微波在有机化学中的应用

评述了微波加热技术的原理及概况,及近几年来该技术在有机化学领域中的应用情况.     

Ba1-xSrxTiO3（x=0,0.1,0.2,0.3,0.4）陶瓷材料的结构及介电性能的研究

采用传统固相反应方法制备了(Ba1-xSrxTiO3,BST)(x=0,0.1,0.2,0.3,0.4)陶瓷材料,用X射线衍射方法和介电谱方法研究了所制备陶瓷材料的结构和介电性能,结果表明,所制备样品,Sr2+进入BaTiO3后与Ba2+形成了钙钛矿型连续固溶体;随着Sr2+含量的增加,峰位向高衍射角度移动,晶粒尺寸减小,说明Sr2+的掺入抑制了晶粒的生长;BST的系列样品随着温度的升高,介电常数增大,但是随着频率的增大介电常数减小,且峰值随着Sr2+含量的增加都向低温区移动,Sr2+的掺入,有明显的压峰效应,具有弥散相变的特征.     

表面活性剂对水溶性氮杂环卡宾钯催化Suzuki反应的影响

开展了添加表面活性剂对带15个左右的乙二醇单元的氮杂环卡宾钯催化剂（5）在水介质中催化Suzuki偶联反应性能的影响研究;发现常见的阳离子或阴离子表面活性剂均可将催化剂5在水介质中的催化性能恢复到在二氧六环中的水平;故发现了一条提高催化剂5在水介质的性能途径.     

Theoretical Study on Isomerization of Intermediate in the CCl2O＋ O（1D） Reaction System

运用一种建立在多步计算水平上的CBS—QB3理论方法对光气与氧原子反应体系中生成的中间体之间的异构化反应机理进行了理论研究,计算结果表明M1-trans（ClC（O）OCl）是一种最稳定的中间体构型。     

虎耳草ISSR反应体系的建立及优化

建立并优化虎耳草ISSR-PCR反应体系和扩增程序,为探讨虎耳草种质资源遗传多样性奠定基础.采用正交设计方法和单因子试验,研究TaqDNA聚合酶、dNTP、Mg2+、引物、模板DNA、延伸时间及循环次数对PCR扩增的影响.结果表明:虎耳草ISSR-PCR的最佳反应体系为:在25μL的反应体系中含模板DNA 35ng,Mg2+1.25mmo/lL、dNTP 380μmo/lL、引物1.2μmo/lL、Taq DNA聚合酶1.5U.反应程序为:95℃预变性5min;94℃变性1min,50℃(据不同引物的退火温度)退火70s,72℃延伸1.5min,40个循环;72℃延伸10min,4℃保存.经过11份虎耳草种质检验,证明该体系稳定可靠,可用于虎耳草种质资源遗传多样性分析及居群鉴别的研究.     

钯催化Suzuki反应的研究进展

钯催化Suzuki偶联反应是有机合成中构建分子中碳-碳键的重要反应之一,由于该反应产物容易分离、催化剂可重复使用等特点,已引起人们的广泛关注.综述了近年来钯催化Su-zuki反应的研究进展,包括Suzuki反应机理、载体催化剂及其在有机合成中的应用等.     

7-氨基-4,6-二硝基苯并氧化呋咱的合成反应研究

分析和讨论了以3-氯苯胺为原料,经酰化、硝化、叠氮化热解脱氮及水解合成7-氨基-4,6-二硝基苯并氧化呋咱反应的机理及反应条件.此反应收率高,条件温和.     

C_2(a~3Π_u)自由基与C_2H_6反应的动力学计算

用密度泛函理论B3LYP方法,在6-311G(d,p)基组下,优化得到C2(a3Πu)+C2H6→C2H+C2H5反应各驻点(反应物、过渡态和产物)的几何构型,对其进行振动分析,并计算了它们的能量.在CCSD/6-311G(d,p)水平下单点能计算得到的反应势垒为24.47kJ/mol.采用传统过渡态理论,计算了温度范围50K～2000K的反应速率常数.实验结果表明,随着反应温度的升高,反应速率逐渐升高,反应的平均活化能也随着温度的不断升高而不断增大.     

DEL RBC transfusion should be avoided in particular blood recipient in East Asia due to allosensitization and ineffectiveness

Previously, both primary and secondary anti-D alloimmunizations induced by "Asian type" DEL (RHD1227A allele) were observed in two incidents. We investigated how often these alloimmunization events occur. The transfusions of any D-negative patients were investigated in the First Affiliated Hospital of Xi’an Jiaotong University Medical College, China, during the entire 2009. The antigens of D, C, c, E, and e were routinely serotyped. The "Asian type" DEL variant was genotyped and the RHD heterozygote was determined through two published methods. The changes in anti-D levels were monitored by the indirect antiglobulin test (IAT) and flow cytometry. Thirty D-negative transfused patients were included in the study. We focused on 11 recipients who were transfused with packed red blood cells (RBCs) from DEL donors at least one time. Of those 11 recipients, seven were anti-D negative before transfusion and four were anti-D positive (one patient with an autoantibody). One of the seven pre-transfusion anti-D negative patients produced a primary-response anti-D after being transfused with 400 ml of DEL blood twice. All four pre-transfusion antibody positive patients were not observed hemoglobin (Hb) levels increased, as expected after transfusions. Two patients had an increase in anti-D from 1:8 to 1:64 by IAT, which was also shown by flow cytometry. None of the patients experienced an acute hemolytic episode. Our data indicated that the primary anti-D induced by DEL transfusion or the secondary anti-D elevated by DEL in a truly D-negative patient might not be unusual. We suggest that a truly D-negative childbearing-aged woman should avoid DEL transfusion to protect her from primary anti-D allosensitization. In addition, anti-D positive recipients should also avoid DEL red cell transfusion due to the delayed hemolytic transfusion reaction (DHTR).     

丙烯与氧原子反应机理的理论研究

利用密度泛函理论(DFT)中的B3LYP方法,在6-31+G(d,p)理论水平上对丙烯与氧原子的反应机理进行了研究.对反应物、产物、中间体及过渡态进行了优化,并通过内禀反应坐标(IRC)计算和振动分析对反应过渡态进行了确认.计算结果表明,氧原子与丙烯可以快速复合形成多种中间体,然后经历异构化、解离反应生成各种产物如CH3CH2CHO、CH3COCH3、不饱和烃以及H2O、OH、H.丙烯与氧原子反应通道主要有异构化、置氢和脱水反应3个过程.