超分子化学 英文.pdf

超分子化学超分子化学 孙俊奇 第一章超分子化学导论第一章超分子化学导论 Chemistry in our life Health Energy water food Population control Information Technology Global environmental stability National security Reinventing the supply chain Understanding the living material and information based worlds 1 Molecular chemistry the chemistry of the covalent bond is concerned with uncovering and mastering the rules that govern the structures properties and transformations of molecular species 2 Supramolecular chemistry may be defined as chemistry beyond the molecule bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces Its development requires the use of all resources of molecular chemistry combined with the designed manipulation of non covalent interactions so as to form supramolecular entities supermolecules possessing features as well delined as those of molecules themselves One may say that supermolecules are to molecules and the intermolecular bond what molecules are to atoms and the covalent bond Supramolecular Chemistry 超分子化学超分子化学 Chemistry MOLECULAR SUPRAMOLECULAR A B C D SYNTHESIS covalent bonds RECEPTOR SUBSTRATE INTERACTION intermolecular bonds SUPRAMOLECULE RECOGNITION TRANSFORMATION TRANSLOCATION SELF ASSEMBLY SELF ORGANISATION FUNCTIONAL COMPONENTS polymolecular assembly MOLECULAR AND SUPRAMOLECULAR DEVICES Pederson C J 1967 the compound dissolved sparingly in methanol but its solubility was enhanced significantly on addition of alkali metal salts He eventually concluded the potassium ion had fallen into the hole at the center of the molecule Discovery of crown ether 0 4 C J Pedersen J Am Chem Soc 89 2495 7017 1967 Molecular Receptors Design Principles In order to achieve high recognition it is desirable that receptor and substrate be in contact over a large area The simplest recognition spherical recognition in crown ethers spherical substrates positively charged metal cations alkali alkaline earth lanthanide ions or the negative halide anions Ethers esp crown ethers are good ligands for alkali metals 18 Crown 6complex 2 cryptand 穴醚 穴醚 and cryptate 1967年以来 年以来 J M Lehn等合成了一些双环的多元醚 即穴醚 穴醚 与碱金属配合物的稳定常数比类似冠醚配合物高二个数量级以上 穴醚是天然离子载体和细胞膜的良好模拟物 由于冠醚 穴醚可以 作为主体 或受体 在主客体化学和超分子化学中已得到了广泛 的关注 等合成了一些双环的多元醚 即穴醚 穴醚 与碱金属配合物的稳定常数比类似冠醚配合物高二个数量级以上 穴醚是天然离子载体和细胞膜的良好模拟物 由于冠醚 穴醚可以 作为主体 或受体 在主客体化学和超分子化学中已得到了广泛 的关注 1 Li 2 Na 3 K a Spherical recognition 3与与K 形成的 配合物 形成的 配合物 Donald J Cram Host guest chemistry 1974 Complexes are composed of two or more molecules or ions held together in unique structural relationships by electrostatic forces other than those of full covalent bonds The host component is defined as an organic molecule or ion whose binding sites converge in the complex The guest component is defined as any molecule or ion whose binding sites diverge in the complex We tried to interest graduate students in synthesizing chiral crown ethers from 1968 on the efforts were unsuccessful In 1970 we insisted that several postdoctoral co workers enter the field During 1973 we published five Communications on the subject In 1974 with Jane M Cram we published a general article entitled Host Guest Chemistry which defined our approach to this research The Nobel Prize in Chemistry 1987 Donald J Cram 1 3 of the prize USA 主客体化学主客体化学 University of California Los Angeles CA USA b 1919 d 2001 Jean Marie Lehn 1 3 of the prize France 发现穴醚配合物 超分 子化学概念 发现穴醚配合物 超分 子化学概念 Universit Louis Pasteur Strasbourg France Coll ge de France Paris France b 1939 Charles J Pedersen 1 3 of the prize USA 发现冠醚配合物发现冠醚配合物 Du Pont Wilmington DE USA b 1904 in Fusan Korea d 1989 超分子科学的研究对象是分子聚集体 分子聚集 体形成的本质是分子间相互作用 分子自组装是构 筑各种各样分子聚集体的有效手段 超分子科学的研究对象是分子聚集体 分子聚集 体形成的本质是分子间相互作用 分子自组装是构 筑各种各样分子聚集体的有效手段 立项依据及拟解关键科学问题立项依据及拟解关键科学问题 原子 原子 原子 原子 共价键共价键 分子 分子 分子 分子 非共价键非共价键 分子聚集体分子聚集体 分子层次分子以上层次分子层次分子以上层次 纳米科学 结构生物学 分子电子学 纳米科学 结构生物学 分子电子学 超分子科学超分子科学 合成合成 自组装自组装 超分子科学是21世纪新概念和高技术的一个重要源头超分子科学是21世纪新概念和高技术的一个重要源头 History of Supramolecular Chemistry The origin of supramolecular chemistry can be traced back to 1894 E Fishcer in 1894 Lock and Key implying geometrical complementarity that lays the basis of molecular recognition K L Wolf et al Z Phys Chem 1937 B36 237 Molecular associations have been recognized and studied for a long time and the term bermolek le i e supermolecules was introduced already in the mid 1930 s to describe entities of higher organization resulting from the association of coordinatively saturated species The partners of a supramolecular species have been named molecular receptor 分子受体 and substrate 底物 the substrate being usually the smaller component whose binding is being sought Supramolecular chemistry has been defined conceptualized and structured into a coherent system Its roots extend into different subjects of chemistry and other physical science 有机化学 有机化学 分子构筑基元的合成分子构筑基元的合成 配位化学 配位化学 分子受体化学的基础分子受体化学的基础 物理化学 物理化学 分子间相互作用的理论与实验研究分子间相互作用的理论与实验研究 生物化学 生物化学 生物的过程均从底物的结合与识别开始生物的过程均从底物的结合与识别开始 高分子科学高分子科学 材料科学与生物科学的桥梁 材料科学与生物科学的桥梁 纳米科学 Bottom up 纳米构建 生命科学 超分子生物学 结构生物学 物理学 介观物理 Functional supramolecular systems BiomembraneLiposome Micelles Monolayers Multilayers Liquid crystals Surface functionalization Host guest systems 2D Protein crystallization Enzyme function E Life science Life science Molecular recognition Molecular recognition Molecular self organization Molecular self organization Function via organization Function via organization Order and mobility Order and mobilityMaterials science Materials science Helmut Ringsdorf Angew Chem Int Ed 1988 23 113 Self assembly 自组装自组装 Molecular recognition 分子识别分子识别 Supermolecules 超分子超分子 Molecular assemblies 分子组装体分子组装体 Supramolecular chirality 超分子手性超分子手性 Molecular and supramolecular devices 分子和超分子器件分子和超分子器件 Supramolecular polymers 超分子聚合物超分子聚合物 超分子化学是关于分子间相互作 用和分子聚集体的化学 超分子化学是关于分子间相互作 用和分子聚集体的化学 在超分子层次 分子组装的重要性 就如同分子化学中的合成 在超分子层次 分子组装的重要性 就如同分子化学中的合成 Self assembly may be defined as the process by which a supramolecular species forms spontaneously from its components Self assembly 关键词 关键词 自发 有序 非共价键自发 有序 非共价键 Molecular Recognition Recognition Information Complementarity Molecular recognition has been defined as a process involving both binding and selection of substrate s by a given receptor molecule as well as possibly a specific function Mere binding is not recognition although it is often taken as such One may say that recognition is binding with a purpose like receptors are ligands with a purpose It implies a structurally well defined pattern of intermolecular interactions 分子识别可定义为这样一个过程 对于一个给定的受体或者一个特殊功能 底物选择性地与之键合 仅有键合并不是识别 因为识别和目的键合连在一 起 分子识别可定义为这样一个过程 对于一个给定的受体或者一个特殊功能 底物选择性地与之键合 仅有键合并不是识别 因为识别和目的键合连在一 起 自然界的一切生命都是分子通过弱相互作用以非 常精密 准确 可控的方式自发自组装得到的 因此要揭开生命起源的奥秘必须研究超分子自组 装 自然界的一切生命都是分子通过弱相互作用以非 常精密 准确 可控的方式自发自组装得到的 因此要揭开生命起源的奥秘必须研究超分子自组 装 超分子化学与生命科学 1 超分子化学与生命科学 超分子化学与生命科学 核小体 一级纳米纤维 二级螺线管 三级超 螺旋 四级染色体单体 染色体的多 级组装结构 染色体的多 级组装结构 染色质 着丝粒 10nm 外径为30nm 内径10nm 螺距11nm的螺线管 直径为 0 4 m的 圆筒状结 构 长2 10 m Figure 1 Time sequence of fusion images of two giant polymer vesicles The number in the symbol labeled on each image denotes the elapsed time in seconds and the time of first image is set as zero The scale bar represents 50 m Real Time Membrane Fusion of Giant Polymer Vesicles J AM CHEM SOC 2005 127 10468 10469 The nature of the cell is an entirely molecular problem It has nothing to do with biology G Whitesides 2 Supramolecular Devices and Machines Dynamic chemical devices Modulation of contraction extension molecular motion by coupled ion bindingpH changeinducedstructural switching helical coil linear chain The gray spherical objects represent Pb II ions AH CF3SO3H B Et3N Rotaxane 轮烷 轮烷 J F Stoddart Nature 1994 369 133 137 3 Supramolecular polymers Supramolecular polymers are chains of monomers held together by non covalent interactions such as hydrogen bonds or metal ligand interactions When they were just discovered the term living polymers was often used because of the possibility of the chains to break and recombine Nowadays the term supramolecular polymers is generally used referring to the fact that the chains are assemblies of small molecules 一种制备对 外界刺激敏 感的聚合物 材料的新方 法 超分子聚合物的应用超分子聚合物的应用 Thermoplastic elastomer good mechanical properties at room temperature and low melt viscosity at elevated temperature Adv Mater 2000 12 874 Self Healing Polymers Self healing and thermoreversible rubber from supramolecular assembly Nature 2008 451 977 Kleppinger R et al JACS 1997 119 4097 Visual Detection of Melamine in Raw Milk and Infant Formula J AM CHEM SOC 2009 131 9496 9497 O O O O O O O m intramolecular photodimer O O O O O O O m O O O O O O O m N Pn N CB 8 O O O O O O O m H2O hvextraction hv O O O OC OCHCH2 4 O C OCHCH2 4 O Intermolecular photodimer O O O O O O m O O O O O O m 在水溶液中底物分子自绕曲 一个分子的两末端和葫芦脲形 成包结络合物 在底物浓度很高的情况下高产率地合成了大 环化合物 在水溶液中底物分子自绕曲 一个分子的两末端和葫芦脲形 成包结络合物 在底物浓度很高的情况下高产率地合成了大 环化合物 X L Wu L Z Wu C H Tung et al J Org Chem 2008 73 491 化学选择性 化学选择性 大环化合物的合成大环化合物的合成 Membrance Science Decher G Hong J D Ber Bunsen Ges Phys Chem 1991 95 1430 始于1991年G Decher始于1991年G Decher Process of Layer by Layer Assembly Useful coatings made by layer by layer assembly CibaVision researcher announced the use of layer by layer assembly for making the surfaces of contact lenses water friendly Potential Applications artificial muscles flexible electronic circuits antennae or mirrors Metal rubber mirrors would be light and rugged and would be ideal for use in cameras space probes or satellites Researchers from Virginia Polytechnic Institute and NanoSonic Metal Rubber 高负载的微凝胶聚合物膜高负载的微凝胶聚合物膜 Langmuir 2008 24 1902 J Mater Chem 2008 18 4042 Langmuir 2009 25 7990 J Mater Chem 2009 accepted 原位合成 纳米粒子 原位合成 纳米粒子 手术缝合线表面药物负手术缝合线表面药物负手术缝合线表面药物负手术缝合线表面药物负 载与缓释载与缓释载与缓释载与缓释 功能集成的膜材料功能集成的膜材料 14 nm SiO2 Langmuir 2