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排序方式: 共有92条查询结果,搜索用时 15 毫秒
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The retention characteristics of two novel 21-aminosteroid antioxidants, 21-[4-(2,6-di-1-pyrrolidinyl-4-pyrimidinyl)-1-piperazinyl]-16 alpha-methylpregna-1,4,9(11)-triene-3,20-dione dimethanesulfonate (I) and 21-[4-(2,5-di-N-diethylamine-2-pyridinyl)-1-piperazinyl]-16 alpha-methylpregna-1,4,9(11)-triene-3,20-dione hydrochloride (II), in octylsilane bonded-phase high-performance liquid chromatography were examined in detail. Both I and II exhibited irregular retention behaviour which could be explained by the dual retention mechanism model proposed by A. Nahum and Cs. Horváth [J. Chromatogr., 203 (1981) 53]. Unless an amine modifier was added to competitively inhibit association with exposed silanol binding sites, the retention of both compounds in a 70% acetonitrile mobile phase was primarily due to silanophilic interactions. Addition of amine modifiers, lowering the pH, and increasing the sodium ion concentration of the mobile phase all decreased retention times, and modifiers capable of hydrogen bonding diminished peak tailing. 相似文献
54.
Abaye DA Pullen FS Nielsen BV 《Rapid communications in mass spectrometry : RCM》2011,25(23):3597-3608
Electrospray ionisation (ESI) is a selective process and, for similar sized analytes, the intrinsic properties of the molecules affect the ionisation process and their response. This research sets out to determine the effect of some of these properties in peptides: peptide polarity and the presence of arginine at positions 1 and 4 in the amino acid sequence on the ESI response. Six peptides; molecular mass ranges 1.3-1.6 kDa; substance P (SP) and glutamate fibrinopeptide (GFP) and 3.2-3.7 kDa; calcitonin gene-related peptide (CGRP), vasoactive intestinal peptide (VIP), glucagon-like peptide 1 (GLP1) and defensin human neutropeptide 2 (DHNP2), were investigated. We have demonstrated that in positive ESI, for similar sized peptides and the same charge state, the responsiveness is in the order: Peptides with N or C terminal arginine > most non-polar peptides > least non-polar peptides. Therefore, arginine at the terminal position is a source of selectivity. Data from matrix-assisted laser desorption ionisation (MALDI) analysis supports that of the ESI experiments: Peptides with a terminal arginine residue generated higher signal intensities. Our observations extend our understanding of the ESI process and provide a rational approach to optimising sensitivity of electrospray conditions where a narrow mass range of peptides are poorly chromatographically resolved. This information will provide for a more effective method development process, especially during label-free quantitative determination of peptides extracted in solution. 相似文献
55.
Shihuai Wang Dr. Sonja Pullen Valentin Weippert Dr. Tianfei Liu Prof. Sascha Ott Assoc. Prof. Reiner Lomoth Prof. Leif Hammarström 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11135-11140
[FeFe(Cl2-bdt)(CO)6] ( 1 ; Cl2-bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e− reduction at −1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H −, which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency. 相似文献
56.
Patricia Wright Alexander Alex Tsitsi Nyaruwata Teresa Parsons Frank Pullen 《Rapid communications in mass spectrometry : RCM》2010,24(7):1025-1031
Tandem mass spectrometry (MS/MS) is widely used for the identification of metabolites at all stages of the pharmaceutical discovery and development process. The assignment of ions in the product ion spectra can be time‐consuming and hence delay feedback of results that may influence the direction of a project. A deeper understanding of the processes involved in generation of the product ions formed via collision‐induced dissociation may allow development of chemically intelligent software to aid spectral interpretation. Current commercially available spectral interpretation software takes a mainly arithmetical approach resulting in extensive lists of numerically plausible ions, many of which may not be chemically feasible. In this study, high‐resolution MS/MS spectra were obtained for maraviroc and two of its synthetic metabolites, and structures for the product ions proposed. Density functional theory (DFT) based on in silico modelling was undertaken to investigate whether the fragmentation observed was potentially a result of bond lengthening (and hence weakening) as a consequence of protonation of the molecule at the most thermodynamically stable site(s). It was determined that for all three compounds, where the product ions resulted from simple bond cleavages (not rearrangements), the bonds that cleaved had been calculated to elongate after protonation. It was also noted that the protonated molecule may represent a mixture of singly charged protonated species and that the most basic sites in the molecule may not necessarily be the most thermodynamically stable for protonation. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
57.
Bonalde I Yanoff BD Salamon MB Van Harlingen DJ Chia EM Mao ZQ Maeno Y 《Physical review letters》2000,85(22):4775-4778
We report measurements of the magnetic penetration depth in single crystals of Sr2RuO4 down to 0.04 K using a tunnel-diode based, self-inductive technique. We observe a power law temperature dependence below 0.8 K, with no sign of a second phase transition nor of a crossover predicted for a multiband superconductor. A power law dependence suggests that the gap function has nodes, inconsistent with candidate p-wave states. We argue that nonlocal effects, rather than impurity scattering, can explain the observed T2 dependence instead of the T-linear behavior expected for line nodes. 相似文献
58.
DJ Smith KW Ledingham RP Singhal T McCanny P Graham HS Kilic P Tzallas C Kosmidis AJ Langley PF Taday 《Rapid communications in mass spectrometry : RCM》1999,13(14):1366-1373
With the development of high intensity femtosecond lasers, the ionisation and dissociation dynamics of molecules has become an area of considerable interest. Using the technique of femtosecond laser mass spectrometry (FLMS), the molecules carbon disulphide, pyrimidine, toluene, cyclohexanone and benzaldehyde are studied with pulse widths of 50 fs in the near infrared (IR) wavelength region (790 nm). Results are presented and contrasted for laser beam intensities around 10(15) and 10(16) W cm(-2). For the lower intensities, the mass spectra yield dominant singly charged parent ions. Additionally, the appearance of doubly charged parent ions is evident for carbon disulphide, toluene and benzaldehyde with envelopes of doubly charged satellite species existing in these local regions. Carbon disulphide also reveals a small triply charged component. Such atomic-like features are thought to be a strong fingerprint of FLMS at these intensities. However, upon increasing the laser intensity to approximately 10(16) W cm(-2), parent ion dominance decreases and the appearance of multiply charged atomic species occurs, particularly carbon. This phenomenon has been attributed to Coulomb explosions in which the fast absorption of many photons may produce transient highly ionised parent species which can subsequently blow apart. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
59.
X Fang KW Ledingham P Graham DJ Smith T McCanny RP Singhal AJ Langley PF Taday 《Rapid communications in mass spectrometry : RCM》1999,13(14):1390-1397
The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
60.
Frank S. Pullen George L. Perkins Keith I. Burton Richard S. Ware Mathew S. Teague Jeffrey P. Kiplinger 《Journal of the American Society for Mass Spectrometry》1995,6(5):394-399
The ease of use of the newer liquid chromatography-mass spectrometry interfaces has made possible the automated acquisition of spectra from large batch queues of samples. This fact, combined with the realization that unit molecular mass determination was the only datum desired by a majority of drug discovery synthetic chemists, led us to develop open access mass spectrometry in the early 1990s. Open access spectrometers now scan over 100,000 samples per year from synthesis laboratories at Pfizer. Our experiences with this novel use of mass spectrometry in a large research facility are discussed and we detail some of the pitfalls we believe to be common to this approach. In addition, we offer some reflection on the cultural changes we have observed in our research environment since this experiment began. 相似文献