GEOCHEMISTY OF BICYCLIC ALKANES IN SEDIMENTS, COAL AND CRUDE OILS

By using GC-MS to analyze the extracts of source rocks, coal and crude oil samplesformed in different sedimentary environments in China, New Zealand and Australia, twenty-two compounds of five types of bicyclic alkanes have been dis covered in the samples. Thispaper makes an exposition of stereochemical structure, abundance and distributive features ofthese compounds and their relation to sedimentary environments and thermal evolution. Furt-thermore, it demonstrates how the abundance ratios of bicyclic alkanes to steranes and ter-panes, drimane to homodramane and the relative abundance of C_(15),C_(16),C_(12)-C_(14) series of bicyclic-alkane compounds can be used to judge and determine types of oil and gas forming environ-ments (the depositive environments of source rocks from which the oil and gas wereformed), characteristics of source rocks and degree of maturation.     

马心血红蛋白在氧化铟电极上的直接电子传递反应

马心血红蛋白在氧化铟电极上的直接电子传递反应杨秀娟，菊，陆天虹（中国科学院长春应用化学研究所电分析化学开放实验室，长春，１３００２２）关键词血红蛋白，氧化铟电极，循环伏安法蛋白质与电极之间的电子转移在某种程度上类似于生物体内蛋白质分子之间的电子转移过...     

运用NMR和DFT研究Michael加成反应的动力学行为及反应机理：(CO)5W=C(OEt)C2Ph作为底物

利用核磁共振方法研究了取代吡唑对炔基Fischer卡宾化合物的Michael加成的动力学行为，该反应为典型的二级反应。当吡唑的3，5-位由较大基团取代时，反应速率常数变小，而活化焓和活化熵明显增大。利用密度泛函理论研究了炔基钨卡宾为底物的Michael加成反应机理，发现吡唑上取代基团的增大可以导致第三步反应的活化能大于第一步，从而使反应的决速步骤由原来的第一步转变为第三步。     

Solid Phase Catalytic Oxidation of Alcohols by Polymer Supported Rare Earth Catalysts

Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results.     

273.15 K下Li2B4O7-LiCl-H2O体系热力学性质的等压研究及离子作用模型

用等压法研究了273.15 K下Li₂B₄O₇-LiCl-H₂O体系不同质量摩尔浓度分数的等压平衡浓度和水活度; 计算了LiCl和Li₂B₄O₇混合盐溶液的渗透系数等热力学性质. 用273.15 K下的实验数据对Pitzer离子相互作用模型进行了参数化研究, 拟合求取了273.15 K下Pitzer离子相互作用参数, 用获得的参数计算了LiCl和Li₂B₄O₇在Li₂B₄O₇-LiCl-H₂O体系中的活度系数. 273.15 K下由相应的Pitzer模型计算的渗透系数值与实验结果一致. 这对完善含锂、硼盐湖卤水体系的热力学模型具有重要意义.     

新型聚醚的合成与表征

用高活性催化剂催化环氧丙烷开环聚合得到一类新型高质量聚醚。对产物进行IR和NMR表征和分析,并探讨了合成工艺条件。结果表明,调节单体与调节剂的比例,控制反应温度在100 5℃,压力在0.15 ~ 0.25 MPa ,可得到不饱和度低、相对分子质量可控、相对分子质量分布窄的聚醚产品。     

Theory on the molecular characteristic contour (II)--Molecular intrinsic characteristic contours of several typical organic molecules

The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary.     

Comparative study on the inclusion behaviour of cyclodextrin derivatives with venoruton and rutin by thin layer chromatography

The interaction of rutin and venoruton (troxerutin), with alpha-, beta- and gamma-cyclodextrin (CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and methyl-beta-cyclodextrin (M-beta-CD) was investigated by reversed-phase thin layer chromatography on polyamide plates. A mobile phase consisted of NH(4)OH; NH(4)Cl buffer solution containing various CD concentrations (pH = 9.7, 20 degrees C) was used as mobile phase. The equilibrium constants (K(f)) and the retention factor (R(f)) were determined and used to study the inclusion process. The in fluence of CDs on the solubility of rutin and venoruton was characterized by R(M) values and the increasing hydrophilicity of drugs. The results show that the inclusion capacity of cyclodextrins follows the order HP-beta-CD > M-beta-CD > beta-CD > gamma-CD, and rutin is more easily included by the studied cyclodextrins than venoruton. In addition, the thermodynamic parameters (Delta H, Delta S) for the formation of complexes were obtained from the van't Hoff equation, displaying the enthalpy-entropy compensation effect.     

α-Tetralone glycosides from the green walnut husks of Juglans mandshurica Maxim. and their cytotoxic activities

Abstract

Five new α-tetralone glycosides, juglanbiosides A-E (1–5), together with an α-tetralone derivative (15) and nine known 1,4-naphthoquinones (6–14) were isolated from the 95% EtOH extract of green walnut husks of Juglans mandshurica Maxim. Their structures were elucidated by comprehensive spectroscopic methods (¹H, ¹³C NMR, DEPT, HSQC, HMBC, CD, HR-ESI-MS). In vitro cytotoxicities of all the isolated compounds were evaluated against BGC-823, HCT-15 and K562 cancer cell lines.