N,N,N,′N′-四丁基丁二酰胺的合成及其萃取稀土离子Pr(Ⅲ)的研究

合成了四取代双酰胺萃取剂N,N,N,′N′-四丁基丁二酰胺(TBSA),并对萃取剂的结构进行了表征。研究了其萃取Pr(Ⅲ)的性能,考察了硝酸浓度、萃取剂浓度、硝酸锂浓度以及温度等对萃取分配比的影响。萃取反应在298K时,TBSA以甲苯为稀释剂时的热力学焓变为-12.83 kJ/mol。萃合物的组成结构为Pr(NO3)3.3TBSA。     

Organic functionalization of the sidewalls of carbon nanotubes by diels-alder reactions: a theoretical prediction

[structure: see text] The viability of the Diels-Alder (DA) cycloaddition of conjugated dienes onto the sidewalls of single-wall carbon nanotubes is assessed by means of a two-layered ONIOM(B3LYP/6-31G:AM1) approach. Whereas the DA reaction of 1,3-butadiene on the sidewall of an armchair (5,5) nanotube is found to be unfavorable, the cycloaddition of quinodimethane is predicted to be viable due to the aromaticity stabilization at the corresponding transition states and products.     

C2-symmetric bis(oxazolinato)lanthanide catalysts for enantioselective intramolecular hydroamination/cyclization

C(2)-symmetric bis(oxazolinato)lanthanide complexes of the type [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), [(4S,5R)-Ar(2)Box]La[N(TMS)(2)](2), and [(4S)-Ph-5,5-Me(2)Box]La[N(TMS)(2)](2) (Box = 2,2'-bis(2-oxazoline)methylenyl; Ar = 4-tert-butylphenyl, 1-naphthyl; TMS = SiMe(3)) serve as precatalysts for the efficient enantioselective intramolecular hydroamination/cyclization of aminoalkenes and aminodienes. These new catalyst systems are conveniently generated in situ from the known metal precursors Ln[N(TMS)(2)](3) or Ln[CH(TMS)(2)](3) (Ln = La, Nd, Sm, Y, Lu) and 1.2 equiv of commercially available or readily prepared bis(oxazoline) ligands such as (4R,5S)-Ph(2)BoxH, (4S,5R)-Ar(2)BoxH, and (4S)-Ph-5,5-Me(2)BoxH. The X-ray crystal structure of [(4S)-(t)BuBox]Lu[CH(TMS)(2)](2) provides insight into the structure of the in situ generated precatalyst species. Lanthanides having the largest ionic radii exhibit the highest turnover frequencies as well as enantioselectivities. Reaction rates maximize near 1:1 BoxH:Ln ratio (ligand acceleration); however, increasing the ratio to 2:1 BoxH:Ln decreases the reaction rate, while affording enantiomeric excesses similar to the 1:1 BoxH:Ln case. A screening study of bis(oxazoline) ligands reveals that aryl stereodirecting groups at the oxazoline ring 4 position and additional substitution (geminal dimethyl or aryl) at the 5 position are crucial for high turnover frequencies and good enantioselectivities. The optimized precatalyst, in situ generated [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), exhibits good rates and enantioselectivities, comparable to or greater than those achieved with chiral C(1)-symmetric organolanthanocene catalysts, even for poorly responsive substrates (up to 67% ee at 23 degrees C). Kinetic studies reveal that hydroamination rates are zero order in [amine substrate] and first order in [catalyst], implicating the same general mechanism for organolanthanide-catalyzed hydroamination/cyclizations (intramolecular turnover-limiting olefin insertion followed by the rapid protonolysis of an Ln-C bond by amine substrate) and implying that the active catalytic species is monomeric.     

温州高校体育课程增设"定向运动"探讨

定向运动是一项新型体育运动项目．通过文献资料法、问卷调查法和数理统计法等，探讨了定向运动在高校推广和普及的可行性，为将定向运动列入我市高校体育课程内容提供理论依据．     

B值极限鞅差序列的Brunk型大数定律

分别对于取值于p-致光滑空间的极限鞅、概率极限鞅和L1极限鞅的差序列证明了Brunk型大数定律，推广了Woyczynski中关于鞅的相应结论。     

变压器式可控电抗器的磁场和参数计算

采用场路耦合的有限元似稳电磁场分析方法,对只有一个控制绕组的变压器式可控电抗器在不同负载下的稳态磁场进行了分析,推导了磁场和参数的计算公式,确定了与控制绕组交链方向相反的两部分磁通的分界线位置,给出了解析计算参数与有限元数值分析结果的比较,说明两者具有很好的一致性.     

塔里木-中朝板块北缘的志留纪岛弧公婆泉群火山岩地质地球化学及构造意义

公婆泉群位于北山中部，可分为：北、南两带。南带为弧后盆地玄武岩-安山岩组合，北带为岛弧火山岩组合，西段窑洞努如为火山角砾岩和熔火山角砾岩组合，中段公婆泉一带为玄武岩-安山岩-流纹岩-粗面岩组合，东段东七一山地区为玄武岩-安山岩-流纹岩组合。岩石组合，地球化学综合分析认为，公婆泉群是中-晚志留世哈萨克斯坦板块俯冲与塔里木-中朝板块的产物。岛弧西段窑洞努如位于近大陆或者在水下陆壳。公婆泉位于近海沟陆壳，而东七一山则远离海沟，是在洋壳的基础上发育的。说明塔里木-中朝板块是一个统一的板块，同时在早古生代存在哈萨克斯坦板块向塔里木-中朝板块的俯冲。     

Advances in identification and application of tumor antigen inducing anti-cancer responses

Tumor antigen is one of the important bases of tumor immunotherapy . With the discovery of novel tumor antigens, interest in specific immunotherapy for treatment of malignancies has increased substantially. Nowadays more and more scientists paid close attention to various tumor antigens with their roles or/and applications in anti-cancer immune responses, immune tolerance, tumor markers,     

新课程下的数学教师培训

师资培训工作是课程改革实验工作的关键。其中，观念的转变是教师培训的核心内容，为了适应新课程，数学教师的数学观、数学学习观、数学教学观、数学评价观都需要做很大的调整。同时，数学教师的知识面和能力也需要拓广，促使教师改变的培训方式是多样的，案例加反思是具有代表性的一种方式。