分子团簇内的化学反应

本文综述了分子团簇内化学反应研究的进展, 介绍了发生在团簇内部的电子或电荷转移、质子转移、Penning 电离、激发原子与分子的反应及双分子反应等各类反应的研究现状。     

Introducing tox-Profiles of Chemical Reactions

In this Essay, we present a critical analysis of two common practices in modern chemistry—that is, of using speculations about the “greenness” and “nontoxicity” of developed synthesis procedures and of a priori labelling various compounds derived from natural sources as being environmentally safe. We note that every organic molecule that contains functional groups should be biologically active. Thus, analysis of the particular greenness and the potential environmental impact of a given chemical process should account for the biological activity of all its components in a measureable (rather than empirical) way. We highlight the necessity of clarifying discussions on biological activity and toxicity and propose possible ways of introducing tox-Profiles as a reliable overview of the overall toxicity of chemical reactions.     

非线性化学反应动力学*

本文从实验和理论的角度综述非线性化学反应动力学。介绍了若干非线性化学反应动力学现象如时钟反应、反馈、混合振荡、化学混沌及反应扩散图案等; 对时空序列、功率谱、Lyapunov 指数、吸引子及其维数、Poincare 截面及分叉理论等常用于分析非线性动力学特征的手段作了介绍; 探讨了对非线性化学反应的实验装置、测试方法、机理和模型研究的方法; 简要回顾了非线性化学反应动力学的发展历史, 并展望了其发展趋势。     

过渡金属团簇M+2(M=Fe、Co、Ni)与CO的化学反应

利用离子讲质谱计和激光溅射技术相结合,研究了Fe2＋、CO2＋、Ni2＋与CO气体的吸附反应,比较了它们的反应活性,给出了化学反应的速率常数及随反应气体压强的变化关系,并从理论上模拟了化学反应过程,测量结果与已有的实验值符合较好．     

The Chemical Reactions of 11-Hydroxycephalotaxine

1l-HydroxycephalotaxinelisoneofthethreeC,,-oxygenatedalkaloidsisolatedfromthegenusCePhalotaxus.Onlyafewreportsonthechemicaland,biologicalactivityandderivationsoflwerefoundl-3.Someofthechemicalreactionsofll-hydroxy-cephalotaxinel,whichwereencounteredduringthederivationoflandtherelatedcompoundsweredescribedinthispaPeLAcetylationoflwithlessthantwomolarofaceticanhydrideformedtWomonoacetateA,(C,-acetate)andB,(C,,-acetate)infavorofC,,acetylationduetothestericdifference(AandBstridthosecomPOunds…     

Kinetic On-line Evaluation of Chemical Reactions

A computer program was developed for kinetic evaluations of calorimetric experiments to predict the further reaction run under adiabatic conditions. Kinetic modeling is based on elementary reaction steps whose rate laws form a set of differential equations. For the continuous parameter optimization time-temperature data and their derivatives are used. A special calorimeter of the ACTRON series with safety equipment was applied to investigate the kinetics of chemical reactions and to test kinetic on-line evaluations. In the paper, examples for the reaction of n-propanol with o-chlornitrobenzene and for the alcoholysis of phenyl isocyanate are given.This revised version was published online in November 2005 with corrections to the Cover Date.     

Stationary Kinetic Structures of Chemical Reactions

Kinetics and Catalysis - Stationary structures corresponding to non-stationary experiments with different initial conditions have been established for multistage reactions. Such structures are...     

Spontaneous Emulsification Produced by Chemical Reactions

Self-assembled monolayer (SAM) formation of alkanethiols with ionic, hydrophilic terminal functionalities onto various O(2) plasma/ethanol pretreated gold substrates was characterized to explore the effect of gold surface oxide on the SAM packing quality. Oxygen adsorption induced by the Au(2)O(3) surface residuals are observed on the plasma-oxidized and O(2) plasma/ethanol-rinsed pretreated Au surfaces while no obvious adsorbed oxygen is found on freshly coated and O(2) plasma/ethanol sonication pretreated Au substrates. A model for the formation of hydrophilic terminated SAMs, -OH, -COOH, and -PO(3)H(2) is proposed. According to this model, the ionic and/or other binding interactions between the surface Au(2)O(3) and the alkanethiol hydrophilic terminal end as well as the interactions between the terminal SAM functionalities could cause the packing disorder found on these three SAMs formed on Au substrates containing Au(2)O(3) surface species. Copyright 2001 Academic Press.     

缩醛/缩酮的合成研究进展

民以食为天。然而,鲜有中文文献专业、系统地介绍与食物相关的化学反应,这无疑导致化学课程的教学脱离现实生活,阻碍了大众透过现象看到食物背后的本质。因此,本文重点介绍了为食物带来独特美味及色泽的非酶褐变反应,主要包括焦糖反应、美拉德反应、维生素C的氧化反应等;并从化学的角度探讨食物中与医学相关的分子转变现象,如食盐中碘在体内的转化,反式脂肪酸对健康的影响,酒精的代谢过程等。使化学课程的教学密切联系现实生活,为化学与食品科学、医学等学科之间架起桥梁。     

古生物化学中的凝聚态化学反应

研究古生物学,必须从古生物变“化”之学的方向着手,深入化石骨头和细胞里面,探讨在漫长时间内、该古生物的化学组成、细微构造等起了什么变化?化成了什么?如今保留的是什么?保存这些有机残留物的化学机制(Mechanism)是什么?凝聚态化学在此又扮演了什么关键角色?在此我以个人所知一点点从凝聚态化学的角度,来探讨古生物领域诸多古化学相关的最基本底层奥秘,本文举三个实例说明可能的凝聚态化学反应,肯定在古生物化学中扮演了关键的基本机制,等着我们去揭发;如：一般认为化石就是古代生物变化成为石头,从有机体变成无机的矿物质,有机体不可能保存成千万上亿年;然而,我们团队却在1.95亿年前的禄丰龙胚胎骨头内,发现了被保存下来的原生I型胶原蛋白(Native Collagen I);又在22亿年前化石内发现多种氨基酸,和证明为最早多细胞真核生物的甾烷;这是地球生命演化重大的发现;从这些古生物化石的实例来说,可以看出凝聚态化学绝非仅是个理论化学的旁观者,而是关键角色,它的重要性,非常值得我们投入去深入探讨,揭开从古代生物到你我手中化石无数化学反应最底层化学的奥秘。     

超临界二氧化碳中的化学反应

超临界流体;溶剂;超临界二氧化碳中的化学反应     

基本化学反应形式的系统分类

The old classification of basic chemical reactions was evaluated and a new systematic classification of basic reactions was proposed.In the new classification,all the chemical reactions were divided into oxidation-reduction reactions and non-oxidation-reduction reactions,and both can be divided into combination reaction,decomposition reaction and replacement reaction,respectively.In addition,a new class of basic reactions,the complicated decomposition reaction,was appended to reaction system.     

Enhancement of Chemical Reactions by Microwave Irradiation

Microwaves are low electromagnetic energy which induce molecular perturbation by stimulation of ionic diffusion and by enhancement of dipole rotation without causing rearrangement of molecular structures. Microwave energy irradiated on the samples in various liquid media is lost or absorbed to the samples by the following two mechanisms: ionic conduction and dipole rotation. These two effects take place simultaneously to account for the phenomenon of rapid heating associated with many practical applications of microwave irradiation. In contrast to conventional heating, the salient feat ure of “dipole rotation” constitutes one efficient form of “molecular agitation” or “molecular stirring” which can be explored for many aspects in chemical reactions. We will discuss some of the useful application of “molecular agitation” by means of microwave irradiation such as: 1. rapid hydrolysis of proteins and peptides, 2. selective hydrolysis of aspartyl peptide bond, 3. the racemization of amino acids, 4. rapid hydrolysis of sugars, 5. continuous-flow process of microwave reactions, and 6. the enhancement of coupling reactions in peptide synthesis.     

具有双稳态的化学反应中的涨落现象

化学反应中的非线性动力学行为一直受到人们的普遍的关注[1-3]Schlogl等人[4,5]曾用两个自催化反应模式说明连续的二级相变和不连续的一级相变特征．而在文献[6，7]中，我们提出在具有双稳态的化学反应中，存在类一级与类二级相变之间的转变点，而此转变点也具有类似Landau二级     

Autonomous Kinetic Invariants of Linear Chemical Reactions

Kinetics and Catalysis - A method has been developed for calculating the exact autonomous kinetic invariants of multistage linear chemical reactions occurring in a gradientless isothermal reactor...     

Multi-Reagent Autonomous Kinetic Invariants of Chemical Reactions

Kinetics and Catalysis - New exact multi-reagent autonomous kinetic invariants for chemical reactions occurring in a gradientless isothermal reactor have been established. Invariants are...     

超临界甲醇在化学反应中的应用

超临界流体技术在绿色化工过程中的应用范围不断拓宽。由于超临界甲醇具有独特的物理和化学性质,它既是反应介质,也是反应物,因此,超临界甲醇下的化学反应研究得到人们广泛的关注。本文在介绍超临界甲醇独特的物理化学特性的基础上,综述了近年来超临界甲醇体系在有机合成、生物柴油的制备、生物质处理和高聚物的降解等方面的应用研究进展,重点对超临界甲醇下各种反应的影响因素进行了分析讨论。最后,展望了超临界甲醇在甲醇化工中的应用前景。     

Quantum Chemical Exploration of Intermolecular Reactions of Acetylene

Quantum chemical explorations of potential energy surfaces showed that acetylene produces various products starting from molecular arrays in short distances of 1.3–2.5 Å. Arrays of (C₂H₂)₂ gave cyclobutadiene, tetrahedrane, and acetylene dimers. Arrays of (C₂H₂)₃ gave benzene, prismane, benzvalene, Dewar benzene, and acetylene trimers. Arrays of (C₂H₂)₄ gave cubane, cyclooctatetranene, and acetylene tetramers. Different forms of initial arrays yielded different sets of products; a parallel array of two monomers gave cyclobutadiene, whereas a cross array gave tetrahedrane. Initial molecular arrays with unusually close contacts were estimated to require local forces of 1–9 × 10⁻⁸ N. © 2019 Wiley Periodicals, Inc.