Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-l-phenyl-l-propanone with borane catalyzed by (S)-4-benzyl-5,5-diphenyl-l,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step Ⅲ exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-l-phenyl-l-propanone spontaneously, resulting in the need of 2 tool BH3 in the reaction.     

栝楼蛋白 2: 栝楼蛋白部分化学结构的初步测定

栝楼蛋白(Trichobitacin)是从栝楼(Trichosanthes kirilowiiMaxim, Cucurbitaceae)中新发现的核糖体失活蛋白, 分子量为27,228; pI为9.6。应用基质辅助的激光解析飞行时间质谱(MALDI-TOF-MS)和快原子轰击质谱法(FAB-MS)分别测定胰蛋白酶酶解栝楼蛋白和天花粉蛋白(Trichosanthin)的混合肽质谱, 通过比较发现了一些分子量相同的肽。由于这两种蛋白质都来源于栝楼块根, 同源性比较强, 所以这些肽序列在两种蛋白质中基本一样; 再结合蛋白N-端自动顺序仪测定栝楼蛋白N-端的结果, 确定了栝楼蛋白N-端38个氨基酸的顺序, 栝楼蛋白经胰蛋白酶酶解后所得肽段用HPLC分离纯化, 再用蛋白质自动顺序仪, DABITC/PITC双偶合手工法和质谱法共确定了栝楼蛋白N-端, C-端等100多个氨基酸残基的序列。     

B20N20团簇的结构与稳定性

B3LYP/6-31G* density functional theory calculations have been carried out on the structure and stability of ten B20N20 clusters. It was found that two new proposed isomers with two octagons, twelve hexagons, eight squares in Cab and C2 symmetry were more stable than the isomer with sixteen hexagons and six squares in C2 symmetry which was previously deemed to the most stable by 79.5 and 13.8 kJ/mol respectively. The isomer with two decagons in S10 symmetry is much higher in energy than the most stable structure in C4h symmetry by 637.2 kJ/mol.     

CdS和CdSe新型纳米结构的高效溶剂热合成

采用快速高效的溶剂热法合成了海星形CdS纳米结构和一维CdSe纳米结构。用XRD、SEM和UV-Vis等表征手段对产物进行了表征，结果表明产物为单一的CdS和CdSe纳米结构，且CdS纳米结构具有良好的分散性，其形成极大地受到pH值影响，而CdSe先形成层状的二维结构、再形成一维纳米结构。     

以Si为联合原子的分子系列双原子分子的里德伯能级结构

本文在独立电子近似的基础上,利用多重散射自洽场理沦方法,计算一些以Si为联合原子的双原子分子N₂,CO,BF,AlH,LiNa,“BeNe”,“MgHe”的里德伯能级结构。根据分子的电子组态极限,确定了各里德伯系列初始态的主量子数。阐明了这些双原子分子里德伯能级结构的变化规津。理论计算结果与已有的实验数据符合得较好,从而为超越独立电子近似的计算打下基础。 关键词：     

铜到钼的类钠离子能级结构及软X射线光谱理论计算

本文采用Hartree-Fock自洽场方法,从理论上计算了铜到钼的类钠离子1s~22s~22p~6nl(n=3～6,l=O～5)各能级能量。给出了有可能实现软X射线激光的跃迁(5g—4f,5f—4d,6g—4f,6f—4d)的光谱性质:跃迁波长、振子强度,并和实验值进行了比较,跃迁波长的相对误差不超过千分之二。从计算结果可知,Se的6f—4d跃迁,Br的6g—4f跃迁,Zr的5f—4l跃迁,Nb的5g—4f跃迁都已进入水窗波段。     

基于三维静电势参数研究C60溶解性的构效关系

在量子化学从头算基础上,对一系列溶剂化合物分子进行了结构优化和三维静电势参数计算,运用多元线性回归分析和神经网络方法对C60在121种不同溶剂的溶解性与计算的结构参数进行了构效关系研究.用建立起来的QSPR 关系式对15种不同结构类型溶剂进行了预测,并阐述了C60溶质与不同溶剂之间的相互作用,获得了满意的结果.     

热致型液晶聚合物的近晶相结构研究

本文借助于不同热处理样品的WAXD研究和变温FTIR分析,从液晶态与结晶态面间距的变化,晶态、液晶态和各向同性液态下结构构象的差异出发,研究了聚合物液晶态下的近晶相结构模型。     

Synthesis and Characterization of p—[Perfluoro—1—（2—fluorosulfonylethoxy）]ethylated Polystyrene

A new fluorinated polystyrene bearing a p-sulbstiuted perfluoro[1-(2-fluorosulfonylethoxy)]ethyl group was synthesized via one-electron oxidation of polystyrene by perfluoro[2-(2-fluorosulfonylethoxy)]propionyl peroxide at different peroxide to polystyrene molar ratios.The yield of perfluoroalkylation decreases with the increase of the reactant molar ratio.The modified polymer has been characterized by various techniques:the ring pefluoro[1-(2-fluorosulfonylethoxy)]ethylation has been proved by FT-IR and ^19FNMR;the X-ray photoelectron spectra(XPS) show the maximum binding energy of F18,O18,C18(two kinds of carbon atoms,namely C-H and C-F)and S2p,respectively; desulfonylation of the fluorinated polystyrene appearing at 217℃ has been found by its thermogravimetric analysis (TGA).The determinations of contact angle,refractive index and glass transition temperature of the modified polymer have disclosed that when the contact angle increases with the increase of the molar ratio,the refractive index and glass transition temperature decrease.The polydispersity values indicate that the degradation of the polymer chains did not occur during the reaction.     

Fe2O3/Al2O3催化氧化苯偶姻制备苯偶酰

考察了几种常用载体负载金属氧化物催化分子氧氧化苯偶姻制备苯偶酰的性能 ，发现氧化铁、三氧化二铝催化活性较高，稳定性较好。以吡啶为溶剂，用483K下 活化的含铁14．8％的氧化铁／三氧化二铝作催化剂，当其用量为苯偶姻用量20％ （质量分数），253K下反应1h,苯偶酰平均产率98．1％。用IR，MS，和^1H NMR光 谱对其结构进行了表征。