N-杂环卡宾为配体的金属络合物的合成及其在催化领域的应用

N-杂环卡宾的金属络合物作为一类新型的催化剂已被广泛使用在有机合成领域,其主要的催化反应类型有烯烃的复分解反应、偶联反应、硅氢化反应等,催化效果明显.     

烯烃复分解反应--2005年诺贝尔化学奖成果介绍

法国科学家伊夫·肖万(Yves Chauvin)和美国科学家罗伯特·格拉布(Robert H Grubbs)、理查德·施罗克(Richard R Schrock)3人因为发展了烯烃复分解反应在有机合成中的应用,而共享了2005年度的诺贝尔化学奖.简要介绍了烯烃复分解反应的原理、应用和发展简况,以及发现过程.     

Proline-catalysed Mannich reactions of acetaldehyde

Small organic molecules recently emerged as a third class of broadly useful asymmetric catalysts that direct reactions to yield predominantly one chiral product, complementing enzymes and metal complexes. For instance, the amino acid proline and its derivatives are useful for the catalytic activation of carbonyl compounds via nucleophilic enamine intermediates. Several important carbon-carbon bond-forming reactions, including the Mannich reaction, have been developed using this approach, all of which are useful for making chiral, biologically relevant compounds. Remarkably, despite attempts, the simplest of all nucleophiles, acetaldehyde, could not be used in this way. Here we show that acetaldehyde is a powerful nucleophile in asymmetric, proline-catalysed Mannich reactions with N-tert-butoxycarbonyl (N-Boc)-imines, yielding beta-amino aldehydes with extremely high enantioselectivities-desirable products as drug intermediates and in the synthesis of other biologically active molecules. Although acetaldehyde has been used as a nucleophile in reactions with biological catalysts such as aldolases and thiamine-dependent enzymes, and has also been employed indirectly, its use as an inexpensive and versatile two-carbon nucleophile in asymmetric, small-molecule catalysis will find many practical applications.     

开环易位聚合研究进展

简要介绍了开环易位聚合的基本情况,结合开环易位聚合相关研究报道,综述了开环易位聚合最新研究进展,着重介绍了新型聚合催化剂的研究与应用情况,特别是新型选择性催化剂、扩环复分解催化剂、负载型催化剂和结构不确定催化剂。在开环易位聚合研究与应用方面,重点介绍了遥爪型聚合物、嵌段聚合物、接枝共聚物和液晶聚合物的研究情况。在此基础上,指出了今后开环易位聚合的研究与应用方向。     

Enzyme dynamics and hydrogen tunnelling in a thermophilic alcohol dehydrogenase.

Biological catalysts (enzymes) speed up reactions by many orders of magnitude using fundamental physical processes to increase chemical reactivity. Hydrogen tunnelling has increasingly been found to contribute to enzyme reactions at room temperature. Tunnelling is the phenomenon by which a particle transfers through a reaction barrier as a result of its wave-like property. In reactions involving small molecules, the relative importance of tunnelling increases as the temperature is reduced. We have now investigated whether hydrogen tunnelling occurs at elevated temperatures in a biological system that functions physiologically under such conditions. Using a thermophilic alcohol dehydrogenase (ADH), we find that hydrogen tunnelling makes a significant contribution at 65 degrees C; this is analogous to previous findings with mesophilic ADH at 25 degrees C. Contrary to predictions for tunnelling through a rigid barrier, the tunnelling with the thermophilic ADH decreases at and below room temperature. These findings provide experimental evidence for a role of thermally excited enzyme fluctuations in modulating enzyme-catalysed bond cleavage.     

新型烯烃聚合催化剂研究进展

由于过渡金属催化剂在烯烃聚合方面具有高活性和良好的分子剪裁性，通过调节催化荆的微结构或温度、压力等聚合环境的变化，可以在分子层次上实现烯烃聚合物的分子设计与组装，实现聚合物物理性质的调控，最近引起了人们的广泛关注。本文介绍了过渡金属催化荆的合成及其负载化，水相烯烃聚合及活性聚合等方面的研究进展。     

氢甲酰化铑催化剂立体化学的量子化学研究

氢甲酰化铑催化剂立体化学的量子化学研究廖代伟，林银钟，黄遵楠，彭亦如（化学系物理化学研究所固体表面物理化学国家重点实验室）均相和多相氢甲酸化反应及其催化剂自本世纪三、四十年代以来一直是催化界活跃的研究课题之一［１］．最近，徐奕德等［２］发表了关于氢甲...     

The chemical repertoire of natural ribozymes

Although RNA is generally thought to be a passive genetic blueprint, some RNA molecules, called ribozymes, have intrinsic enzyme-like activity--they can catalyse chemical reactions in the complete absence of protein cofactors. In addition to the well-known small ribozymes that cleave phosphodiester bonds, we now know that RNA catalysts probably effect a number of key cellular reactions. This versatility has lent credence to the idea that RNA molecules may have been central to the early stages of life on Earth.     

HZSM-5/堇青石整体式催化剂的制备及催化性能

以整体式堇青石蜂窝陶瓷为载体,经预处理后涂覆HZSM-5分子筛,制备出含不同HZSM-5质量分数的HZSM-5/堇青石整体式催化剂。采用XRD和BET对催化剂的结构进行了表征,在常压微型固定床反应装置上评价催化剂的甲醇制烯烃反应性能,并考察了催化剂中HZSM-5分子筛的质量分数、反应温度、气体空速等与烯烃组成分布的关系。结果表明：HZSM-5/堇青石整体式催化剂中仍保持HZSM-5分子筛的XRD特征衍射峰;催化剂的比表面积、孔体积随着HZSM-5质量分数的增加而增加;催化剂中HZSM-5分子筛质量分数为22.5%时具有最好的活性,在反应温度为380℃、气体空速为820mL/(g·h)的条件下,乙烯的选择性为35.22%,丙烯的选择性为30.95%。     

基于粒子群优化算法改进的XGBoost模型制备C4烯烃工艺条件优化

C4烯烃是生产清洁友好燃料等化工产品的重要原料，提升C4烯烃收率，增大C4烯烃产量是生产过程重要的目标之一。针对乙醇偶合制备C4烯烃这一化学反应样本数量多，特征数量少等特点，本文提出一种组合模型：粒子群算法改进的XGBoost模型。首先将XGBoost模型与数据的拟合效果作为粒子群算法的目标函数，通过粒子迭代确定XGBoost模型的最优超参数; 然后通过对变量设置一定的步长构造仿真数据。最后，将优化后的XGBoost模型与仿真数据进行拟合，拟合优度由76%提升至93%。根据预测结果确定了C4烯烃的最大收率和最佳反应条件，得到C4烯烃收率的最大值为43.52%。实验结果表明，改进后的XGBoost模型在误差和精度方面都优于原始模型。     

Enantiospecific electrodeposition of a chiral catalyst

Many biomolecules are chiral--they can exist in one of two enantiomeric forms that only differ in that their structures are mirror images of each other. Because only one enantiomer tends to be physiologically active while the other is inactive or even toxic, drug compounds are increasingly produced in an enantiomerically pure form using solution-phase homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantioselective catalysts that can more readily be separated from the products and reused. In addition, such surfaces might serve as electrochemical sensors for chiral molecules. To date, chiral surfaces have been obtained by adsorbing chiral molecules or slicing single crystals so that they exhibit high-index faces, and some of these surfaces act as enantioselective heterogeneous catalysts. Here we show that chiral surfaces can also be produced through electrodeposition, a relatively simple solution-based process that resembles biomineralization in that organic molecules adsorbed on surfaces have profound effects on the morphology of the inorganic deposits. When electrodepositing a copper oxide film on an achiral gold surface in the presence of tartrate ion in the deposition solution, the chirality of the ion determines the chirality of the deposited film, which in turn determines the film's enantiospecificity during subsequent electrochemical oxidation reactions.     

Recent progress in immobilization of late-transition-metal complexes with diimine ligands for olefin polymerization

Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure.Their less oxyphilicity character,which may promote the production of copolymers from ethylene and polar comonomers,is another aspect that attracts much attention in both academic and industrial fields.The immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry polymerizations.This paper reviews recent developments in supported LTM catalysts for olefin polymerization,and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic,organic,and inorganic-organic materials,and the effects of immobilization on catalytic activity,polymerization mechanism,and polymer morphology.     

The advent and development of organocatalysis

The use of small organic molecules as catalysts has been known for more than a century. But only in the past decade has organocatalysis become a thriving area of general concepts and widely applicable asymmetric reactions. Here I present my opinion on why the field of organocatalysis has blossomed so dramatically over the past decade.     

几类按反Markovnikov规则方向进行的加成反应

在有机化学反应中,大多数不对称结构的烯烃与酸加成时按马氏规则方向进行,但也有一些反应如在过氧化物存在条件下的反应、硼氢化氧化反应和某些烯烃衍生物的加成反应等是按反马氏规则方向进行的,论文对此进行了归纳总结.     

MgCl_2-n-BuOI-SiCl_4-TiCl_4/AlR_3体系的EPR考察

考察了不同载 Ti量的 TiCl_4/MgCl_2-n-BuOH-SiCl_4 与烷基铝相互作用产生的EPR 谱、不同作用时间形成的 EPR 谱的特征变化,以及它们与催化剂催化烯烃聚合活性的关联。结果表明,不同载Ti 量催化剂的 EPR主要是暴露于催化剂表面的孤立 Ti~(3+)离子贡献。表征催化剂中处于不同畸变配体场Ti~(3+)物类的g=1.95与g=1.97信号强度比值随载 Ti量增加而减小;g=1.99 信号的形成和增长与催化剂聚合活性有一定对应关系。     

均相定向聚合催化剂

考察了定向聚合催化剂的发展状况， 重点介绍了均相定向催化剂的结构特征， 催化性能及影响催化剂性能的因素；     

Towards uranium catalysts

The forefront of research into the complexes of uranium reveals chemical transformations that challenge and expand our view of this unique element. Certain ligands form multiple bonds to uranium, and small, inert molecules such as nitrogen and carbon dioxide become reactive when in complex with the metal. Such complexes provide clues to the catalytic future of uranium, in which the applications of the element extend far beyond the nuclear industry. Most excitingly, the ability of uranium to use its outermost f electrons for binding ligands might enable the element to catalyse reactions that are impossible with conventional, transition-metal catalysts.     

茂金属催化剂相关技术中国专利分析

以涉及茂金属催化荆的中国专利数据为样本,从中国专利申请量、申请人、技术构成等多角度详细剖析了国内茂金属专利技术的整体发展状况。研究表明：我国茂金属催化剂产业分布很不均衡,主要集中于催化剂本身。建议国内企业进一步完善和加强茂金属催化剂在烯烃聚合领域的应用和茂金属聚烯烃产品开发方面的研究,促进茂金属催化荆的产业化应用。     

聚烯烃技术的发展趋势及我国的现状

本文概述了世界聚烯烃工业生产技术及其研究开发的现状和发展趋势，包括聚烯烃的生产能力及需求、聚烯烃工艺技术的发展、聚烯烃催化剂和新型聚烯烃树脂材料的研究开发进展；同时也介绍了我国聚烯烃工业的现状，并提出了我们迎接挑战把握机遇所应采取的对策。     

固载杂多酸催化剂的轻汽油醚化反应性能研究

采用不同杂多酸负载于活性炭制成催化剂,并应用于FCC轻汽油醚化反应.结果表明:在反应温度75℃、液时空速1.0h-1、醇与烯物质的量比为1.0的工艺条件下,以负载质量分数20%的Na8GeW11O39.xH2O为活性组分制备的催化剂,对FCC轻汽油醚化反应表现出良好的醚化活性,产物中醚的体积分数可达11.76%,说明其具有一定的应用前景.