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We study the derivation of a Langevin equation from a microscopic basis in order to elucidate the nature of the random force. We arrive at the conclusion that the consistent interpretation of the microscopic Langevin equation in terms of a stochastic differential equation (SDE) is according to I
o rules. In addition, the random force is in general not Gaussian, and it is hence not completely characterized by its second moments. 相似文献
55.
α-Aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is increasingly being used in wide variety of commonly consumed food products. This structure contains ester and peptide bonds. The ester linkage may hydrolyze to produce L-α-aspartyl-L-phenylalanine or cyclohydrolyze to produce the corresponding diketopiperazine ring. This ring can open to form L-α-aspartyl-L-phenylalanine and ultimately this compound can hydrolyze to L-phenylalanine and L-aspartic acid. The pH, buffer type, concentration, the presence of water and temperature are other important factors affecting its stability. Because α-aspartame can lose its sweetness under these conditions determination of aspartame and its breakdown products is extremely important for diet foods quality. The optimum mobile phase for the chromatographic separation was found to be acetonitrile-water (20:80, ν/ν) with 5.10?3 M hexanesulfonic acid and a pH of 2.6. 相似文献
56.
Jagoda M Warzeska S Pritzkow H Wadepohl H Imhof P Smith JC Krämer R 《Journal of the American Chemical Society》2005,127(43):15061-15070
For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two-metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilization, has been proposed. Inspired by the active site structure of this enzyme, we have designed as a synthetic phosphoryl transfer catalyst the dicopper(II) macrocyclic complex LCu(2). Crystal structures of complexes [(L)Cu(2)(mu-NO(3))(NO(3))](NO(3))(2) (1), [(L)Cu(2)(mu-CO(3))(CH(3)OH)](BF(4))(2) (2), and [(L)Cu(2)(mu-O(2)P(OCH(3))(2))(NO(3))](NO(3))(2) (3) illustrate various possibilities for the interaction of oxoanions with the dicopper(II) site. 1 efficiently promotes the transesterification of dimethyl phosphate (DMP) in CD(3)OD, k(cat) = 2 x 10(-)(4) s(-)(1) at 55 degrees C. 1 is the only available catalyst for the smooth transesterification of highly inert simple dialkyl phosphates. From photometric titrations and the pH dependence of reactivity, we conclude that a complex [(L)Cu(2)(DMP)(OCH(3))](2+) is the reactive species. Steric bulk at the -OR substituents of phosphodiester substrates O(2)P(OR)(2)(-) drastically reduces the reactivity of 1. This is explained with -OR leaving group stabilization by Cu coordination, an interaction which is sensitive to steric crowding at the alpha-C-atom of substituent R. A proposed reaction mechanism related to that of the exonuclease unit of DNA polymerase I is supported by DFT calculations on reaction intermediates. The complex [(L)Cu(3)(mu(3)-OH)(mu-CH(3)O)(2)(CH(3)CN)(2)](ClO(4))(3) (4) incorporates a [Cu(OH)(OCH(3))(2)(CH(3)CN)(2)](-) complex anion, which might be considered as an analogue of the [PO(2)(OCH(3))(2)(OCD(3))](2)(-) transition state (or intermediate) of DMP transesterification catalyzed by LCu(2). 相似文献
57.
A. Baştuğ Ö. Söğüt Y. Şahin M. Ertuğrul 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(2):323-327
La and Lb X-ray fluorescence cross sections in Er, Ta, W and Au at excitation energies of 16.896, 22.581, 25.770, 32.890, 38.184, 43.949, 50.214 and 59.5 keV were investigated. Measurements were made using a low energy Si(Li) detector coupled to a model 4096 computerized multi-channel analyser. The experimental results were compared with the theoretically calculated values of L X-rays fluorescence cross sections and other experimental results. Good agreement was observed between experimental and theoretical values. 相似文献
58.
Summary A fully integrated chromatographic system was developed for the determination of leukotrienes in biological samples using
photodiode-array detection (PDAD), which eliminates time consuming manual sample handling steps. A special solid phase extraction,
(SPE) methodology for leucotriene metabolite stability was developed which increased the recoveries and eliminates the contamination
risk of biological samples. The inherent instability (autooxidation) of many of the leukotriene mediators, and the adsorption
effects onto exposed surfaces in vials and in the chromatographic system were found to be very important parameters to control
in order to circumvent high loss of sample analytes. By binding the cell supernatants to the functionalities of the SPE support
stabilised these mediators. Cell culture samples were eluted through a disposable C18 SPE column. The SPE columns were allowed to thaw and deposited in an automated sample handling unit (ASPEC XL). Desorption
of the analytes was followed by a second on-line SPE step, to eliminate remaining interfering matrix compounds. Typical recoveries
when stored at −70°C were in-between 55–97% except for (LTE4) which was found to be around 40% after 72 days of storage. Seven reversed-phase packings were studied. Selectivity factors,
as well as the separation efficiencies, were found to differ for the various C18 bonded silica stationary phases. This integrated on-line column liquid chromatographic system was applied to the determination
of leukotriene B4, leukotriene C4, leukotriene D4, leukotriene and E4 in human cell extracts using prostaglandin B2 as the internal standard. More than 1500 biological samples were analysed. Some validation data are presented for unattended
operations. 相似文献
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Compton scattering normalization method is described for the analysis of uranium bearing ore respect to the usage of K X-rays of uranium. Minimum backscatter energy is obtained at a scatter angle of 180° with fixed point source geometry and collimation in appropriate conclusions. By normalizing the intensities of uranium K-lines to the Compton profile in the measured spectra, the results do not depend on several measuring parameters such as primary radiation intensity, matrix, composition, mass of the sample and measuring time. The method presented in this study indicates the convenience of uranium K-lines analysis for thick targets with an adequate measuring geometry. 相似文献