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181.
M. A. Bueno 《Foundations of Physics Letters》1994,7(4):393-400
In this work it is derived Phipps's Lagrangian function and Phipps's Hamiltonian function. This allows the utilization of Phipps's interaction in the Lagrangian and Hamiltonian frameworks.Dedicated to Thomas E. Phipps, Jr. on the occasion of his 70th birthday (1995). 相似文献
182.
V. Afraimovich A. Babin S.-N. Chow 《Transactions of the American Mathematical Society》1996,348(12):5031-5063
The dynamics described by a system of reaction-diffusion equations with a nonlinear potential exhibits complicated spatial patterns. These patterns emerge from preservation of homotopy classes of solutions with bounded energies. Chaotically arranged stable patterns exist because of realizability of all elements of a fundamental homotopy group of a fixed degree. This group corresponds to level sets of the potential. The estimates of homotopy complexity of attractors are obtained in terms of geometric characteristics of the potential and other data of the problem.
183.
Summary Electrostatic and structural properties of a set of -lactam, -lactam and nonlactam compounds have been analyzed and compared with those of a model of the natural substrate d-alanyl-d-alanine for the carboxy- and transpeptidase enzymes. This first comparison of the electrostatic properties has been based on a distributed multipole analysis of high-quality ab initio wave functions of the substrate and potential antibiotics. The electrostatic similarity of the substrate and active compounds is apparent, and contrasts with the electrostatic properties of the noninhibitors. This has been quantified to give a reasonable correlation with the MIC (Minimum Concentration for Inhibition) and with kinetic data (k2/K) in accordance with the model for interaction of the lactam compounds with dd-peptidase. These correlations provide a better prediction of antibacterial activity than purely structural criteria. 相似文献
184.
Limberg C 《Angewandte Chemie (International ed. in English)》2003,42(48):5932-5954
The oxo-functionalization of organic substrates with the aid of metal oxo moieties is of fundamental importance not only in nature but also in academic and industrial research. Nevertheless the corresponding reaction mechanisms remain among the most enigmatic in chemistry and few of them are understood in detail. Recent research efforts have resulted in significantly improved information: in the cases of many oxygenation reactions evidence has been provided for the occurrence radical intermediates, even though the high selectivity observed suggests to a different mechanism. Examples stem from various areas of chemistry and include processes involving molecular metal oxo complexes, gas-phase and matrix-isolated species, metalloenzymes, and solid-state oxide surfaces. This review treats this seemingly wide variety of systems with the aim of providing an overview of common reactivity patterns and principles, as well as open problems. 相似文献
185.
186.
《Electroanalysis》2006,18(22):2225-2231
The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10?8 to 5×10?6 M with a detection limit of 1×10?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity. 相似文献
187.
A detailed singlet potential energy surface(PES) of [Si,C,O,O] system including a van der Waals (vdW) comples SiO……CO2,eight isomers,and twelve transiton states is investigated by MP2 and QCISD(T) (single-point)methods.At the final QCISD(T)/6-311 G(2df)//MP2/6-311G(d) level with zero-point energy included,the complex SiO……CO is found to be thermodynamically and kinetically the most stable species.Although eight ismoers are located as local energy minima,they are rather unstable toward isomerization to the dissociation fragments or comples.For the reaction of silocon atoms with carbon dioxide,two competitive reaction channels are found,and the primary pathway,which leads to the products of SiO and CO fragments,is the direct oxygen-abstraction process from carbon dioxide by silicon atom with a41.16 kJ/mol reaction barrier height.Our predications are in good agreement with previous experimental and theoretical studies. 相似文献
188.
N. Nandi D. Vollhardt R. Rudert 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):279-287
In the present work, the pair potential of enantiomeric N-palmitoyl aspartic acid amphiphile monolayer at the air/water interface is calculated based on an atomistic model. The molecular structure and partial charges are calculated using two semi empirical (PM3, AM1) and one empirical (Gasteiger and Marcili) methods. A distance-dependent dielectric function is used to represent the interfacial dielectric constant at the aqueous subphase. The present study indicates that a pair of molecules have favorable interaction at specific ranges of mutual orientations. Other orientations are favorable but at larger separations. Favorable electrostatic interaction at a specific combination of orientation and short separations of the head groups significantly contribute to the total energy. The curvature of the domain boundary is suggested to be driven by the favorable arrangement which is dependent on the pair potential of molecules. The use of charges obtained by the PM3 and GM do not lead to a significant variation of the orientation-dependent features, while the AM1 predicts higher partial charges and interactions are stronger than the former two methods. However, orientation-dependent features remain the same. The variations in the LJ parameters and charges indicate that the conclusions made are insensitive to the choice of parameters. The mutual favorable interaction predicted by calculation agree with the handedness of curvature of domains. 相似文献
189.
电位法测定异价阳离子通过阳离子交换膜时的选择透过性 总被引:2,自引:0,他引:2
从理论上导出了不等价的两种阳离子在通过阳离子交换膜时的选择透过性与膜电位的关系,并用电位法对一些不等价阳离子组合在两种商品膜中的选择透过性进行了测定。本方法测定结果与电渗析实际分离效果相符。 相似文献
190.
研究了4个偶氮染料在酸性介质中的电还原性质。偶氮基在酸性介质中的还原均为不可逆四电子一步全还原。邻、对位上有吸电子基(如—CO_2Bu-n)的偶氮基较间位有吸电子基时更易被还原。分子中同时含有偶氮基和硝基时,偶氮基先被还原。 相似文献