr+· with C6F14 also yield the products BF+· and BF2+, but only in extremely low abundances and with no preference for double fluorine abstraction. Ion,surface reactions were also investigated for BBrn+ (n = 0,2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B+ ion and dissociative reactions of BBr+· result in the formation of BH2+, while the thermodynamically less favorable product BH+· is not observed. Collisions of BBr2+ with the H-SAM surface yield the dissociative ion,surface reaction products, BBrH+ and BBrCH3+. Substitution of bromine atoms on the projectile by hydrogen or alkyl radicals suggests that Br atoms may be transferred to the surface in a Br-for-H or Br-for-CH3 transfer reaction in an analogous fashion to known transhalogenation reactions at the F-SAM surface. The results for the H-SAM surface stand in contrast to those for the F-SAM surface in that enhanced neutralization of the primary ions gives secondary ion signals one to two orders of magnitude smaller than those obtained when using the F-SAM surface, consistent with the relative ionization energies of the two materials. Copyright © 2001 John Wiley & Sons, Ltd. [source] Direct injection horse-urine analysis for the quantification and confirmation of threshold substances for doping control.DRUG TESTING AND ANALYSIS, Issue 8 2009Abstract Levodopa and dopamine have been abused as performance-altering substances in horse racing. Urinary 3-methoxytyramine is used as an indicator of dopaminergic manipulation resulting from dopamine or levodopa administration and is prohibited with a urinary threshold of 4 µg mL,1 (free and conjugated). A simple liquid chromatographic (LC)/mass spectrometric (MS) (LCMS) method was developed and validated for the quantification and identification of 3-methoxytyramine in equine urine. Sample preparation involved enzymatic hydrolysis and protein precipitation. Hydrophilic interaction liquid chromatography (HILIC) was selected as a separation technique that allows effective retention of polar substances like 3-methoxytyramine and efficient separation from matrix compounds. Electrospray ionization (ESI) in positive mode with product ion scan mode was chosen for the detection of the analytes. Quantification of 3-methoxytyramine was performed with fragmentation at low collision energy, resulting in one product ion, while a second run at high collision energy was performed for confirmation (at least three abundant ions). Studies on matrix effects showed ion suppression depending on the horse urine used. To overcome the variability of the results originating from the matrix effects, isotopic labelled internal standard was used and linear regression calibration methodology was applied for the quantitative determination of the analyte. The tested linear range was 1,20 µg mL,1. The relative standard deviations of intra- and inter- assay analysis of 3-methoxytyramine in horse urine were lower than 4.2% and 3.2%, respectively. Overall accuracy (relative percentage error) was less than 6.2%. The method was applied to case samples, demonstrating simplicity, accuracy and selectivity. Copyright © 2009 John Wiley & Sons, Ltd. [source] UPLC/MSE; a new approach for generating molecular fragment information for biomarker structure elucidationRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 13 2006Robert S. Plumb A new approach to obtain fragmentation information in liquid chromatography/mass spectrometry (LC/MS) studies of small molecules in complex mixtures is presented using simultaneous acquisition of exact mass at high and low collision energy, MSE. LC/MS-TOF and LC/MS/MS-TOF are powerful tools for the analysis of complex mixtures, especially those for biological fluids allowing the elucidation of elemental composition and fragmentation information. In this example the composition of rat urine was studied using this new approach, allowing the structures of several endogenous components to be confirmed in one analytical run by the simultaneous acquisition of exact mass precursor and fragment ion data. The spectral data obtained using this new approach are comparable to those obtained by conventional LC/MS/MS as exemplified by the identification of endogenous metabolites present in rat urine. Copyright © 2006 John Wiley & Sons, Ltd. [source] Cluster ions of diquat and paraquat in electrospray ionization mass spectra and their collision-induced dissociation spectraRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2003Boris L. Milman Cluster ions such as [Cat+X+nM]+ (n,=,0,4); [Cat-H+nM]+ (n,=,1,3); and [2(Cat-H)+X+nM]+ (n,=,0,2), where Cat, X, and M are the dication, anion, and neutral salt (CatX2), respectively, are observed in electrospray ionization (ESI) mass spectrometry of relatively concentrated solutions of diquat and paraquat. Collision-induced dissociation (CID) reactions of the clusters were observed by tandem mass spectrometry (MS/MS), including deprotonation to form [Cat-H]+, one-electron reduction of the dication to form Cat+., demethylation of the paraquat cation to form [Cat-CH3]+, and loss of neutral salt to produce smaller clusters. The difference in acidity and reduction power between diquat and paraquat, evaluated by thermodynamical estimates, can rationalize the different fractional yields of even-electron ([Cat-H]+ and its clusters) and odd-electron (mostly Cat+.) ions in ESI mass spectra of these pesticides. The [Cat+n,·,Solv]2+ doubly charged cluster ions, where n,,,2 and Solv is the solvent molecule (methanol and/or water), are only observed as very weak peaks in precursor ion CID spectra of the Cat2+ salt cation at low collision energy. The presence of an anion and a solvent molecule in a cluster is assumed to be related to existence of tight and loose ion pairs, respectively, in multiply charged droplets/ions formed by ESI. The results emphasize again the role of solution chemistry concepts such as acidity/basicity, redox power, and ion-pair formation, for ESI. Copyright © 2003 John Wiley & Sons, Ltd. [source] |