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71.
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
72.
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
73.
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
74.
We investigate the dynamics and mechanism of the IR-driven cis-trans isomerization of nitrous acid (HONO) in a low-temperature krypton matrix applying ultrafast time resolved IR spectroscopy. After excitation of the OH-stretching mode the trans HONO state decays biexponentially on a 8 and 260 ps time scale. The initially excited cis HONO state decays on a 20 ps time scale. Cis HONO isomerizes with 10% quantum yield on a 20 ps time scale to trans HONO. The quantum yield we observe is significantly smaller than the previously reported 100%, which could imply that additional, much slower reaction channels exist. We furthermore developed a four-dimensional model of the system, which includes the three proton intramolecular degrees of freedom of HONO fully quantum mechanically and one intermolecular translational degree of freedom of the molecule in the crystal cage. We find that cis-trans isomerization necessarily is accompanied by a translation of the molecule as a whole in the crystal cage. The translational degree of freedom tunes the intramolecular proton states of HONO with respect to each other. When resonances occur, the proton states might couple and transfer population. We suggest a possible reaction pathway, where the cis OH-stretch excited state first couples to a high cis torsional mode, which then may transfer almost instantaneously to the trans side. The model qualitatively explains all experimental observations. 相似文献
75.
J. Kučera J. Kučera A. R. Byrne A. R. Byrne J. Mizera J. Mizera M. Lučaníková M. Lučaníková Z. Řanda Z. Řanda 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):251-257
Summary Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform
from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed
for accurate determination of rhenium in biological and environmental samples at the sub-ng . g-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng . g-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng . g-1 was found. Significantly elevated values of Re, up to 90 ng . g-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated 99Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process. 相似文献
76.
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
77.
G. Erdogduğ 《Journal of Analytical Chemistry》2002,57(7):620-623
A gold electrode was modified with electropolymerized films of 4-methoxyphenol by its oxidative polymerization from an alkaline solution by cyclic voltammetry. The modified electrode was then used to determine epinephrine (EP) in the presence of a high concentration of ascorbic acid (AA) by differential pulse voltammetry. The peak positions as well as relative sensitivity EP/AA were affected by the potential window used for the polymerization. For polymerization between 0 and 1.3 V, the peak potentials recorded in a phosphate buffer solution (pH = 7.2) were 516 and 312 mV vs. Ag/AgCl for EP and AA, respectively. In addition the effects of pH and the type of electrolyte on the linearity range and detection limit are investigated. The detection limit for 3s-test is 0.1 M. The high selectivity and sensitivity for epinephrine was found to be due to charge discrimination/analyte accumulation. 相似文献
78.
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
79.
Gürses A Karaca S Doğar C Bayrak R Açikyildiz M Yalçin M 《Journal of colloid and interface science》2004,269(2):310-314
In this study, adsorption of methylene blue onto clay was investigated. The effect of adsorption time and temperature on the adsorption process was studied. To reveal the adsorptive characteristics of the clay studied, porosity and BET surface area measurements were made. It was observed that the adsorption capacity decreases with increasing temperature, and adsorption equilibrium was attained within 1 h. It was found that the data fit well to Langmuir, Halsey, Henderson, and Harkins-Jura models but experimental data deviate significantly from BET and Freundlich models at especially high concentrations. Furthermore, isosteric adsorption enthalpy and entropy are calculated as -7.99 kJ mol(-1) and 25.41 JK(-1)mol(-1), respectively. 相似文献
80.
Barluenga J Diéguez A Rodríguez F Flórez J Fañanás FJ 《Journal of the American Chemical Society》2002,124(31):9056-9057
Eight-membered carbocycles with up to five new stereogenic centers are enantioselectively obtained following a one-pot procedure that involves the coupling of three components: an alkenyl Fischer carbene complex, a ketone enolate, and allyl lithium. 相似文献