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排序方式: 共有115条查询结果,搜索用时 46 毫秒
1.
The use of a direct liquid introduction type liquid chromatographic-mass spectrometric interface to study highly thermally labile rifamycin antibiotics is described. Using negative ionization, abundant molecular ions were observed, and the spectra, also contained structurally significant fragments. Variation of the high-performance liquid chromatographic parameters did not change the spectra, thus making it easy to change chromatographic conditions. In quantitative studies, a surprising correlation was found, indicating that the mass spectrometric signal was proportional to the square of the sample concentration. 相似文献
2.
The kinetic method is one of the most widely used experimental techniques for the measurement of thermochemical parameters by mass spectrometry. Recently it has been realized that it can also be used to determine reaction entropies, but the validity of this approach has not been established. This Perspective evaluates kinetic method plots in cases where there is a significant entropy difference between the competing fragmentation channels (i.e. between sample and reference compounds in the dissociating cluster ion). The concept underlying this study is to calculate mass spectra theoretically, based on known thermochemical parameters and as a function of experimental conditions. This can be done accurately using the RRKM-based MassKinetics software. The resulting mass spectra are then interpreted by the kinetic method, yielding DeltaH and DeltaS values. These values are, in turn, compared with the true values used to generate the calculated mass spectra. The results show that the reaction entropy difference between sample and reference has a very large influence on kinetic method plots. This should always be considered when studying energy-dependent mass spectra (using metastable ions or low- or high-energy collision-induced dissociation (CID)), even if only DeltaH is to be determined. Kinetic method plots are not strictly linear and this becomes a serious issue in the case of small molecules showing a large entropy effect. In such cases, results obtained at a low degree of excitation are more accurate. Energy and entropy effects can be evaluated in a relatively straightforward manner: first, the apparent Gibbs energy (DeltaG(app)) and effective temperature (T(eff)) are determined from kinetic method plots (intercept and slope, respectively), obtained from experiments using various degrees of excitation. Second, the resulting DeltaG(app) is plotted against T(eff), the slope yielding DeltaS while the intercept (extrapolation to zero temperature) yields DeltaH. This data evaluation yields more accurate results than alternative methods used in the literature. The resulting DeltaH values are fairly accurate, with errors, in most cases, <4 kJ mol(-1). On the other hand, DeltaS is systematically underestimated by 20-40%. Empirically scaling DeltaS values determined by the kinetic method by 1.35 results in a DeltaS value within 20% (or 10 J mol(-1) K(-1)) of the theoretical value. 相似文献
3.
Kroly Vkey Duncan M. F. Edwards Luigi F. Zerilli Marianna Mk Jzsef Tams Vittorio Raverdino Antonio Selva 《Journal of mass spectrometry : JMS》1990,25(9):465-474
Results of 16 different mass spectrometric ionization and sample-introduction methods are compared for the case of a thermally very labile antibiotic, rifapentine. These suggest that extensive thermal decomposition occurs during evaporation when the sample can come into contact with hot metal parts, usually the source housing. The intensity of the molecular ion and the extent of fragmentation depend on various parameters, such as the ionization process, positive or negative-ion detection and the type of sample introduction. The most informative methods for rifapentine seem to be ‘in-beam’ electron impact, negative ionization with particle beam and direct liquid introduction interfaces and positive- and negative-ion fast atom bombardment. 相似文献
4.
Examples of various chemical reactions occurring in the matrix or in the selvedge region in fast atom bombardment (FAB) mass spectrometry are discussed. These are categorized as oxidations and reductions; substitutions; clusterings and additions; and sample decomposition or transformation. Some reactions observed showed significant time behaviour and in one case it was possible to determine rate constants. These data suggest that chemical reactions can be accelerated significantly by fast atom bombardment. 相似文献
5.
Karoly Vkey Jzsef Tams Arpd Somogyi Antonella Bertazzo Carlo Costa Graziella Allegri Roberta Seraglia Piero Traldi 《Journal of mass spectrometry : JMS》1992,27(11):1216-1219
Structural studies of a synthetic melanin, obtained by means of performic acid oxidation of tryptophan, were carried out by pyrolysis gas chromatography/mass Spectrometry (Py-GC/MS). To identify the best pyrolysis conditions, both Curie-point pyrolysis and filament pyrolysis were employed and the effects of pyrolysis temperatures and times were studied. Using the first approach, various compounds were identified: toluene, ethylbenzene, styrene, indole, methylindole, ethylindole, phenol, cresol and ethylphenol. Using filament pyrolysis some interesting differences could be observed. Whereas toluene, ethylbenzene, phenol, cresol and methylindole were found, neither indole nor ethylindole was detected. Instead, new pyrolysis products were evident, such as methylpyrrole and indolin-2-one. Hence filament pyrolysis seems to activate different thermal decomposition pathways of the melanin under study. It is suggested that tryptophan melanin is a polymer containing indole and hydroxyindole derivatives as subunits. 相似文献
6.
Imre T Schlosser G Pocsfalvi G Siciliano R Molnár-Szöllosi E Kremmer T Malorni A Vékey K 《Journal of mass spectrometry : JMS》2005,40(11):1472-1483
A new anionic surfactant (RapiGest SF) was successfully used for site-specific analysis of glycosylation in human alpha-1-acid glycoprotein (AGP). By means of this analytical approach combined with capillary HPLC-mass spectrometry (and tandem mass spectrometry), the N-linked glycosylation pattern of AGP was explored. On the basis of mass matching and MS/MS experiments ca 80 different AGP-derived glycopeptides were identified. Glycosylation shows a markedly different pattern for the various glycosylation sites. At sites I and II, triantennary complex-type oligosaccharides predominate and at sites III, IV and V, tetra-antennary complex-type oligosaccharides predominate. Sites IV and V show the presence of additional N-acetyl lactosamine (Gal-GlcNAc) units (even higher degree of branching and/or longer antennae are also present). 相似文献
7.
QI GuoPeng JIANG Feng SUN XueWen & ZHAO SuoQi School of Chemical Engineering Tianjin University Tianjin China State key Laboratory of Heavy Oil Processing Petroleum University of China Beijing China 《中国科学:化学》2010,(5)
The isotope exchange method was employed to investigate the catalytic mechanism of ionic liquid in alkylation of benzenes with olefins.It is proposed that alkylation was induced by the Lewis acid AlCl3 which attracted π electrons of 1-dodecene to shift toward 1-carbon,thus forming a carbonium ion.The carbonium ion further reacted with benzenes to form a complex.Due to unstabilit of the complex,a deuterated ring proton was transferred into an electronegative 1-carbon of the side chain to substitute for the A... 相似文献
8.
Serena Indelicato David Bongiorno Sergio Indelicato Laszlo Drahos Vincenzo Turco Liveri Lilla Turiák Karoly Vékey Leopoldo Ceraulo 《Journal of mass spectrometry : JMS》2013,48(3):379-383
The characteristic collision energy (CCE) to obtain 50% fragmentation of positively and negatively single charged noncovalent clusters has been measured. CCE was found to increase linearly with the degrees of freedom (DoF) of the precursor ion, analogously to that observed for synthetic polymers. This suggests that fragmentation behavior (e.g. energy randomization) in covalent molecules and clusters are similar. Analysis of the slope of CCE with molecular size (DoF) indicates that activation energy of fragmentation of these clusters (loss of a monomer unit) is similar to that of the lowest energy fragmentation of protonated leucine–enkephalin. Positively and negatively charged aggregates behave similarly, but the slope of the CCE versus DoF plot is steeper for positive ions, suggesting that these are more stable than their negative counterparts. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
9.
A simple method capable of generating and investigating various solvent clusters and solvated ions was developed. The technique opens a door to studying these complexes on commercially available instruments. Formation of the desired solvated ion in the gas phase was achieved by introducing the appropriate volatile solvent vapour into the curtain gas stream. Capabilities of the technique are illustrated by generating alkali, alkaline earth and transition metal cations solvated by various volatile compounds such as water, methanol and acetonitrile. Depending on the ligands and on the experimental conditions, clusters of 2-100 molecules may be observed. Isotope labelling suggests that these are formed by a re-solvation process in the curtain gas region. 相似文献
10.
Tibor Novák Péter Bakó György Keglevich András Dobó Károly Vékey László Tóke 《Journal of inclusion phenomena and macrocyclic chemistry》2001,40(3):207-212
Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee). 相似文献