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31.
酰胺是肽的基本结构单元, 而且在蛋白质的二级结构中与酰胺联系的氢键对蛋白质的稳定起着十分重要的作用. 作为蛋白质模型化合物热力学性质研究的一部分, 报道了甲酰胺在乙二醇水溶液中的稀释焓. 相似文献
32.
苯并三氮唑及其羧酸酯衍生物对铜缓蚀机理的分子动力学模拟研究 总被引:1,自引:0,他引:1
用分子动力学(MD)方法, 模拟计算了5种铜缓蚀剂[苯并三氮唑(BTA)、苯并三氮唑-5-羧酸甲酯(MBTC)、苯并三氮唑-5-羧酸丁酯(BBTC)、苯并三氮唑-5-羧酸己酯(HBTC)、苯并三氮唑-5-羧酸辛酯(OBTC)]与Cu2O晶体的相互作用. 结果发现, 中性条件下缓蚀剂分子与Cu2O晶体的结合能均大于酸性条件下的数值, 但两种条件下结合能的大小排序均为OBTC>HBTC>BBTC>MBTC>BTA. 对体系各种相互作用以及对关联函数g(r)的分析表明, 体系结合能主要由库仑作用提供, Cu2O晶体中的Cu原子与缓蚀剂分子中的N原子之间形成了配位键. 在与Cu2O(001)晶面结合过程中, BTA及其衍生物分子发生了扭曲变形, 但形变能远小于体系的非键相互作用能. 相似文献
33.
The interaction of carbenium ion pairs with silica is studied by means of UV-spectroscopy, electrokinetic and adsorption measurements using triphenylmethyl derivatives, (RC6H4)3CX, (X=F, Cl, Br, SCN, OH; R=Cl, I, H, CH3, C(CH3)3, OCH3, N(CH3)2) in interaction with silica particles suspended in 1,2-dichloroethane. The adsorption of triarylmethyl-halides onto silica is accompanied by the heterolytic dissociation of the tertiary carbonhalogen bond. The degree of ionization depends on the basicity of the counter anion and acidity of the cation, respectively. The influences of both concentration and structure of triarylmethyl halides on the zeta-potential are discussed with regard to steric and electronic factor. The zeta-potential values of the adsorbates decrease significantly, as compared with the free silica surface, from a certain triarylmethyl halide concentration where ionization takes place, to a constant level which is characteristic of the carbenium ion pair. These constant zeta-potential values of the adsorbates depend on the basicity of the counter ion and the
p
Hammett constants of the ring substitutents, with exclusion of sterically hindered substituents and salt derivatives, e.g., crystal violet and malachite green. 相似文献
34.
In this paper, the nanosecond transient absorption spectra and the fluorescence spectraof Hypocrellin A(HA) are examined in solvents of varying polarity. There are three absorp-tion bands in dilute HA solutions: Ⅰa, Ⅱa are defined as the triplet-triplet absorption ofHA, the band Ⅲa is supposed to be the absorption of the solvent--sepatated ion pair (SSIP).In more concentrated solutions, only the absorption of SSIP was observed. The effects ofsolvent polarity on transient absorption spectra and fluorescence spectra of HA and the effectof oxygen on the intensities of the fluorescence of HA are discussed. Then a reasonablemechanism for the photolysis of HA is proposed. 相似文献
35.
原子发射光谱法间接测定黄连素片剂中盐酸小檗碱的研究 总被引:1,自引:0,他引:1
本文提出了离子对-原子发射光谱间接测定黄连素片剂中盐酸小檗碱的新方法。发现用1,2-二氯乙烷作萃取剂效果最佳。用此怯测定实际样品的结果与药典法一致,相对误差为0.61%,单一测定的相对标准偏差为0.67%。本法还可在盐酸普鲁卡因共存下单独测定盐酸小檗碱。方法可靠、适用,选择性较好。 相似文献
36.
The apparent molal volume and adiabatic compressibilities of some transition metal (Mn2+, Co2+ Ni2+, Cu2+, Zn2+, and Cd2+) sulfates have been determined at 25°C. Values of
to 11.4 cm3-mole–1 and
to 31.3 × 10–4cm3-mole–1-bar–1 at 1 atm were found for the formation of the transition metal sulfate ion pairs. These results are in good agreement with the values obtained from the high-pressure conductance measurements of Fisher et al., Shimizu et al., and Taniguchi et al. The volume and compressibility data indicate that 3.1±0.7 water molecules are lost when transition metals form ion pairs with SO
4
2–
. The fractions of inner-sphere ion pairs (20%) estimated in this study are in good agreement with the values obtained from ultrasonic measurements. 相似文献
37.
A multireference configurational interaction method based on the separated electron pair (SEP) wave functions, SEP‐CI approach, has been developed as an approximation to the traditional CASSCF method. It differs from the CASSCF method in that active orbitals are obtained from the SEP wave function without further optimization in the subsequent CI calculations, and the active space is automatically constructed according to the occupation coefficients of SEP natural orbitals. These features make the present SEP‐CI method computationally much less demanding than the CASSCF method. The applicability of the SEP‐CI method is illustrated with sample calculations on the insertion reaction of BeH2 and dissociation energies of LiH, BH, FH, H2O, and N2. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 39–47, 2006 相似文献
38.
39.
V. R. Kartashov T. N. Sokolova O. A. Leksina A. B. Radbil N. V. Malisova Yu. K. Grishin 《Russian Chemical Bulletin》1995,44(3):527-531
The reaction of Hg(OAc)2 with bornylene in THF-H2O and CH3CN-H2O mixed solvents (75 25, v/v) was studied. The effects of the addition of NaOAc on the reaction rate and the composition of products were investigated. In the CH3CN-H2O mixture, the addition of NaOAc decreases the amount of the rearranged product, fundamentally changes the ratio between the regioisomeric solvoadducts, and promotes the formation of products of Hg(OAc)2 addition. The reaction proceedsvia an ion pair and free mercurinium ion; the cation of the ion pair and the free mercurinium ion have dissimilar structures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 544–548, March, 1995. 相似文献
40.
N. I. Golovina R. F. Trofimova L. O. Atovmyan A. G. Korepin P. V. Galkin G. V. Lagodzinskaya M. V. Loginova L. T. Eremenko 《Russian Chemical Bulletin》1994,43(3):398-401
The reaction of -fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown -chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 440–443, March, 1994. 相似文献