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排序方式: 共有253条查询结果,搜索用时 593 毫秒
61.
Asbury JB Steinel T Kwak K Corcelli SA Lawrence CP Skinner JL Fayer MD 《The Journal of chemical physics》2004,121(24):12431-12446
Vibrational echo correlation spectroscopy experiments on the OD stretch of dilute HOD in H(2)O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different infrared pulse bandwidths (pulse durations), making it possible to use data collected from many experiments in which the laser pulse properties are not identical. Accurate measurements of the OD stretch anharmonicity (162 cm(-1)) are presented and used in the data analysis. In addition, the recent accurate determination of the OD vibrational lifetime (1.45 ps) and the time scale for the production of vibrational relaxation induced broken hydrogen bond "photoproducts" ( approximately 2 ps) aid in the data analysis. The data are analyzed using time dependent diagrammatic perturbation theory to obtain the frequency time correlation function (FTCF). The results are an improved FTCF compared to that obtained previously with vibrational echo correlation spectroscopy. The experimental data and the experimentally determined FTCF are compared to calculations that employ a polarizable water model (SPC-FQ) to calculate the FTCF. The SPC-FQ derived FTCF is much closer to the experimental results than previously tested nonpolarizable water models which are also presented for comparison. 相似文献
62.
VladimirA. Azov PhilipJ. Skinner Yoko Yamakoshi Paul Seiler Volker Gramlich Franois Diederich 《Helvetica chimica acta》2003,86(11):3648-3670
We report the synthesis and structural characterization of modified Cram‐type, resorcin[4]arene‐based cavitands. Two main loci on the cavitand backbone were selected for structural modification: the upper part (wall domain) and the lower part (legs). Synthesis of unsymmetrically bridged cavitands with different wall components (i.e., 7, 8 , and 14 – 18 ) was performed by stepwise bridging of the four couples of neighboring, H‐bonded OH‐groups of octol 1a (Schemes 1, 2, 4, and 5). Cavitands with modified legs (i.e., 20, 24, 27 , and 28 ), targeted for surface immobilization, were synthesized by short routes starting from suitable aldehyde starting materials incorporating either the fully preformed leg moieties or functional precursors to the final legs (Schemes 7–10). The new cavitand substitution patterns described in this paper should enable the construction of a wide variety of functional architectures in the future. X‐Ray crystallography afforded the characterization of cavitands 2c (Fig. 3) and 24 (Fig. 7) in the vase conformation, with 2c featuring a well‐ordered CH2Cl2 guest molecule in its cavity. A particular highlight is the X‐ray crystal‐structure determination of octanitro derivative 19 (Scheme 6), which, for the first time, shows a cavitand, lacking substituents in the ortho‐position to the two O‐atoms of the four resorcinol moieties, in the kite‐conformation (Fig. 5). 相似文献
63.
A synthesis of 4,6-dimethoxyindole is described. Formylation or oxalylation reactions gave substitution at position 7 rather than the usual 3-substitution characteristic of other indoles. A synthesis of N,N-dimethyl-4,6-dimethoxytryptamine is presented along with NMR data for 3 and 7-substituted compounds in this series. 相似文献
64.
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66.
High-throughput capillary electrophoresis for the identification and differentiation of seven species of Eimeria from chickens 总被引:2,自引:0,他引:2
A capillary electrophoretic approach has been evaluated for the identification of seven currently recognised species of Eimeria infecting chickens. The second internal transcribed spacer of ribosomal DNA is PCR-amplified from any of the seven species using a single set of oligonucleotide primers (one of which is fluorescently labelled). The amplicons are heat-denatured and subjected to capillary electrophoresis in a MegaBACE 1000 (Amersham). The chromatograms captured are stored electronically and then analysed using MegaBACE Fragment Profiler software. Using control DNA samples representing monospecific lines of Eimeria, specific peaks in the chromatograms were defined for the unequivocal identification of each of the seven species and their differentiation. Electrophoretic reading and analysis are carried out automatically, thus making it a time- and cost-effective method. This procedure should find applicability as a tool for the quality control of Eimeria vaccines, the monitoring of coccidiosis outbreaks and the high-throughput analysis of oocyst samples for epidemiological surveys. 相似文献
67.
Kobzar K Skinner TE Khaneja N Glaser SJ Luy B 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,170(2):282-243
The design of broadband excitation and inversion pulses with compensation of B(1)-field inhomogeneity is a long standing goal in high resolution NMR spectroscopy. Most optimization procedures used so far have been restricted to particular pulse families to keep the scale of the problem within manageable limits. This restriction is unnecessary using efficient numerical algorithms based on optimal control theory. A systematic study of rf-limited broadband excitation by optimized pulses and broadband inversion by optimized pulses with respect to bandwidth and B(1)-field is presented. Upper limits on minimum pulse lengths are set for different degrees of pulse performance. 相似文献
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69.
This review surveys the accomplishments in the separation of peptides and proteins by capillary electrochromatography (CEC) over the last decade. A significant number of research articles have been published on this topic since the last review. Peptide and proteins separations have been carried out in all three formats of CEC, i.e., packed bed, continuous bed and open-tubular (OT) format. In addition to electrophoresis, different chromatographic modes have been successfully exploited with the most prevalent being reversed-phase mode followed by ion-exchange. Although many researchers continue to use model proteins and peptides primarily to evaluate the performance of novel stationary phases some researchers have also applied CEC to the analysis of real-life samples. The potential of CEC to yield complementary information and sometimes a superior separation with respect to established techniques, i.e., microbore HPLC and capillary electrophoresis has been demonstrated. Instrumental modifications in order to facilitate coupling of CEC to mass spectrometry have further upgraded the value of CEC for proteomic analysis. Capillaries are still the separation vehicle of choice for most researchers yet the microfluidic platform is gaining momentum, propelled particularly by its potential for multitasking, e.g., performing different chromatographic modes in series. 相似文献
70.
Ropp J Lawrence C Farrar TC Skinner JL 《Journal of the American Chemical Society》2001,123(33):8047-8052
Experimental NMR measurements of the deuterium and (17)O T(1) relaxation times in deuterium-enriched liquid water have been performed from 275 to 350 K. These relaxation times can yield rotational correlation times of appropriate molecule-fixed unit vectors if the quadrupole coupling constants and asymmetry parameters are known. We determine the latter from ab initio studies of water clusters and experimental chemical shift measurements. We find that the rotational correlation time for the OD bond vector in D(2)(16)O varies from 5.8 ps at 275 K to 0.86 ps at 350 K, and that the rotational correlation time for the out-of-plane vector of dilute D(2)(17)O in D(2)(16)O varies from 4.4 ps at 275 K to 0.64 ps at 350 K. These results indicate that the rotational motion of water is anisotropic. Molecular dynamics simulations of liquid water are in good agreement with these experiments at the higher temperatures, but the simulation results are considerably faster than experiment at the lower temperatures. 相似文献