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991.
诱导效应指数与含硫含氮的低碳直链有机化合物的标准汽化热 总被引:2,自引:0,他引:2
本文利用诱导效应指数建立了含硫含氮的低碳直链有机物的标准汽化热的简单估算方法,我们利用此法计算了一些含硫含氮的直链有机物的标准汽化热,41个可比较值的相对误差均在5%以内。 相似文献
992.
采用络合反应,消除电镀锡溶液中金属离子对分离柱的污染,应用离子色谱法检测电镀液中SO4^2-的含量,回收率为95%-104%。 相似文献
993.
Roxana Irimescu 《Tetrahedron letters》2004,45(3):523-525
Lipase-catalyzed enantioselective acylation of 1-phenylethylamine and 2-phenyl-1-propylamine was performed by reacting the amines with carboxylic acids in a non-solvent system or in ionic liquids as reaction media. The reaction equilibrium was shifted toward amide synthesis by the removal of formed water under reduced pressure. 相似文献
994.
995.
Wenjuan Yin Shihai Yan Mei Qin Zhiqiang Li Yuxiang Bu 《International journal of quantum chemistry》2006,106(7):1528-1543
In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol?1, and the forward/backward barriers are 32.27/12.66 kcal · mol?1, decreased by 33.25/31.21 kcal · mol?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
996.
表面分散过程的分形研究 总被引:5,自引:0,他引:5
盐类和氧化物等活性组分在一定条件下,可在高比表面载体上自发分散。研究这些过程对多相催化剂、吸附剂的制备过程理解和控制无疑是重要的。这类分散过程已被系统地研究,并提出了单层分散模型,对CuCl_2/γ-Al_2O_3、HgCl_2/活性炭等多种体系,测定了单层分散阈值。表面化学习惯上理解为就是二维的化学。早在1931年Tayor就指出表面是不均匀的,但这种不均匀性是作为对理想二维表面的修正而引入的,如TLK模型。表面科学的这些基本概念其数学基础是欧基里德几何学,其物理背景是晶体结构,不规则性就是指晶体结 相似文献
997.
To investigate the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine, this study uses a method based on microdialysis technique and liquid chromatography that allows continuous and concurrent in vivo monitoring of extracellular caffeine in the blood, brain and bile of anesthetized rats following the administration of caffeine (3 or 10 mg/kg, i.v.) through the femoral vein. Dialysates of the blood, brain and bile were directly injected onto the liquid chromatographic system and no further clean-up procedures were required. The study design consisted of two groups of six rats in parallel: the rats of the control group received caffeine (3 or 10 mg/kg, i.v.) alone and those of the cyclosporine treated-group were injected cyclosporine (10 mg/kg, i.v.) 10 min prior to caffeine administration (3 or 10 mg/kg, i.v.). The decline of caffeine in the blood, brain striatum and bile suggested that caffeine had rapid exchange and equilibration between the peripheral compartment and the central nervous system. In addition, the results indicated that caffeine underwent hepatobiliary excretion and was distributed into brain. When cyclosporine was co-administered, the pharmacokinetic parameters were not significantly altered. The results of this study reveal that the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine might not relate to P-glycoprotein. 相似文献
998.
A. A. Chesnyuk S. N. Mikhaylichenko L. D. Konyushkin S. I. Firgang V. N. Zaplishnyi 《Russian Chemical Bulletin》2005,54(8):1900-1906
New 1,2,4-oxadiazolyl-1,3,5-triazines were synthesized from amidoximes derived from sym-triazine mononitriles. The structure of one of the resulting compounds was studied in detail by X-ray diffraction.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1845–1850, August, 2005. 相似文献
999.
1000.