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91.
Langlet J. Claverie P. Pullman B. Piazzola D. Daudey J. P. 《Theoretical chemistry accounts》1977,46(2):105-116
The effect of water on the conformational preferences of acetylcholine has been studied within the discrete, the continuum and the combined discrete-continuum models described in parts I and II of this series. All the models lead to the conclusion that the trans-gauche form which is, following refined quantum-mechanical computations, the intrinsically preferred one and the one observed in the crystal of acetylcholine and of a number of analogues should remain also the preferred conformation in water. This result agrees with NMR studies. The results of the empirical discrete model used here compare favorably to those obtained by an ab initio super-molecule treatment. The continuum model utilized here represents a net improvement above such models utilized in other works. 相似文献
92.
The influence of isopropyl alcohol (IPA) on the size and composition of the mixed micelles in mixtures of tetradecyltrimethylammonium bromide (TTAB) and chlorhexidine digluconate (CG) has been determined as a function of the composition of the systems. The addition of 0.5 M and 1.0 M IPA had little significant effect on the composition of the mixed micelles as determined both by analysis of critical micelle concentration (CMC) data using a theoretical treatment based on excess thermodynamic quantities and by an empirical treatment of conductivity data. Static and quasielastic light scattering measurements showed a progressive decrease of the aggregation number and hydrodynamic radius of TTAB micelles on addition of IPA, but minimal changes in the properties of the small CG aggregates. The results show that the micellar weight in the TTAB/CG/IPA solutions is determined by the ratio of the surfactants in the system and for each TTAB/CG ratio decreases on addition of IPA. 相似文献
93.
I. V. Dlinnykh G. A. Golubeva I. F. Leshcheva V. V. Nesterov M. Yu. Antipin L. A. Sviridova 《Chemistry of Heterocyclic Compounds》2004,40(9):1142-1149
The reaction of oxindoles with 5-hydroxypyrazolidines on the surface of potassium fluoride-modified alumina leads to 3-(5-pyrazolidinyl)oxindoles. The structure of these products was studied. 相似文献
94.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
95.
K. Grob 《Journal of separation science》1980,3(6):286-290
The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects. 相似文献
96.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
97.
研制了酸度在线检测装置,并应用于溶液酸度在线检测,溶液酸度在线检测装置,设有防污过滤器,自动采样器,蠕动泵,小型管道pH传感器和控制电路等,其特点为防污除油,随机自动采样,定时检测,全部管道化,可单独使用和计算机控制系统联网,适用于溶液酸在线分析,测定精度〈pH0.05。 相似文献
98.
99.
Crude extracellular invertase fromSclerotium rolfsii, when coupled to glutaraldehyde activated Indion 48-R, retained 70–80% activity of the soluble enzyme. Immobilization resulted
in a decrease in the pH and temperature optima but it increased the temperature stability. Km and Vmax also increased as a result of immobilization. Both soluble and immobilized invertase showed inhibition at high substrate
concentrations. The bound enzyme showed excellent stability to repeated use and retained approx 90% of its initial activity
after 8 cycles of use. 相似文献
100.
以常见的阴、阳离子的检验为例,研究了如何实施基于标准的教学。校本教材的开发为标准、教材、教学、评价的一致性提供保障;以学生应知的和能做的驱动课堂活动;根据达成标准应有怎样的质量表现,试卷编制先于教学设计。课堂上,“教”“学”双方都明确学习目标,教师提供多种策略来满足学生多样的学习需要,如提供工具,搭建脚手架,并以“微”研究性学习的方式展开教学,给学生提供了充分的进步空间。 相似文献