化学学科的现状及基础化学教育改革问题

1　化学学科现状简介　　自 1 80 2年道尔顿提出原子假说 ,1 81 1年阿佛加德罗又提出分子学说以来 ,化学一直在原子和分子学说的基础上发展着。 1 86 9年门捷列夫所发现的元素周期律及在此基础上构成的元素周期表 ,使化学从而成为一门有着严密体系的学科。由于当时对于原子和分子的结构理论还停留在假说的阶段 ,化学家的研究工作主要侧重于元素的发现、分析或分离组成复杂的样品的方法以及新化合物的合成 ,所以化学的传统定义中只强调合成和分析两个方面。这个传统在基础化学教育中至今仍然有着深刻的影响。 2 0世纪物理学家对原子结构及有…     

卤键在化学传感和分子识别中的应用

卤键是一种新的分子间非共价作用力,它存在于卤素原子(路易斯酸)和具有孤电子对的原子或π-电子体系(路易斯碱)之间,在超分子化学、材料科学、生物识别和药物设计等领域已经显示出独特的优势。本文主要从卤键的特征和在化学传感和分子识别中的应用以及发展前景等几方面进行了介绍,期望引起人们对卤键的更多关注。     

化学基元组学与药物创新

化学基元组学（chemomics）是与化学信息学、生物信息学、合成化学等学科相关的交叉学科．生物系统从内源性小分子（天然砌块）出发,通过酶催化的化学反应序列制造天然产物．生物系统通过化学反应和天然砌块向目标天然产物“砌入”一组原子,这样的一组原子称为化学基元（chemoyl）．化学基元组（chemome）是生物组织中所含有的化学基元的全体．化学基元组学研究各种化学基元的结构、组装与演化的基本规律．在生存压力和繁衍需求的驱动下,生物系统已经进化出有效手段来合成天然产物以应付环境的变化,并产生了丰富多彩的生物和化学多样性．近年来,人们意识到药物创新的瓶颈之一是药物筛选资源的日益枯竭．化学基元组学可以解决这个瓶颈问题,它通过揭示生物系统制备化学多样性的规律,发展仿生合成方法制备类天然化合物库（quasi natural product libraries）以供药物筛选．本文综述了化学基元组学的主要研究内容及其在药物创新各领域中的潜在应用．     

超分子化学药物研究

超分子药物化学是超分子化学在药学领域的新发展．该领域研究活跃,发展迅速,是一个充满活力的新兴交叉学科领域,并正在逐渐变成一个相对独立的研究领域．迄今已有许多两个或两个以上分子通过非共价键力形成的超分子化学药物应用于临床．超分子化学药物可具有良好的安全性、低毒性、不良反应少、高生物利用度、药物靶向性强、多药耐药性小、生物相容性好、高疗效以及其开发成本低、周期短、成功可能性大等诸多优点而备受关注,显示出超分子化学药物具有很大的发展潜力．本文首次给出了超分子药物的定义．结合自己的工作,参考国内外文献综述了超分子化学药物在抗肿瘤、抗炎镇痛、抗疟、抗菌、抗真菌、抗结核、抗病毒、抗癫痫、作为心血管和磁共振成像药物等医药领域的研究与开发状况,并展望其发展趋势与应用前景．     

化学生物学中识别与组装的若干问题

化学与生物学的交叉与融合产生了新学科——化学生物学，开拓了化学和生物学研究的新领域，使人类得以从分子水平来阐释生命过程，揭示生命的奥秘。分子识别和组装是体系的构筑与功能集成的基础，也是自然界生物进行信息存贮、复制和传递的基础，以此来研究构筑具有特定生物学功能的超分子体系，对揭示生命现象和过程具有重要意义。本文结合我们的研究工作从（1）谷胱甘肽过氧化物酶(GPX)模拟与底物识别；（2）医用再生材料与活性支架；（3）类病毒颗粒的组装与解组装3个方面讨论了化学生物学中的识别与组装的意义。     

超分子化学和分子器件—配位化学的一个前沿领域

重点介绍配位化学在超分子化学和分子器件－一门新学科领域中的研究进展。     

吉林大学超分子化学生物学学科的建设与发展:从超分子化学到生命机制探索及疫苗、药物研发

吉林大学是国内较早进行化学与生物学交叉研究的高校之一。为了推动吉林大学化学与生物学的深度融合,同时结合本校在超分子化学领域的积累与优势形成研究特色,本校提出了发展超分子化学生物学的构想,并建立了吉林大学超分子化学生物学研究中心。回顾了吉林大学化学与生物学交叉融合的发展历程,介绍了超分子化学生物学学科的发展现状及未来发展方向。     

基于超分子化学的核酸表观遗传修饰研究

核酸是生物体的遗传物质,在生命体系中发挥着重要作用.除了构成核酸的经典碱基之外,核酸中还存在天然修饰的碱基,这被称为核酸的表观遗传修饰.核酸的表观遗传修饰在基因表达过程中具有重要的调控作用,对生物体遗传和生命生长过程影响很大,并且核酸表观遗传与疾病密切相关.超分子化学是研究分子间键的化学,而许多生物分子都需要通过超分子化学作用来发挥其生物功能,可以说生物体内天然存在着大量的超分子化学过程.本文综合评述了基于超分子化学的核酸表观遗传修饰研究的一些代表性工作.     

国家自然科学基金委化学科学部“十五”优先资助领域

化学科学部“十五”优先资助领域以加速化学和化工学科的发展 ,增强基础研究工作的活力 ,发挥其中心科学的作用为目标。以开展泛分子 ( panmolecules)的研究 ,寻求不同层次上分子的多样性与多型性和控制化学反应与过程为主线 ;面向国民经济和社会发展的重大科学问题 ,结合生命、材料、能源、信息、资源与环境等领域 ,展示和发挥化学与化工科学的作用 ;加强化学理论研究和发展实验方法和测试技术相配合。打破传统学科的界限 ,突出创新与交叉 ,瞄准学科前沿 ,推动化学与化工科学的发展。在研究对象上发展从原子、分子聚集体的多层次和多尺度的…     

卤键在超分子化学中的应用进展

卤键是指作用在卤原子(路易斯酸)和具有孤对电子的原子或π电子体系(路易斯碱)之间的新型弱相互作用,其在超分子多维自组装和分子识别(如超分子催化、超分子选择拆分、超分子传感)等领域有着广泛的应用。本文介绍了卤键的类别、特性、功能及在超分子化学结构与功能领域中的应用。     

Fundamentals of Silicon Chemistry: Molecular States of Silicon-Containing Compounds

Silicon and its compounds have made possible the design of new materials, which, from computers to space travel, have helped to shape the technology of our 20th century. Conversely, the demands of new technology have stimulated the fast development of silicon chemistry as part of the “renaissance” of inorganic chemistry. This article uses selected examples of predominantly organosilicon compounds to discuss in simplified terms the measurement and assignment of suitable spectroscopic “molecular fingerprints” as well as the resulting benefit for the preparative chemist. The comparison of “equivalent” states of “chemically related” molecules is emphasized, based on perturbation arguments and supporting quantum-chemical models. Special attention is given to the relation between structure and energy, which allows us to understand and to predict the connectivity between and the spatial arrangement of silicon “building blocks”, the energy-dependent electron distribution over the effective nuclear potentials of a molecular framework, and, especially, the partly considerable effects of “silicon substituents” on molecular properties. Future-directed extensions and applications include polysilane band structures, Rydberg states of chromophores containing silicon centers, redox reactions and ion-pair formation of silicon-substituted π systems, and molecular dynamic phenomena in solution or on thermal fragmentation in the gas phase. The main objective is a set of clear and practical rules for interpreting measurements and planning experiments.     

The ‘Sceptical Chemist’– Fundamental concepts in the history of the scientific process of chemical education

The 17th century was witness to scientific chemistry’s emergence from the odd experiments of alchemy. We cannot ascertain its precise date of birth, we can, however, its precise date of christening: in 1661 “The Sceptical Chymist”, the first classical work in the history of chemistry was published by Robert Boyle. Boyle called his chemistry »sceptical« because he had made up his mind to leave aside all mystical explanations and occult attributes as the holy shrine of ignorance. Since those days concepts and theories have been constantly refined under the eyes of the »sceptical chemist« in dialogue with nature. In terms of methodology and concepts the path of recognition was laid down in advance by a contemporary of R. Boyle. It has led in a spiro-cyclical style right up to the end of the 20th century: the principle of the sciences of the 17th century mutated from “corso/ricorso” of then to the “recycling” of today. This principle is discussed.     

Stereochemical language in supramolecular polymer chemistry: How we can do better

Stereochemical nomenclature remains a point of attention; especially now different fields in chemistry become more and more entwined. The ubiquitously used terminology “amplification of chirality” is fundamentally incorrect, as chirality cannot be amplified. Instead, we now recommend “amplification of asymmetry” as an alternative in the field of (supramolecular) polymer chemistry. Amplification of asymmetry refers to the increase of the magnitude of the asymmetry in the enantiomeric composition either at the molecular or the supramolecular level, and covers observations of nonproportional increase in optical activity in helical (supramolecular) polymers and in high enantiomeric excesses found when nonlinear effects are operative in asymmetric catalysis.     

Uncovering the Intramolecular Emission and Tuning the Nonlinear Optical Properties of Organic Materials by Cocrystallization

The spectroscopic and photophysical properties of organic materials in the solid‐state are widely accepted as a result of their molecular packing structure and intermolecular interactions, such as J‐ and H‐aggregation, charge‐transfer (CT), excimer and exciplex. However, in this work, we show that Spe‐F₄DIB cocrystals (SFCs) surprisingly retain the energy levels of photoluminescence (PL) states of Spe crystals, despite a significantly altered molecular packing structure after cocrystallization. In comparison, Npe‐F₄DIB cocrystals (NFCs) with new spectroscopic states display different spectra and photophysical behaviors as compared with those of individual component crystals. These may be related to the molecular configuration in crystals, and we propose Spe as an “intramolecular emissive” material, thus providing a new viewpoint on light‐emitting species of organic chromophores. Moreover, the nonlinear optical (NLO) properties of Npe and Spe are firstly demonstrated and modulated by cocrystallization. The established “molecule‐packing‐property” relationship helps to rationally control the optical properties of organic materials through cocrystallization.     

Molecular Tweezers: Concepts and Applications

Taken to the molecular level, the concept of “tweezers” opens a rich and fascinating field at the convergence of molecular recognition, biomimetic chemistry and nanomachines. Composed of a spacer bridging two interaction sites, the behaviour of molecular tweezers is strongly influenced by the flexibility of their spacer. Operating through an “induced‐fit” recognition mechanism, flexible molecular tweezers select the conformation(s) most appropriate for substrate binding. Their adaptability allows them to be used in a variety of binding modes and they have found applications in chirality signalling. Rigid spacers, on the contrary, display a limited number of binding states, which lead to selective and strong substrate binding following a “lock and key” model. Exquisite selectivity may be expressed with substrates as varied as C₆₀, nanotubes and natural cofactors, and applications to molecular electronics and enzyme inhibition are emerging. At the crossroad between flexible and rigid spacers, stimulus‐responsive molecular tweezers controlled by ionic, redox or light triggers belong to the realm of molecular machines, and, applied to molecular tweezing, open doors to the selective binding, transport and release of their cargo. Applications to controlled drug delivery are already appearing. The past 30 years have seen the birth of molecular tweezers; the next many years to come will surely see them blooming in exciting applications.     

基于创新能力培养的化学专业本科实验教学新体系的构建与实践

课程体系是人才培养的载体。为了更好地培养拔尖创新人才,南京大学化学国家级实验教学示范中心依据化学学科的特点和发展趋势,以科学内容的内在联系和研究规律为主线构建了“化学实验基础?化学合成与表征+化学原理与测量?化学功能分子实验+化学生物学综合实验+基于项目的研究实验”实验课程新体系,按照一流课程建设要求(高阶性、创新性和挑战度)对实验教学内容进行了优化,并建立起与之相适应的实验教学平台。新课程体系综合考虑了化学一级学科的整体性和关联学科的交叉性,在南京大学化学化工学院“拔尖计划”和“强基计划”学生中实施,教学效果显著。     

Synthetisches Blau als Wegbereiterin des Impressionismus

Up until the 18th century stable, strong blue pigments for painting were very expensive. Only well‐off painters or their wealthy patrons could afford them. Progress in chemistry changed this situation during the 18th and 19th centuries by synthesizing good quality blue pigments at reasonable prices. Pigments in primary colors in ready‐to‐paint tubes paved the way for painters from all social classes to join the new “plein‐air” movement of impressionism.     

The structural theory and physical organic chemistry

Woolley's revolutionary proposal that quantum mechanics does not sanction the concept of “molecular structure”—which is but only a “metaphor”—has fundamental implications for physical organic chemistry. On the one hand, the Uncertainty Principle limits the precision with which transition state structures may be defined; on the other, extension of the structure concept to the transition state may be unviable. Attempts to define transition states have indeed caused controversy. Consequences for molecular recognition, and a mechanistic classification, are also discussed.     

Remarques sur les définitions des acides et des bases

In the present state of knowledge it is not possible to account for the reactions used in analytical chemistry by setting up a single table of the “acids” and “bases” defined according to LEWIS.The most general definition which can be usefully adopted involves taking into account the exchange of “particles” (electrons, protons, ions, molecules) in the reactions. It follows from this that there arc as many types of reactions as there are “particles”.In accordance with the brönsted theory, in the case where the “particle” exchanged is the proton, an acid-base reaction is involved.