甲苯定向硝化的理论研究

运用密度泛函理论(DFT)B3LYP方法，在6-31G~(* *)基组水平上，全优化计算 了硝酰阳离子NO_2~+对苯和从0-，m-,p-位进攻甲苯亲电取代硝化后应，求得4条反 应途径上包括反应物、过渡态和Wheland中间体共(4×3)12个反应驻点σ络合物的 分子几何、电子结构、能量和IR光谱等性质，阐明了反应中无同位素效应的实验事 实，求得各反应途径的活化能排序：p-＞o-＞PhH＞m-和σ络合物(R,TSak或INT)的 相对稳定化能排序：p-ArCH_3-NO_2~+＞o-ArCH_3-NO_2~+＞m-ArCH_3-NO_2~+＞ PhH-NO_2~+，从而阐明了甲基对苯环致活(或致钝)以及增加甲苯硝化络合物稳定性 的双重功能，对甲苯定向硝化的理论预示与实验结果相吻合。     

一种模拟沸石分子筛扩散反应的Monte Carlo方法

在考虑了沸石分子筛中吸附、脱附、扩散和反应的特点的基础上，发展了一种模拟沸石分子筛中扩菜反应的ＭｏｎｔｅＣａｒｌｏ方法。用Ｌａｎｇｍｕｉｒ吸附等温式验证了该方法的合理性，并证明了轰击频率λ代表了反应物气相压力，而吸附、脱附几率之比即为吸附平衡常数。同时，通过改变轰击频率λ和反应几率Ｐｔ，得到了吸附等温线和有效因子随Ｔｈｉｅｌｅ模数变化的曲线。     

Strong influences of cocatalyst on ethylene/propylene copolymerization with a MgCl2/SiO2/TiCl4/diester type Ziegler-Natta catalyst

Using triethylaluminum (TEA), triisobutylaluminum (TIBA) or TEA/TIBA mixtures of molar ratio 75/25, 50/50 and 25/75 as the cocatalyst, five different ethylene-propylene copolymer samples were synthesized by a MgCl₂/SiO₂/TiCl₄/diester type Ziegler-Natta catalyst in a slurry polymerization process. The synthesized copolymers are strongly heterogeneous in chain structure and were fractionated into part of nearly random copolymer and part of segmented copolymer. Both polymerization activity and copolymer structure were found to be markedly changed when the cocatalyst was changed from TEA to TEA/TIBA mixtures or pure TIBA. As the content of TEA in cocatalyst increases, yield of the random part of product increases and the yield of the crystalline segmented copolymer part decreases. There is also a decrease in ethylene content of the whole product with increasing TEA amount. Copolymerization behaviors of the TEA/TIBA mixture activated catalysis systems are not simple superposition of those activated by pure TEA and TIBA. When a 50/50 TEA/TIBA mixture was used as cocatalyst, the copolymerization activity became the highest, and yields of both the random copolymer part and the segmented copolymer part are close to the highest level. On the other hand, both parts of the copolymer produced with a 50/50 TEA/TIBA mixture are relatively more blocky than the products of TEA or TIBA systems, and difference in ethylene content between the random part and the segmented part was the smallest. The segmented copolymer part of three typical samples was further fractionated by temperature-gradient extraction fractionation into fractions of different ethylene content and sequence distribution. Changing TEA content in the cocatalyst exerted strong influences also on the fraction distribution of the segmented part of copolymer.     

Nd（P_（507））_3－Al（i－Bu）_3催化马来酸酐与环氧丙烷开环交替共聚

本文研究了马来酸酐和环氧丙烷交替共聚，发现Ｎｄ（Ｐ_（５０７））_３－Ａｌ（ｉ－Ｂｕ）_３是马来酸酐（ＭＡｎ）和环氧丙烷（ＰＯ）交替共聚的良好催化剂，并用红外光谱，核磁共振谱研究了共聚物的结构。     

Free energy perturbation approach to the critical assessment of selective cyclooxygenase-2 inhibitors

The discovery of selective cyclooxygenase-2 (COX-2) inhibitors represents a major achievement of the efforts over the past few decades to develop therapeutic treatments for inflammation. To gain insights into designing new COX-2-selective inhibitors, we address the energetic and structural basis for the selective inhibition of COX isozymes by means of a combined computational protocol involving docking experiment, force field design for the heme prothetic group, and free energy perturbation (FEP) simulation. We consider both COX-2- and COX-1-selective inhibitors taking the V523I mutant of COX-2 to be a relevant structural model for COX-1 as confirmed by a variety of experimental and theoretical evidences. For all COX-2-selective inhibitors under consideration, we find that free energies of binding become less favorable as the receptor changes from COX-2 to COX-1, due to the weakening and/or loss of hydrogen bond and hydrophobic interactions that stabilize the inhibitors in the COX-2 active site. On the other hand, COX-1-selective oxicam inhibitors gain extra stabilization energy with the change of residue 523 from valine to isoleucine because of the formations of new hydrogen bonds in the enzyme-inhibitor complexes. The utility of the combined computational approach, as a valuable tool for in silico screening of COX-2-selective inhibitors, is further exemplified by identifying the physicochemical origins of the enantiospecific selective inhibition of COX-2 by -substituted indomethacin ethanolamide inhibitors.     

MgCl_2晶型对丙烯聚合MgCl_2载体催化剂活性的影响

ＭｇＣｌ_２晶型对丙烯聚合ＭｇＣｌ_２载体催化剂活性的影响张明辉，肖世镜中国科学院化学研究所，北京，１００８０）关键词丙烯聚合、ＭｇＣｌ２、载体催化剂近年来，有关ＭｇＣＩ。载体催化剂的研究报道和综述文章不少，但涉及载体晶型对催化剂结构性能的影响却少见．...     

丙烯选择氧化铋钼铁复氧化物催化剂组成,结构及性能的研究

采用XRD、Raman、XPS及催化剂性能评价等手段,考察了Bi_3(FeO_4)(MoO_4)_2和Fe_2(MoO_4)_3分别存在及两者共存时对Bi-Mo复氧化物体系催化性能的影响.结果表明,这两种含Fe物种的存在都有助于改善Bi-Mo系复氧化物催化剂对丙烯选择氧化反应的催化性能.但两者在作用机理上有所不同.Fe_2(MoO_4)_3本身无催化活性,但在反应条件下可部分还原为FeMoO_4形成Fe~(3+)/Fe~(2+)氧化还原对;且其地结构上与α-Bi_2(MoO_4)_3相匹配,这些因素都有助于促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生,从而提高催化性能.Bi_3(FeO_4)(MoO_4)_2在反应条件下也可形成Fe~(3+)/Fe~(2+)氧化还原对,但由于其Fe~(3-)所处的化学环境与Fe_2(MoO_4)_3很不相同,且Fe的含量也不及Fe_2(MoO_4)_3,因此它在促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生等方面的性能较差,但它对提高催化剂表面的活性中心(Bi-Mo对)数目有贡献.     

丙烯／长链α－烯烃共聚物的~（13）C—NMR和红外光谱法测定组成

丙烯／长链α－烯烃共聚物的~（１３）Ｃ—ＮＭＲ和红外光谱法测定组成陈辉，王建国，景凤英，庞德仁，黄葆同（中国科学院长春应用化学研究所，长春，１３００２２）关键词丙烯／长链α－烯烃共聚物，（１３）~Ｃ—ＮＭＲ，红外光谱法，组成测定聚丙烯（ＰＰ）作为通用塑...     

二氧化碳与环氧化物的调节共聚合反应速率

在二氧化碳和环氧化物共聚时加入特定的调节剂，生成有规定的分子量和端基官能度的产物．这种调节聚合的本质是调节剂所含活泼氢与活性中心之间的链转移反应．根据建议的历程，提出了调节共聚速率方程，计算结果与实验一致．     

Dicyanobiphenyl polysioloxane stationary phases for capillary column gas chromatography

Summary The chromatographic performance of newly developed dicyanobiphenyl polysiloxane stationary phases were evaluated and compared with the performance of other polar stationary phases, including the previously reported monocyanobiphenyl polysiloxanes. Due to the unique combination of polarizable biphenyl and polar cyano functionalities in the side chains of the flexible polysiloxane backbone, and by virtue of their mild liquid crystalline properties, the new stationary phases provide excellent resolution of a wide variety of analytes, both polar and nonpolar, in both GC and SFC. They can be easily coated and cross-linked in open tubular columns, and the resultant columns demonstrate excellent efficiency and performance at temperatures up to 280–300°C. The new stationary phases exhibit enhanced selectivities for various types of isomeric compounds.