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51.
The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions. 相似文献
52.
Palladium-catalyzed Heck condensation of C-p-bromophenyl delta2-glycopyranoside with methyl vinyl ketone, methyl acrylate, acrylonitrile, or N-acetyldehydroalanine methyl ester occurred in quite good yields (60-82%). 相似文献
53.
54.
A new highly sensitive and selective chromogenic reagent, 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic
acid (1), was synthesized and applied to the spectrophotometric determination of trace thorium. In 5 mL of a 6 M perchloric acid
medium, which greatly increases the selectivity, thorium reacts with 1 to form a 1: 2 green complex, having a sensitive absorption peak at 670 nm. Under optimal conditions, Beer’s law is obeyed
over the range from 0 to 0.8 μg/mL Th(IV) and the apparent molar absorptivity is 2.09 × 105 L/mol cm. It is found that, uranium(VI), Ti(IV), heavy rare earths, and most of other common metal ions do not interfere.
The method has been tested on the determination of thorium in food samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
55.
巯基葡聚糖凝胶分离富集光度法测定镉的研究 总被引:2,自引:0,他引:2
研究了在TritonX-100存在下,新显色剂邻羧基苯基重氮氨基偶氮苯(CDAA)与镉的显色体系,在pH10.6的Na2B4O7-NaOH体系中,显色反应灵敏度很高。络合物的最大吸收位于545nm处,其摩尔吸光系数为2.22×10^5L·mol^-1·cm^-1。镉含量在0 ̄12μg/25mL符合比耳定律。将该体系用于巯基葡聚糖凝胶分离富集-光度法测水样中微量镉,结果令人满意。 相似文献
56.
近年来,中草药有效成分的研究引起国内外有关学者普遍关注。氚标记中草药有效成分是研究其相应的药代动力学和代谢产物的主要手段,它具有操作简便,条件温和等优点,但是一般氚化方法均不能明确给出氚化位置。而研究氚化定位效应又是药理工作者急待解决的重要课题,所以在很大程度上限制了该项技术的使用范围。最近,郑冬珠等人用FX—100型核磁共振谱仪给出了在PdO催化剂存在条件下,低压氚化亮石松碱的氚化位置及其相对含量。本文在前文基础上,以亮石松碱为底物,根据Fraser和Garnett等人提出的氢—氚同位素交换反应动力学理论,采用CNDO/2法,对PdO催化亮石松碱的立体构型讲行了计算,得出一些有意义的结果。 相似文献
57.
本文采用XRD,NH_3-TPD,IR以及TEM等方法考察了Pt/BaKL沸石中Ba~(2+)的作用。NH_3-TPD结果表明,交换Ba~(2+)后的L型沸石的酸性,由于阳离子的作用仅在弱酸范围内有些改变,但与载铂的沸石的催化活性无明显的对应关系。IR及XRD谱线表明,BaKL沸石中Ba~(2+)在最佳交换度(26.3%)时,随预培烧温度的提高,使Ba~(2+)处于沸石孔道中B、C、D位置,接近于最佳分布,此时IR谱线上1421cm~(-1)处有一新峰。当沸石负载铂后,因铂与Ba~(2+)的相互作用,新峰消失,导致铂粒在沸石上分布更加均匀;铂粒在1.5—3.0nm之间占有最大比例,使得Pt/BaKL沸石呈现芳构化活性及选择性高于Pt/KL沸石,分别为~98%和~95%。 相似文献
58.
Ai‐Hua Zhao Yan Zhang Zhao‐Hui Xu Jian‐Wen Liu Wei Jia 《Helvetica chimica acta》2004,87(12):3160-3166
Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3). 相似文献
59.
Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4 总被引:3,自引:0,他引:3
Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena. 相似文献
60.
[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents. 相似文献